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.

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.

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

In situ observations of water production and distribution in an operating H2/O2 PEM fuel cell assembly using 1H NMR microscopy.

PubMed

Feindel, Kirk W; LaRocque, Logan P-A; Starke, Dieter; Bergens, Steven H; Wasylishen, Roderick E

2004-09-22

Proton NMR imaging was used to investigate in situ the distribution of water in a polymer electrolyte membrane fuel cell operating on H2 and O2. In a single experiment, water was monitored in the gas flow channels, the membrane electrode assembly, and in the membrane surrounding the catalysts. Radial gradient diffusion removes water from the catalysts into the surrounding membrane. This research demonstrates the strength of 1H NMR microscopy as an aid for designing fuel cells to optimize water management.

Microscale Chemistry in a Plastic Petri Dish: Preparation and Chemical Properties of Chlorine Gas

NASA Astrophysics Data System (ADS)

Choi, Martin M. F.

2002-08-01

This experiment demonstrates some of the chemistry of chlorine on a microscale, about the size of a water droplet. Chlorine gas was prepared from an acidified bleach solution in a plastic petri dish. The chlorine gas generated in situ reacted with other chemical reagents in the dish by diffusion. Some of the oxidizing properties and bleaching power of chlorine gas were shown visually and could be observed within 10 minutes. These experiments provide suitable hands-on experience for students at secondary-school level.

In situ temperature monitoring in single-molecule FRET experiments

NASA Astrophysics Data System (ADS)

Hartmann, Andreas; Berndt, Frederic; Ollmann, Simon; Krainer, Georg; Schlierf, Michael

2018-03-01

Thermodynamic properties of single molecules including enthalpic and entropic contributions are often determined from experiments by a direct control and precise measurement of the local temperature. However, common temperature monitoring techniques using, for example, ultrafine temperature probes can lead to uncertainties as the probe cannot be placed in the vicinity of the molecule of interest. Here, we devised an approach to measure the local temperature in freely diffusing confocal single-molecule Förster Resonance Energy Transfer (smFRET) experiments in situ by directly adding the temperature-sensitive fluorescent dye Rhodamine B, whose fluorescence lifetime serves as a probe of the local temperature in the confocal volume. We demonstrate that the temperature and FRET efficiencies of static and dynamic molecules can be extracted within one measurement simultaneously, without the need of a reference chamber. We anticipate this technique to be particularly useful in the physicochemical analyses of temperature-dependent biomolecular processes from single-molecule measurements.

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

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.

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.

40Ar* loss in experimentally deformed muscovite and biotite with implications for 40Ar/39Ar geochronology of naturally deformed rocks

USGS Publications Warehouse

Cosca, M.; Stunitz, H.; Bourgeix, A.-L.; Lee, J.P.

2011-01-01

The effects of deformation on radiogenic argon (40Ar*) retentivity in mica are described from high pressure experiments performed on rock samples of peraluminous granite containing euhedral muscovite and biotite. Cylindrical cores, ???15mm in length and 6.25mm in diameter, were drilled from granite collected from the South Armorican Massif in northwestern France, loaded into gold capsules, and weld-sealed in the presence of excess water. The samples were deformed at a pressure of 10kb and a temperature of 600??C over a period 29 of hours within a solid medium assembly in a Griggs-type triaxial hydraulic deformation apparatus. Overall shortening in the experiments was approximately 10%. Transmitted light and secondary and backscattered electron imaging of the deformed granite samples reveals evidence of induced defects and for significant physical grain size reduction by kinking, cracking, and grain segmentation of the micas.Infrared (IR) laser (CO2) heating of individual 1.5-2.5mm diameter grains of muscovite and biotite separated from the undeformed granite yield well-defined 40Ar/39Ar plateau ages of 311??2Ma (2??). Identical experiments on single grains separated from the experimentally deformed granite yield results indicating 40Ar* loss of 0-35% in muscovite and 2-3% 40Ar* loss in biotite. Intragrain in situ ultraviolet (UV) laser ablation 40Ar/39Ar ages (??4-10%, 1??) of deformed muscovites range from 309??13 to 264??7Ma, consistent with 0-16% 40Ar* loss relative to the undeformed muscovite. The in situ UV laser ablation 40Ar/39Ar ages of deformed biotite vary from 301 to 217Ma, consistent with up to 32% 40Ar* loss. No spatial correlation is observed between in situ 40Ar/39Ar age and position within individual grains. Using available argon diffusion data for muscovite the observed 40Ar* loss in the experimentally treated muscovite can be utilized to predict average 40Ar* diffusion dimensions. Maximum 40Ar/39Ar ages obtained by UV laser ablation overlap those of the undeformed muscovite, indicating argon loss of <1% and an average effective grain radius for 40Ar* diffusion ???700??m. The UV laser ablation and IR laser incremental 40Ar/39Ar ages indicating 40Ar* loss of 16% and 35%, respectively, are consistent with an average diffusion radius ???100??m. These results support a hypothesis of grain-scale 40Ar* diffusion distances in undeformed mica and a heterogeneous mechanical reduction in the intragrain effective diffusion length scale for 40Ar* in deformed mica. Reduction in the effective diffusion length scale in naturally deformed samples occurs most probably through production of mesoscopic and submicroscopic defects such as, e.g., stacking faults. A network of interconnected defects, continuously forming and annealing during dynamic deformation likely plays an important role in controlling both 40Ar* retention and intragrain distribution in deformed mica. Intragrain 40Ar/39Ar ages, when combined with estimates of diffusion kinetics and distances, may provide a means of establishing thermochronological histories from individual micas. ?? 2011.

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.

Solute source depletion control of forward and back diffusion through low-permeability zones

NASA Astrophysics Data System (ADS)

Yang, Minjune; Annable, Michael D.; Jawitz, James W.

2016-10-01

Solute diffusive exchange between low-permeability aquitards and high-permeability aquifers acts as a significant mediator of long-term contaminant fate. Aquifer contaminants diffuse into aquitards, but as contaminant sources are depleted, aquifer concentrations decline, triggering back diffusion from aquitards. The dynamics of the contaminant source depletion, or the source strength function, controls the timing of the transition of aquitards from sinks to sources. Here, we experimentally evaluate three archetypical transient source depletion models (step-change, linear, and exponential), and we use novel analytical solutions to accurately account for dynamic aquitard-aquifer diffusive transfer. Laboratory diffusion experiments were conducted using a well-controlled flow chamber to assess solute exchange between sand aquifer and kaolinite aquitard layers. Solute concentration profiles in the aquitard were measured in situ using electrical conductivity. Back diffusion was shown to begin earlier and produce larger mass flux for rapidly depleting sources. The analytical models showed very good correspondence with measured aquifer breakthrough curves and aquitard concentration profiles. The modeling approach links source dissolution and back diffusion, enabling assessment of human exposure risk and calculation of the back diffusion initiation time, as well as the resulting plume persistence.

Solute source depletion control of forward and back diffusion through low-permeability zones.

PubMed

Yang, Minjune; Annable, Michael D; Jawitz, James W

2016-10-01

Solute diffusive exchange between low-permeability aquitards and high-permeability aquifers acts as a significant mediator of long-term contaminant fate. Aquifer contaminants diffuse into aquitards, but as contaminant sources are depleted, aquifer concentrations decline, triggering back diffusion from aquitards. The dynamics of the contaminant source depletion, or the source strength function, controls the timing of the transition of aquitards from sinks to sources. Here, we experimentally evaluate three archetypical transient source depletion models (step-change, linear, and exponential), and we use novel analytical solutions to accurately account for dynamic aquitard-aquifer diffusive transfer. Laboratory diffusion experiments were conducted using a well-controlled flow chamber to assess solute exchange between sand aquifer and kaolinite aquitard layers. Solute concentration profiles in the aquitard were measured in situ using electrical conductivity. Back diffusion was shown to begin earlier and produce larger mass flux for rapidly depleting sources. The analytical models showed very good correspondence with measured aquifer breakthrough curves and aquitard concentration profiles. The modeling approach links source dissolution and back diffusion, enabling assessment of human exposure risk and calculation of the back diffusion initiation time, as well as the resulting plume persistence. Copyright © 2016 Elsevier B.V. All rights reserved.

Lithium diffusion in polyether ether ketone and polyimide stimulated by in situ electron irradiation and studied by the neutron depth profiling method

NASA Astrophysics Data System (ADS)

Vacik, J.; Hnatowicz, V.; Attar, F. M. D.; Mathakari, N. L.; Dahiwale, S. S.; Dhole, S. D.; Bhoraskar, V. N.

2014-10-01

Diffusion of lithium from a LiCl aqueous solution into polyether ether ketone (PEEK) and polyimide (PI) assisted by in situ irradiation with 6.5 MeV electrons was studied by the neutron depth profiling method. The number of the Li atoms was found to be roughly proportional to the diffusion time. Regardless of the diffusion time, the measured depth profiles in PEEK exhibit a nearly exponential form, indicating achievement of a steady-state phase of a diffusion-reaction process specified in the text. The form of the profiles in PI is more complex and it depends strongly on the diffusion time. For the longer diffusion time, the profile consists of near-surface bell-shaped part due to Fickian-like diffusion and deeper exponential part.

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.

Oxidation of metals and alloys in controlled atmospheres using in situ transmission electron microscopy and Auger spectrography

NASA Technical Reports Server (NTRS)

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

1976-01-01

Single-crystalline thin films of copper were oxidized at an isothermal temperature of 425 C and at an oxygen partial pressure of .005 Torr in situ in a high-resolution electron microscope. The specimens were prepared by epitaxial vapor deposition onto polished 100 and 110 faces of rocksalt and mounted in a hot stage inside an ultra-high-vacuum specimen chamber of the microscope. Large amounts of sulfur, carbon, and oxygen were detected by Auger electron spectroscopy on the surface of the as-received films and were removed in situ by ion-sputter etching immediately prior to the oxidation. The nucleation and growth characteristics of Cu2O on Cu were studied. Results show that neither stacking faults nor dislocations are associated with the Cu2O nucleation sites. The growth of Cu2O nuclei is linear with time. The experimental findings, including results from oxygen dissolution experiments and from repetitive oxidation-reduction-oxidation sequences, fit well into the framework of an oxidation process involving (a) the formation of a surface-charge layer, (b) oxygen saturation in the metal and (c) nucleation, followed by surface diffusion of oxygen and bulk diffusion of copper for lateral and vertical oxide growth, respectively.

Study of mass transfer in supercritical carbon dioxide (SCCO2) using optical methods

NASA Astrophysics Data System (ADS)

Hu, M.; Benning, R.; Ertunç, Ö.; Delgado, A.; Nercissian, V.; Berger, M.

2017-12-01

The purpose of this work is to design and develop a type of experiment setup that would enable the direct observation of steady diffusion process in situ. Two different optical methods - shadowgraph and shearing interferometry - were used for the first time to visualise and quantitatively analyse the diffusion around a droplet of organic substance in supercritical carbon dioxide (SCCO2) as well as in its direct vicinity. We constructed and tested a cylindrical high-pressure chamber and an experiment system with a high speed camera. The solute/solvent combination of DL- α-tocopherol/SCCO2 was applied using shadowgraph. The diffusion coefficients at temperatures of 40o C, 50o C and 60o C and pressures between 75 bar and 90 bar were calculated based on the displacement of the droplet contour in the captured images. The shearing interferometry with a Wollaston-prism was then applied not only for the combination of DL- α-tocopherol/SCCO2, but also for other substances in SCCO2, for example for a type of rose oil and lubricant oil as well as for acetone, benzene, toluene and naphthalene. The changes of the refractive index gradient were directly measured and evaluated with the interferograms; afterwards changes of the density gradients and the diffusion coefficients were determined. We propose then a multivariate regression model to capture the relationship between the diffusion coefficient, the pressure and the temperature. To minimize the influence of gravity-driven convections in the solvent during diffusion, the experiments were also carried out under microgravity condition, i.e. in two parabolic flight campaigns.

Experimental and theoretical comparison of Sb, As, and P diffusion mechanisms and doping in CdTe

NASA Astrophysics Data System (ADS)

Colegrove, E.; Yang, J.-H.; Harvey, S. P.; Young, M. R.; Burst, J. M.; Duenow, J. N.; Albin, D. S.; Wei, S.-H.; Metzger, W. K.

2018-02-01

Fundamental material doping challenges have limited CdTe electro-optical applications. In this work, the As atomistic diffusion mechanisms in CdTe are examined by spatially resolving dopant incorporation in both single-crystalline and polycrystalline CdTe over a range of experimental conditions. Density-functional theory calculations predict experimental activation energies and indicate that As diffuses slowly through the Te sublattice and quickly along GBs similar to Sb. Because of its atomic size and associated defect chemistry, As does not have a fast interstitial diffusion component similar to P. Experiments to incorporate and activate P, As, and Sb in polycrystalline CdTe are conducted to examine if ex situ Group V doping can overcome historic polycrystalline doping limits. The distinct P, As, and Sb diffusion characteristics create different strategies for increasing hole density. Because fast interstitial diffusion is prominent for P, less aggressive diffusion conditions followed by Cd overpressure to relocate the Group V element to the Te lattice site is effective. For larger atoms, slower diffusion through the Te sublattice requires more aggressive diffusion, however further activation is not always necessary. Based on the new physical understanding, we have obtained greater than 1016 cm-3 hole density in polycrystalline CdTe films by As and P diffusion.

40Ar ∗ loss in experimentally deformed muscovite and biotite with implications for 40Ar/ 39Ar geochronology of naturally deformed rocks

NASA Astrophysics Data System (ADS)

Cosca, Michael; Stunitz, Holger; Bourgeix, Anne-Lise; Lee, John P.

2011-12-01

The effects of deformation on radiogenic argon ( 40Ar ∗) retentivity in mica are described from high pressure experiments performed on rock samples of peraluminous granite containing euhedral muscovite and biotite. Cylindrical cores, ˜15 mm in length and 6.25 mm in diameter, were drilled from granite collected from the South Armorican Massif in northwestern France, loaded into gold capsules, and weld-sealed in the presence of excess water. The samples were deformed at a pressure of 10 kb and a temperature of 600 °C over a period 29 of hours within a solid medium assembly in a Griggs-type triaxial hydraulic deformation apparatus. Overall shortening in the experiments was approximately 10%. Transmitted light and secondary and backscattered electron imaging of the deformed granite samples reveals evidence of induced defects and for significant physical grain size reduction by kinking, cracking, and grain segmentation of the micas. Infrared (IR) laser (CO 2) heating of individual 1.5-2.5 mm diameter grains of muscovite and biotite separated from the undeformed granite yield well-defined 40Ar/ 39Ar plateau ages of 311 ± 2 Ma (2σ). Identical experiments on single grains separated from the experimentally deformed granite yield results indicating 40Ar ∗ loss of 0-35% in muscovite and 2-3% 40Ar ∗ loss in biotite. Intragrain in situ ultraviolet (UV) laser ablation 40Ar/ 39Ar ages (±4-10%, 1σ) of deformed muscovites range from 309 ± 13 to 264 ± 7 Ma, consistent with 0-16% 40Ar ∗ loss relative to the undeformed muscovite. The in situ UV laser ablation 40Ar/ 39Ar ages of deformed biotite vary from 301 to 217 Ma, consistent with up to 32% 40Ar ∗ loss. No spatial correlation is observed between in situ40Ar/ 39Ar age and position within individual grains. Using available argon diffusion data for muscovite the observed 40Ar ∗ loss in the experimentally treated muscovite can be utilized to predict average 40Ar ∗ diffusion dimensions. Maximum 40Ar/ 39Ar ages obtained by UV laser ablation overlap those of the undeformed muscovite, indicating argon loss of <1% and an average effective grain radius for 40Ar ∗ diffusion ⩾700 μm. The UV laser ablation and IR laser incremental 40Ar/ 39Ar ages indicating 40Ar ∗ loss of 16% and 35%, respectively, are consistent with an average diffusion radius ≪100 μm. These results support a hypothesis of grain-scale 40Ar ∗ diffusion distances in undeformed mica and a heterogeneous mechanical reduction in the intragrain effective diffusion length scale for 40Ar ∗ in deformed mica. Reduction in the effective diffusion length scale in naturally deformed samples occurs most probably through production of mesoscopic and submicroscopic defects such as, e.g., stacking faults. A network of interconnected defects, continuously forming and annealing during dynamic deformation likely plays an important role in controlling both 40Ar ∗ retention and intragrain distribution in deformed mica. Intragrain 40Ar/ 39Ar ages, when combined with estimates of diffusion kinetics and distances, may provide a means of establishing thermochronological histories from individual micas.

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.

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.

Temperature-Dependent Lithium-Ion Diffusion and Activation Energy of Li1.2Co0.13Ni0.13Mn0.54O2 Thin-Film Cathode at Nanoscale by Using Electrochemical Strain Microscopy.

PubMed

Yang, Shan; Yan, Binggong; Wu, Jiaxiong; Lu, Li; Zeng, Kaiyang

2017-04-26

This paper presents the in situ mapping of temperature-dependent lithium-ion diffusion at the nanometer level in thin film Li 1.2 Co 0.13 Ni 0.13 Mn 0.54 O 2 cathode using electrochemical strain microscopy. The thin-film Li 1.2 Co 0.13 Ni 0.13 Mn 0.54 O 2 cathode exhibits higher lithium-ion diffusivities with increasing temperature, which explains the higher capacity observed in the lithium-ion batteries with a Li-rich cathode at elevated temperature. In addition, the activation energy for lithium-ion diffusion can be extracted in an Arrhenius-type plot at the level of grain structure with the assumption that the ionic movement is diffusion controlled. Compared with the grain interiors, the grain boundaries show relatively lower activation energy; hence, it is the preferred diffusion path for lithium ions. This study has bridged the gap between atomistic calculations and traditional macroscopic experiments, showing direct evidence as well as mechanisms for ionic diffusion for Li-rich cathode material.

New Layer Thickness Parameterization of Diffusive Convection

NASA Astrophysics Data System (ADS)

Zhou, Sheng-Qi; Lu, Yuan-Zheng; Guo, Shuang-Xi; Song, Xue-Long; Qu, Ling; Cen, Xian-Rong; Fer, Ilker

2017-11-01

Double-diffusion convection is one of the most important non-mechanically driven mixing processes. Its importance has been particular recognized in oceanography, material science, geology, and planetary physics. Double-diffusion occurs in a fluid in which there are gradients of two (or more) properties with different molecular diffusivities and of opposing effects on the vertical density distribution. It has two primary modes: salt finger and diffusive convection. Recently, the importance of diffusive convection has aroused more interest due to its impact to the diapycnal mixing in the interior ocean and the ice and the ice-melting in the Arctic and Antarctic Oceans. In our recent work, we constructed a length scale of energy-containing eddy and proposed a new layer thickness parameterization of diffusive convection by using the laboratory experiment and in situ observations in the lakes and oceans. The new parameterization can well describe the laboratory convecting layer thicknesses (0.01 0.1 m) and those observed in oceans and lakes (0.1 1000 m). This work was supported by China NSF Grants (41476167,41406035 and 41176027), NSF of Guangdong Province, China (2016A030311042) and the Strategic Priority Research Program of the Chinese Academy of Sciences (XDA11030302).

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.

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.

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.

Integrating spatial and temporal oxygen data to improve the quantification of in situ petroleum biodegradation rates.

PubMed

Davis, Gregory B; Laslett, Dean; Patterson, Bradley M; Johnston, Colin D

2013-03-15

Accurate estimation of biodegradation rates during remediation of petroleum impacted soil and groundwater is critical to avoid excessive costs and to ensure remedial effectiveness. Oxygen depth profiles or oxygen consumption over time are often used separately to estimate the magnitude and timeframe for biodegradation of petroleum hydrocarbons in soil and subsurface environments. Each method has limitations. Here we integrate spatial and temporal oxygen concentration data from a field experiment to develop better estimates and more reliably quantify biodegradation rates. During a nine-month bioremediation trial, 84 sets of respiration rate data (where aeration was halted and oxygen consumption was measured over time) were collected from in situ oxygen sensors at multiple locations and depths across a diesel non-aqueous phase liquid (NAPL) contaminated subsurface. Additionally, detailed vertical soil moisture (air-filled porosity) and NAPL content profiles were determined. The spatial and temporal oxygen concentration (respiration) data were modeled assuming one-dimensional diffusion of oxygen through the soil profile which was open to the atmosphere. Point and vertically averaged biodegradation rates were determined, and compared to modeled data from a previous field trial. Point estimates of biodegradation rates assuming no diffusion ranged up to 58 mg kg(-1) day(-1) while rates accounting for diffusion ranged up to 87 mg kg(-1) day(-1). Typically, accounting for diffusion increased point biodegradation rate estimates by 15-75% and vertically averaged rates by 60-80% depending on the averaging method adopted. Importantly, ignoring diffusion led to overestimation of biodegradation rates where the location of measurement was outside the zone of NAPL contamination. Over or underestimation of biodegradation rate estimates leads to cost implications for successful remediation of petroleum impacted sites. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2014-03-01

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

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

NASA Astrophysics Data System (ADS)

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

2014-10-01

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

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.

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

Scanning tunneling spectroscopy study of the proximity effect in a disordered two-dimensional metal.

PubMed

Serrier-Garcia, L; Cuevas, J C; Cren, T; Brun, C; Cherkez, V; Debontridder, F; Fokin, D; Bergeret, F S; Roditchev, D

2013-04-12

The proximity effect between a superconductor and a highly diffusive two-dimensional metal is revealed in a scanning tunneling spectroscopy experiment. The in situ elaborated samples consist of superconducting single crystalline Pb islands interconnected by a nonsuperconducting atomically thin disordered Pb wetting layer. In the vicinity of each superconducting island the wetting layer acquires specific tunneling characteristics which reflect the interplay between the proximity-induced superconductivity and the inherent electron correlations of this ultimate diffusive two-dimensional metal. The observed spatial evolution of the tunneling spectra is accounted for theoretically by combining the Usadel equations with the theory of dynamical Coulomb blockade; the relevant length and energy scales are extracted and found in agreement with available experimental data.

Microtomography-based Inter-Granular Network for the simulation of radionuclide diffusion and sorption in a granitic rock

NASA Astrophysics Data System (ADS)

Iraola, Aitor; Trinchero, Paolo; Voutilainen, Mikko; Gylling, Björn; Selroos, Jan-Olof; Molinero, Jorge; Svensson, Urban; Bosbach, Dirk; Deissmann, Guido

2017-12-01

Field investigation studies, conducted in the context of safety analyses of deep geological repositories for nuclear waste, have pointed out that in fractured crystalline rocks sorbing radionuclides can diffuse surprisingly long distances deep into the intact rock matrix; i.e. much longer distances than those predicted by reactive transport models based on a homogeneous description of the properties of the rock matrix. Here, we focus on cesium diffusion and use detailed micro characterisation data, based on micro computed tomography, along with a grain-scale Inter-Granular Network model, to offer a plausible explanation for the anomalously long cesium penetration profiles observed in these in-situ experiments. The sparse distribution of chemically reactive grains (i.e. grains belonging to sorbing mineral phases) is shown to have a strong control on the diffusive patterns of sorbing radionuclides. The computed penetration profiles of cesium agree well with an analytical model based on two parallel diffusive pathways. This agreement, along with visual inspection of the spatial distribution of cesium concentration, indicates that for sorbing radionuclides the medium indeed behaves as a composite system, with most of the mass being retained close to the injection boundary and a non-negligible part diffusing faster along preferential diffusive pathways.

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.

In situ microscopy of the self-assembly of branched nanocrystals in solution

DOE PAGES

Sutter, Eli; Tkachenko, Alexei V.; Sutter, Peter; ...

2016-04-04

Here, solution-phase self-assembly of nanocrystals into mesoscale structures is a promising strategy for constructing functional materials from nanoscale components. Liquid environments are key to self-assembly since they allow suspended nanocrystals to diffuse and interact freely, but they also complicate experiments. Real-time observations with single-particle resolution could have transformative impact on our understanding of nanocrystal self-assembly. Here we use real-time in situ imaging by liquid-cell electron microscopy to elucidate the nucleation and growth mechanism and properties of linear chains of octapod-shaped nanocrystals in their native solution environment. Statistical mechanics modelling based on these observations and using the measured chain-length distribution clarifiesmore » the relative importance of dipolar and entropic forces in the assembly process and gives direct access to the interparticle interaction. Our results suggest that monomer-resolved in situ imaging combined with modelling can provide unprecedented quantitative insight into the microscopic processes and interactions that govern nanocrystal self-assembly in solution.« less

In situ microscopy of the self-assembly of branched nanocrystals in solution

NASA Astrophysics Data System (ADS)

Sutter, Eli; Sutter, Peter; Tkachenko, Alexei V.; Krahne, Roman; de Graaf, Joost; Arciniegas, Milena; Manna, Liberato

2016-04-01

Solution-phase self-assembly of nanocrystals into mesoscale structures is a promising strategy for constructing functional materials from nanoscale components. Liquid environments are key to self-assembly since they allow suspended nanocrystals to diffuse and interact freely, but they also complicate experiments. Real-time observations with single-particle resolution could have transformative impact on our understanding of nanocrystal self-assembly. Here we use real-time in situ imaging by liquid-cell electron microscopy to elucidate the nucleation and growth mechanism and properties of linear chains of octapod-shaped nanocrystals in their native solution environment. Statistical mechanics modelling based on these observations and using the measured chain-length distribution clarifies the relative importance of dipolar and entropic forces in the assembly process and gives direct access to the interparticle interaction. Our results suggest that monomer-resolved in situ imaging combined with modelling can provide unprecedented quantitative insight into the microscopic processes and interactions that govern nanocrystal self-assembly in solution.

Visualizing the chemistry and structure dynamics in lithium-ion batteries by in-situ neutron diffraction

PubMed Central

Wang, Xun-Li; An, Ke; Cai, Lu; Feng, Zhili; Nagler, Stephen E.; Daniel, Claus; Rhodes, Kevin J.; Stoica, Alexandru D.; Skorpenske, Harley D.; Liang, Chengdu; Zhang, Wei; Kim, Joon; Qi, Yue; Harris, Stephen J.

2012-01-01

We report an in-situ neutron diffraction study of a large format pouch battery cell. The succession of Li-Graphite intercalation phases was fully captured under an 1C charge-discharge condition (i.e., charge to full capacity in 1 hour). However, the lithiation and dilithiation pathways are distinctively different and, unlike in slowing charging experiments with which the Li-Graphite phase diagram was established, no LiC24 phase was found during charge at 1C rate. Approximately 75 mol. % of the graphite converts to LiC6 at full charge, and a lattice dilation as large as 4% was observed during a charge-discharge cycle. Our work demonstrates the potential of in-situ, time and spatially resolved neutron diffraction study of the dynamic chemical and structural changes in “real-world” batteries under realistic cycling conditions, which should provide microscopic insights on degradation and the important role of diffusion kinetics in energy storage materials. PMID:23087812

The polar thermosphere of Venus

NASA Astrophysics Data System (ADS)

Mueller-Wodarg, Ingo; Rosenblatt, Pascal; Bruinsma, Sean; Yelle, Roger; Svedhem, Håkan; Forbes, Jeffrey M.; Withers, Paul; Keating Sci. Gerald, Sr.; Lopez-Valverde, Miguel Angel

The thermosphere of Venus has been extensively observed in-situ primarily by the Pioneer Venus Orbiter, but those measurements concentrated on the low latitude regions. Until recently, no in-situ observations were made of the polar thermosphere of Venus, and reference atmospheres such as the VTS3 and VIRA models relied on solar zenith angle trends inferred at low latitudes in order to extrapolate to polar latitudes. The Venus Express Atmospheric Drag Experiment (VExADE) carries out accurate orbital tracking in order to infer for the first time ever the densities in Venus' polar thermosphere near 180 km altitude at solar minimum. During 3 recent tracking campaigns we obtained density measurements that allow us to compare actual densities in those regions with those predicted by the reference atmosphere models. We constructed a hydrostatic diffusive equilibrium at-mosphere model that interpolates between the Venus Express remote sensing measurements in the upper mesosphere and lower thermosphere region and the in-situ drag measurements by VExADE. This paper will present and discuss our latest findings.

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.

Simultaneous in situ electron temperature comparisons using Alouette 2 probe and plasma resonance data

NASA Technical Reports Server (NTRS)

Benson, R. F.

1973-01-01

The electron temperatures deduced from Alouette 2 diffuse resonance observations are compared with the temperature obtained from the Alouette 2 cylindrical electrostatic probe experiment using data from 5 mid-to-high latitude telemetry stations. The probe temperature is consistently higher than the diffuse resonance temperature. The average difference ranged from approximately 10% to 40% with the lower values occurring at the lowest altitudes sampled (near 500 km) and at high latitudes (dip latitude greater than 55 deg), and the larger values occurring at high altitudes and lower latitudes. The discrepancy appears to be of geophysical origin since it is dependent on the location of the data sample. The present observations support the view that the often observed radar backscatter - probe electron temperature discrepancy is also of geophysical origin.

Density Determination of Metallic Melts from Diffuse X-Ray Scattering

NASA Astrophysics Data System (ADS)

Brauser, N.; Davis, A.; Greenberg, E.; Prakapenka, V. B.; Campbell, A.

2017-12-01

Liquids comprise several important structural components of the deep Earth, for example, the present outer core and a hypothesized magma ocean early in Earth history. However, the physical properties of the constituent materials of these structures at high pressures and temperatures are less well constrained than their crystalline counterparts. Determination of the physical properties of these liquids can inform geophysical models of the composition and structure of the Earth, but methods for studying the physical properties of liquids at high pressure and temperatures are underdeveloped. One proposed method for direct determination of density of a melt requires analysis of the diffuse scattered X-ray signal of the liquid. Among the challenges to applying this technique to high-pressure melts within a laser heated diamond anvil cell are the low signal-to-noise ratio and overlapping diffraction peaks from the crystalline components of the sample assembly interfering with the diffuse scattering from the liquid. Recent advances in instrumentation at synchrotron X-ray sources have made this method more accessible for determination of density of melted material. In this work we present the technique and report the densities of three high-pressure melts of the FCC metals iron, nickel, and gold derived from diffuse scattered X-ray spectra collected from in situ laser-heated diamond anvil cell synchrotron experiments. The results are compared to densities derived from shock wave experiments.

Using Noise and Fluctuations for In Situ Measurements of Nitrogen Diffusion Depth

PubMed Central

Samoila, Cornel; Ursutiu, Doru; Schleer, Walter-Harald; Jinga, Vlad; Nascov, Victor

2016-01-01

In manufacturing processes involving diffusion (of C, N, S, etc.), the evolution of the layer depth is of the utmost importance: the success of the entire process depends on this parameter. Currently, nitriding is typically either calibrated using a “post process” method or controlled via indirect measurements (H2, O2, H2O + CO2). In the absence of “in situ” monitoring, any variation in the process parameters (gas concentration, temperature, steel composition, distance between sensors and furnace chamber) can cause expensive process inefficiency or failure. Indirect measurements can prevent process failure, but uncertainties and complications may arise in the relationship between the measured parameters and the actual diffusion process. In this paper, a method based on noise and fluctuation measurements is proposed that offers direct control of the layer depth evolution because the parameters of interest are measured in direct contact with the nitrided steel (represented by the active electrode). The paper addresses two related sets of experiments. The first set of experiments consisted of laboratory tests on nitrided samples using Barkhausen noise and yielded a linear relationship between the frequency exponent in the Hooge equation and the nitriding time. For the second set, a specific sensor based on conductivity noise (at the nitriding temperature) was built for shop-floor experiments. Although two different types of noise were measured in these two sets of experiments, the use of the frequency exponent to monitor the process evolution remained valid. PMID:28773941

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.

Direct Observation Through In Situ Transmission Electron Microscope of Early States of Crystallization in Nanoscale Metallic Glasses

NASA Astrophysics Data System (ADS)

Xie, Y.; Sohn, S.; Schroers, J.; Cha, J. J.

2017-11-01

Crystallization is a complex process that involves multiscale physics such as diffusion of atomic species over multiple length scales, thermodynamic energy considerations, and multiple possible intermediate states. In situ crystallization experiments inside a transmission electron microscope (TEM) using nanostructured metallic glasses (MGs) provide a unique platform to study directly crystallization kinetics and pathways. Here, we study the embryonic state of eutectic growth using Pt-Ni-Cu-P MG nanorods under in situ TEM. We directly observe the nucleation and growth of a Ni-rich polymorphic phase, followed by the nucleation and slower growth of a Cu-rich phase. The suppressed growth kinetics of the Cu-rich phase is attributed to locally changing chemical compositions. In addition, we show that growth can be controlled by incorporation of an entire nucleus instead of individual atoms. Such a nucleus has to align with the crystallographic orientation of a larger grain before it can be incorporated into the crystal. By directly observing the crystallization processes, particularly the early stages of non-polymorphic growth, in situ TEM crystallization studies of MG nanostructures provide a wealth of information, some of which can be applied to typical bulk crystallization.

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

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.

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

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.

Diffusion induced atomic islands on the surface of Ni/Cu nanolayers

NASA Astrophysics Data System (ADS)

Takáts, Viktor; Csik, Attila; Hakl, József; Vad, Kálmán

2018-05-01

Surface islands formed by grain-boundary diffusion has been studied in Ni/Cu nanolayers by in-situ low energy ion scattering spectroscopy, X-ray photoelectron spectroscopy, scanning probe microscopy and ex-situ depth profiling based on ion sputtering. In this paper a new experimental approach of measurement of grain-boundary diffusion coefficients is presented. Appearing time of copper atoms diffused through a few nanometer thick nickel layer has been detected by low energy ion scattering spectroscopy with high sensitivity. The grain-boundary diffusion coefficient can be directly calculated from this appearing time without using segregation factors in calculations. The temperature range of 423-463 K insures the pure C-type diffusion kinetic regime. The most important result is that surface coverage of Ni layer by Cu atoms reaches a maximum during annealing and stays constant if the annealing procedure is continued. Scanning probe microscopy measurements show a Volmer-Weber type layer growth of Cu layer on the Ni surface in the form of Cu atomic islands. Depth distribution of Cu in Ni layer has been determined by depth profile analysis.

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

IN SITU OXIDATION AND ASSOCIATED MASS-FLUX-REDUCTION/MASS-REMOVAL BEHAVIOR FOR SYSTEMS WITH ORGANIC LIQUID LOCATED IN LOWER-PERMEABILITY SEDIMENTS

PubMed Central

Marble, Justin C.; Carroll, Kenneth C.; Janousek, Hilary; Brusseau, Mark L.

2010-01-01

The effectiveness of permanganate for in situ chemical oxidation of organic liquid (trichloroethene) trapped in lower-permeability (K) zones located within a higher-permeability matrix was examined in a series of flow-cell experiments. The permanganate solution was applied in both continuous and pulsed-injection modes. Manganese-oxide precipitation, as confirmed by use of SEM-EDS, occurred within, adjacent to, and downgradient of the lower-K zones, reflective of trichloroethene oxidation. During flow interruptions, precipitate formed within the surrounding higher-permeability matrix, indicating diffusive flux of aqueous-phase trichloroethene from the lower-K zones. The impact of permanganate treatment on mass flux behavior was examined by conducting water floods after permanganate injection. The results were compared to those of water-flood control experiments. The amount of water flushing required for complete contaminant mass removal was reduced for all permanganate treatments for which complete removal was characterized. However, the nature of the mass-flux-reduction/mass-removal relationship observed during water flooding varied as a function of the specific permanganate treatment. PMID:20685008

Unsaturated flow and transport through a fault embedded in fractured welded tuff

USGS Publications Warehouse

Salve, Rohit; Liu, Hui‐Hai; Cook, Paul; Czarnomski, Atlantis; Hu, Qinhong; Hudson, David

2004-01-01

To evaluate the importance of matrix diffusion as a mechanism for retarding radionuclide transport in the vicinity of a fault located in unsaturated fractured rock, we carried out an in situ field experiment in the Exploratory Studies Facility at Yucca Mountain, Nevada. This experiment involved the release of ∼82,000 L of water over a period of 17 months directly into a near‐vertical fault under both constant positive head (at ∼0.04 m) and decreasing fluxes. A mix of conservative tracers (pentafluorobenzoic acid (PFBA) and bromide (applied in the form of lithium bromide)) was released along the fault over a period of 9 days, 7 months after the start of water release along the fault. As water was released into the fault, seepage rates were monitored in a large cavity excavated below the test bed. After the release of tracers, seepage water was continuously collected from three locations and analyzed for the injected tracers. Observations of bromide concentrations in seepage water during the early stages of the experiment and bromide and PFBA concentrations in the seepage water indicate the significant effects of matrix diffusion on transport through a fault embedded in fractured, welded rock.

Matching time and spatial scales of rapid solidification: dynamic TEM experiments coupled to CALPHAD-informed phase-field simulations

NASA Astrophysics Data System (ADS)

Perron, Aurelien; Roehling, John D.; Turchi, Patrice E. A.; Fattebert, Jean-Luc; McKeown, Joseph T.

2018-01-01

A combination of dynamic transmission electron microscopy (DTEM) experiments and CALPHAD-informed phase-field simulations was used to study rapid solidification in Cu-Ni thin-film alloys. Experiments—conducted in the DTEM—consisted of in situ laser melting and determination of the solidification kinetics by monitoring the solid-liquid interface and the overall microstructure evolution (time-resolved measurements) during the solidification process. Modelling of the Cu-Ni alloy microstructure evolution was based on a phase-field model that included realistic Gibbs energies and diffusion coefficients from the CALPHAD framework (thermodynamic and mobility databases). DTEM and post mortem experiments highlighted the formation of microsegregation-free columnar grains with interface velocities varying from ˜0.1 to ˜0.6 m s-1. After an ‘incubation’ time, the velocity of the planar solid-liquid interface accelerated until solidification was complete. In addition, a decrease of the temperature gradient induced a decrease in the interface velocity. The modelling strategy permitted the simulation (in 1D and 2D) of the solidification process from the initially diffusion-controlled to the nearly partitionless regimes. Finally, results of DTEM experiments and phase-field simulations (grain morphology, solute distribution, and solid-liquid interface velocity) were consistent at similar time (μs) and spatial scales (μm).

Matching time and spatial scales of rapid solidification: Dynamic TEM experiments coupled to CALPHAD-informed phase-field simulations

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

Perron, Aurelien; Roehling, John D.; Turchi, Patrice E. A.

A combination of dynamic transmission electron microscopy (DTEM) experiments and CALPHAD-informed phase-field simulations was used to study rapid solidification in Cu–Ni thin-film alloys. Experiments—conducted in the DTEM—consisted of in situ laser melting and determination of the solidification kinetics by monitoring the solid–liquid interface and the overall microstructure evolution (time-resolved measurements) during the solidification process. Modelling of the Cu–Ni alloy microstructure evolution was based on a phase-field model that included realistic Gibbs energies and diffusion coefficients from the CALPHAD framework (thermodynamic and mobility databases). DTEM and post mortem experiments highlighted the formation of microsegregation-free columnar grains with interface velocities varying frommore » ~0.1 to ~0.6 m s –1. After an 'incubation' time, the velocity of the planar solid–liquid interface accelerated until solidification was complete. In addition, a decrease of the temperature gradient induced a decrease in the interface velocity. The modelling strategy permitted the simulation (in 1D and 2D) of the solidification process from the initially diffusion-controlled to the nearly partitionless regimes. Lastly, results of DTEM experiments and phase-field simulations (grain morphology, solute distribution, and solid–liquid interface velocity) were consistent at similar time (μs) and spatial scales (μm).« less

Matching time and spatial scales of rapid solidification: Dynamic TEM experiments coupled to CALPHAD-informed phase-field simulations

DOE PAGES

Perron, Aurelien; Roehling, John D.; Turchi, Patrice E. A.; ...

2017-12-05

A combination of dynamic transmission electron microscopy (DTEM) experiments and CALPHAD-informed phase-field simulations was used to study rapid solidification in Cu–Ni thin-film alloys. Experiments—conducted in the DTEM—consisted of in situ laser melting and determination of the solidification kinetics by monitoring the solid–liquid interface and the overall microstructure evolution (time-resolved measurements) during the solidification process. Modelling of the Cu–Ni alloy microstructure evolution was based on a phase-field model that included realistic Gibbs energies and diffusion coefficients from the CALPHAD framework (thermodynamic and mobility databases). DTEM and post mortem experiments highlighted the formation of microsegregation-free columnar grains with interface velocities varying frommore » ~0.1 to ~0.6 m s –1. After an 'incubation' time, the velocity of the planar solid–liquid interface accelerated until solidification was complete. In addition, a decrease of the temperature gradient induced a decrease in the interface velocity. The modelling strategy permitted the simulation (in 1D and 2D) of the solidification process from the initially diffusion-controlled to the nearly partitionless regimes. Lastly, results of DTEM experiments and phase-field simulations (grain morphology, solute distribution, and solid–liquid interface velocity) were consistent at similar time (μs) and spatial scales (μm).« less

Detailed in situ laser calibration of the infrared imaging video bolometer for the JT-60U tokamak

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

Parchamy, H.; Peterson, B. J.; Konoshima, S.

2006-10-15

The infrared imaging video bolometer (IRVB) in JT-60U includes a single graphite-coated gold foil with an effective area of 9x7 cm{sup 2} and a thickness of 2.5 {mu}m. The thermal images of the foil resulting from the plasma radiation are provided by an IR camera. The calibration technique of the IRVB gives confidence in the absolute levels of the measured values of the plasma radiation. The in situ calibration is carried out in order to obtain local foil properties such as the thermal diffusivity {kappa} and the product of the thermal conductivity k and the thickness t{sub f} of themore » foil. These quantities are necessary for solving the two-dimensional heat diffusion equation of the foil which is used in the experiments. These parameters are determined by comparing the measured temperature profiles (for kt{sub f}) and their decays (for {kappa}) with the corresponding results of a finite element model using the measured HeNe laser power profile as a known radiation power source. The infrared camera (Indigo/Omega) is calibrated by fitting the temperature rise of a heated plate to the resulting camera data using the Stefan-Boltzmann law.« less

Exit, cohesion, and consensus: social psychological moderators of consensus among adolescent peer groups

PubMed Central

Fisher, Jacob C.

2017-01-01

Virtually all social diffusion work relies on a common formal basis, which predicts that consensus will develop among a connected population as the result of diffusion. In spite of the popularity of social diffusion models that predict consensus, few empirical studies examine consensus, or a clustering of attitudes, directly. Those that do either focus on the coordinating role of strict hierarchies, or on the results of online experiments, and do not consider how consensus occurs among groups in situ. This study uses longitudinal data on adolescent social networks to show how meso-level social structures, such as informal peer groups, moderate the process of consensus formation. Using a novel method for controlling for selection into a group, I find that centralized peer groups, meaning groups with clear leaders, have very low levels of consensus, while cohesive peer groups, meaning groups where more ties hold the members of the group together, have very high levels of consensus. This finding is robust to two different measures of cohesion and consensus. This suggests that consensus occurs either through central leaders’ enforcement or through diffusion of attitudes, but that central leaders have limited ability to enforce when people can leave the group easily. PMID:29335675

Microstructure selection in thin-sample directional solidification of an Al-Cu alloy: In situ X-ray imaging and phase-field simulations

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

Clarke, A. J.; Tourret, D.; Song, Y.

We study microstructure selection during during directional solidification of a thin metallic sample. We combine in situ X-ray radiography of a dilute Al-Cu alloy solidification experiments with three-dimensional phase-field simulations. Here we explore a range of temperature gradient G and growth velocity V and build a microstructure selection map for this alloy. We investigate the selection of the primary dendritic spacing Λ and tip radius ρ. While ρ shows a good agreement between experimental measurements and dendrite growth theory, with ρ~V $-$1/2, Λ is observed to increase with V (∂Λ/∂V > 0), in apparent disagreement with classical scaling laws formore » primary dendritic spacing, which predict that ∂Λ/∂V<0. We show through simulations that this trend inversion for Λ(V) is due to liquid convection in our experiments, despite the thin sample configuration. We use a classical diffusion boundary-layer approximation to semi-quantitatively incorporate the effect of liquid convection into phase-field simulations. This approximation is implemented by assuming complete solute mixing outside a purely diffusive zone of constant thickness that surrounds the solid-liquid interface. This simple method enables us to quantitatively match experimental measurements of the planar morphological instability threshold and primary spacings over an order of magnitude in V. Lastly, we explain the observed inversion of ∂Λ/∂V by a combination of slow transient dynamics of microstructural homogenization and the influence of the sample thickness.« less

Microstructure selection in thin-sample directional solidification of an Al-Cu alloy: In situ X-ray imaging and phase-field simulations

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

Clarke, A. J.; Tourret, D.; Song, Y.

We study microstructure selection during directional solidification of a thin metallic sample. We combine in situ X-ray radiography of a dilute Al-Cu alloy solidification experiments with three-dimensional phase-field simulations. We explore a range of temperature gradient G and growth velocity V and build a microstructure selection map for this alloy. We investigate the selection of the primary dendritic spacing Lambda and tip radius rho. While rho shows a good agreement between experimental measurements and dendrite growth theory, with rho similar to V-1/2, Lambda is observed to increase with V (partial derivative Lambda/partial derivative V > 0), in apparent disagreement withmore » classical scaling laws for primary dendritic spacing, which predict that partial derivative Lambda/partial derivative V <0. We show through simulations that this trend inversion for Lambda(V) is due to liquid convection in our experiments, despite the thin sample configuration. We use a classical diffusion boundary-layer approximation to semi-quantitatively incorporate the effect of liquid convection into phase-field simulations. This approximation is implemented by assuming complete solute mixing outside a purely diffusive zone of constant thickness that surrounds the solid-liquid interface. This simple method enables us to quantitatively match experimental measurements of the planar morphological instability threshold and primary spacings over an order of magnitude in V. We explain the observed inversion of partial derivative Lambda/partial derivative V by a combination of slow transient dynamics of microstructural homogenization and the influence of the sample thickness.« less

Microstructure selection in thin-sample directional solidification of an Al-Cu alloy: In situ X-ray imaging and phase-field simulations

DOE PAGES

Clarke, A. J.; Tourret, D.; Song, Y.; ...

2017-05-01

We study microstructure selection during during directional solidification of a thin metallic sample. We combine in situ X-ray radiography of a dilute Al-Cu alloy solidification experiments with three-dimensional phase-field simulations. Here we explore a range of temperature gradient G and growth velocity V and build a microstructure selection map for this alloy. We investigate the selection of the primary dendritic spacing Λ and tip radius ρ. While ρ shows a good agreement between experimental measurements and dendrite growth theory, with ρ~V $-$1/2, Λ is observed to increase with V (∂Λ/∂V > 0), in apparent disagreement with classical scaling laws formore » primary dendritic spacing, which predict that ∂Λ/∂V<0. We show through simulations that this trend inversion for Λ(V) is due to liquid convection in our experiments, despite the thin sample configuration. We use a classical diffusion boundary-layer approximation to semi-quantitatively incorporate the effect of liquid convection into phase-field simulations. This approximation is implemented by assuming complete solute mixing outside a purely diffusive zone of constant thickness that surrounds the solid-liquid interface. This simple method enables us to quantitatively match experimental measurements of the planar morphological instability threshold and primary spacings over an order of magnitude in V. Lastly, we explain the observed inversion of ∂Λ/∂V by a combination of slow transient dynamics of microstructural homogenization and the influence of the sample thickness.« less

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

Luce, F. P.; Azevedo, G. de M.; Baptista, D. L.

The formation and time resolved behavior of individual Pb nanoparticles embedded in silica have been studied by in-situ transmission electron microscopy observations at high temperatures (400–1100 °C) and under 200 keV electron irradiation. It is shown that under such extreme conditions, nanoparticles can migrate at long distances presenting a Brownian-like behavior and eventually coalesce. The particle migration phenomenon is discussed considering the influence of the thermal energy and the electron irradiation effects on the atomic diffusion process which is shown to control particle migration. These results and comparison with ex-situ experiments tackle the stability and the microstructure evolution of nanoparticles systems undermore » extreme conditions. It elucidates on the effects of energetic particle irradiation-annealing treatments either as a tool or as a detrimental issue that could hamper their long-term applications in radiation-harsh environments such as in space or nuclear sectors.« 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

Reconstruction of in-situ porosity and porewater compositions of low-permeability crystalline rocks: Magnitude of artefacts induced by drilling and sample recovery

NASA Astrophysics Data System (ADS)

Meier, D. B.; Waber, H. N.; Gimmi, T.; Eichinger, F.; Diamond, L. W.

2015-12-01

Geological site characterisation programmes typically rely on drill cores for direct information on subsurface rocks. However, porosity, transport properties and porewater composition measured on drill cores can deviate from in-situ values due to two main artefacts caused by drilling and sample recovery: (1) mechanical disruption that increases porosity and (2) contamination of the porewater by drilling fluid. We investigated the effect and magnitude of these perturbations on large drill core samples (12-20 cm long, 5 cm diameter) of high-grade, granitic gneisses obtained from 350 to 600 m depth in a borehole on Olkiluoto Island (SW Finland). The drilling fluid was traced with sodium-iodide. By combining out-diffusion experiments, gravimetry, UV-microscopy and iodide mass balance calculations, we successfully quantified the magnitudes of the artefacts: 2-6% increase in porosity relative to the bulk connected porosity and 0.9 to 8.9 vol.% contamination by drilling fluid. The spatial distribution of the drilling-induced perturbations was revealed by numerical simulations of 2D diffusion matched to the experimental data. This showed that the rims of the samples have a mechanically disrupted zone 0.04 to 0.22 cm wide, characterised by faster transport properties compared to the undisturbed centre (1.8 to 7.7 times higher pore diffusion coefficient). Chemical contamination was shown to affect an even wider zone in all samples, ranging from 0.15 to 0.60 cm, in which iodide enrichment was up to 180 mg/kgwater, compared to 0.5 mg/kgwater in the uncontaminated centre. For all samples in the present case study, it turned out that the magnitude of the artefacts caused by drilling and sample recovery is so small that no correction is required for their effects. Therefore, the standard laboratory measurements of porosity, transport properties and porewater composition can be taken as valid in-situ estimates. However, it is clear that the magnitudes strongly depend on site- and drilling-specific factors and therefore our results cannot be transferred simply to other locations. We recommend the approach presented in this study as a route to obtain reliable values in future drilling campaigns aimed at characterising in-situ bedrock properties.

Reconstruction of in-situ porosity and porewater compositions of low-permeability crystalline rocks: Magnitude of artefacts induced by drilling and sample recovery.

PubMed

Meier, D B; Waber, H N; Gimmi, T; Eichinger, F; Diamond, L W

2015-12-01

Geological site characterisation programmes typically rely on drill cores for direct information on subsurface rocks. However, porosity, transport properties and porewater composition measured on drill cores can deviate from in-situ values due to two main artefacts caused by drilling and sample recovery: (1) mechanical disruption that increases porosity and (2) contamination of the porewater by drilling fluid. We investigated the effect and magnitude of these perturbations on large drill core samples (12-20 cm long, 5 cm diameter) of high-grade, granitic gneisses obtained from 350 to 600 m depth in a borehole on Olkiluoto Island (SW Finland). The drilling fluid was traced with sodium-iodide. By combining out-diffusion experiments, gravimetry, UV-microscopy and iodide mass balance calculations, we successfully quantified the magnitudes of the artefacts: 2-6% increase in porosity relative to the bulk connected porosity and 0.9 to 8.9 vol.% contamination by drilling fluid. The spatial distribution of the drilling-induced perturbations was revealed by numerical simulations of 2D diffusion matched to the experimental data. This showed that the rims of the samples have a mechanically disrupted zone 0.04 to 0.22 cm wide, characterised by faster transport properties compared to the undisturbed centre (1.8 to 7.7 times higher pore diffusion coefficient). Chemical contamination was shown to affect an even wider zone in all samples, ranging from 0.15 to 0.60 cm, in which iodide enrichment was up to 180 mg/kg water, compared to 0.5 mg/kg water in the uncontaminated centre. For all samples in the present case study, it turned out that the magnitude of the artefacts caused by drilling and sample recovery is so small that no correction is required for their effects. Therefore, the standard laboratory measurements of porosity, transport properties and porewater composition can be taken as valid in-situ estimates. However, it is clear that the magnitudes strongly depend on site- and drilling-specific factors and therefore our results cannot be transferred simply to other locations. We recommend the approach presented in this study as a route to obtain reliable values in future drilling campaigns aimed at characterising in-situ bedrock properties. Copyright © 2015 Elsevier B.V. All rights reserved.

An approach to spin-resolved molecular gas microscopy

NASA Astrophysics Data System (ADS)

Covey, Jacob P.; De Marco, Luigi; Acevedo, Óscar L.; Rey, Ana Maria; Ye, Jun

2018-04-01

Ultracold polar molecules are an ideal platform for studying many-body physics with long-range dipolar interactions. Experiments in this field have progressed enormously, and several groups are pursuing advanced apparatus for manipulation of molecules with electric fields as well as single-atom-resolved in situ detection. Such detection has become ubiquitous for atoms in optical lattices and tweezer arrays, but has yet to be demonstrated for ultracold polar molecules. Here we present a proposal for the implementation of site-resolved microscopy for polar molecules, and specifically discuss a technique for spin-resolved molecular detection. We use numerical simulation of spin dynamics of lattice-confined polar molecules to show how such a scheme would be of utility in a spin-diffusion experiment.

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.

Thin film growth studies using time-resolved x-ray scattering

NASA Astrophysics Data System (ADS)

Kowarik, Stefan

2017-02-01

Thin-film growth is important for novel functional materials and new generations of devices. The non-equilibrium growth physics involved is very challenging, because the energy landscape for atomic scale processes is determined by many parameters, such as the diffusion and Ehrlich-Schwoebel barriers. We review the in situ real-time techniques of x-ray diffraction (XRD), x-ray growth oscillations and diffuse x-ray scattering (GISAXS) for the determination of structure and morphology on length scales from Å to µm. We give examples of time resolved growth experiments mainly from molecular thin film growth, but also highlight growth of inorganic materials using molecular beam epitaxy (MBE) and electrochemical deposition from liquids. We discuss how scaling parameters of rate equation models and fundamental energy barriers in kinetic Monte Carlo methods can be determined from fits of the real-time x-ray data.

Thin film growth studies using time-resolved x-ray scattering.

PubMed

Kowarik, Stefan

2017-02-01

Thin-film growth is important for novel functional materials and new generations of devices. The non-equilibrium growth physics involved is very challenging, because the energy landscape for atomic scale processes is determined by many parameters, such as the diffusion and Ehrlich-Schwoebel barriers. We review the in situ real-time techniques of x-ray diffraction (XRD), x-ray growth oscillations and diffuse x-ray scattering (GISAXS) for the determination of structure and morphology on length scales from Å to µm. We give examples of time resolved growth experiments mainly from molecular thin film growth, but also highlight growth of inorganic materials using molecular beam epitaxy (MBE) and electrochemical deposition from liquids. We discuss how scaling parameters of rate equation models and fundamental energy barriers in kinetic Monte Carlo methods can be determined from fits of the real-time x-ray data.

Breaking The Ion Frozen-in Condition Via The Non-gyrotropic Pressure Effect In Magnetic Reconnection

NASA Astrophysics Data System (ADS)

Dai, L.; Wang, C.; Angelopoulos, V.; Glassmeier, K. H.

2016-12-01

For magnetic reconnection to proceed, the frozen-in condition for both ion fluid and electron fluid in a localized diffusion region must be violated. In the framework of fluid, the frozen-in can be broken by inertial effects, thermal pressure effects, or inter-species collisions. An essential question in reconnection physics is what effect breaks the ion/electron frozen-in in the diffusion region. We present clear in-situ evidence that the off-diagonal pressure tensor, which corresponds to a non-gyrotropic pressure effect, is mainly responsible for breaking the ion frozen-in condition in reconnection. The non-gyrotropic pressure tensor is a fluid manifestation of ion demagnetization in reconnection. As our experiences indicate, we feel the need to clarify several conceptual points regarding the approach to studying diffusion region. 1) Conceptually, the ion/electron momentum equations ("ion/electron Ohm's law"), rather than the generalized Ohm's law (Rossi and Olbert,1970, equation [12.25] ), are appropriate for investigating the fronzen-in or decoupling of individual fluid species. 2) The reconnection electric field is equally explainable in terms of ion momentum or electron momentum equation.

Enhanced Proton Conductivity in Y-Doped BaZrO3 via Strain Engineering.

PubMed

Fluri, Aline; Marcolongo, Aris; Roddatis, Vladimir; Wokaun, Alexander; Pergolesi, Daniele; Marzari, Nicola; Lippert, Thomas

2017-12-01

The effects of stress-induced lattice distortions (strain) on the conductivity of Y-doped BaZrO 3 , a high-temperature proton conductor with key technological applications for sustainable electrochemical energy conversion, are studied. Highly ordered epitaxial thin films are grown in different strain states while monitoring the stress generation and evolution in situ. Enhanced proton conductivity due to lower activation energies is discovered under controlled conditions of tensile strain. In particular, a twofold increased conductivity is measured at 200 °C along a 0.7% tensile strained lattice. This is at variance with conclusions coming from force-field simulations or the static calculations of diffusion barriers. Here, extensive first-principles molecular dynamic simulations of proton diffusivity in the proton-trapping regime are therefore performed and found to agree with the experiments. The simulations highlight that compressive strain confines protons in planes parallel to the substrate, while tensile strain boosts diffusivity in the perpendicular direction, with the net result that the overall conductivity is enhanced. It is indeed the presence of the dopant and the proton-trapping effect that makes tensile strain favorable for proton conduction.

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.

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.

In Situ Effective Diffusion Coefficient Profiles in Live Biofilms Using Pulsed-Field Gradient Nuclear Magnetic Resonance

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

Renslow, Ryan S.; Majors, Paul D.; McLean, Jeffrey S.

2010-08-15

Diffusive mass transfer in biofilms is characterized by the effective diffusion coefficient. It is well-documented that the effective diffusion coefficient can vary by location in a biofilm. The current literature is dominated by effective diffusion coefficient measurements for distinct cell clusters and stratified biofilms showing this spatial variation. Regardless of whether distinct cell clusters or surface-averaging methods are used, position-dependent measurements of the effective diffusion coefficient are currently: 1) invasive to the biofilm, 2) performed under unnatural conditions, 3) lethal to cells, and/or 4) spatially restricted to only certain regions of the biofilm. Invasive measurements can lead to inaccurate resultsmore » and prohibit further (time dependent) measurements which are important for the mathematical modeling of biofilms. In this study our goals were to: 1) measure the effective diffusion coefficient for water in live biofilms, 2) monitor how the effective diffusion coefficient changes over time under growth conditions, and 3) correlate the effective diffusion coefficient with depth in the biofilm. We measured in situ two-dimensional effective diffusion coefficient maps within Shewanella oneidensis MR-1biofilms using pulsed-field gradient nuclear magnetic resonance methods, and used them to calculate surface-averaged relative effective diffusion coefficient (Drs) profiles. We found that 1) Drs decreased from the top of the biofilm to the bottom, 2) Drs profiles differed for biofilms of different ages, 3) Drs profiles changed over time and generally decreased with time, 4) all the biofilms showed very similar Drs profiles near the top of the biofilm, and 5) the Drs profile near the bottom of the biofilm was different for each biofilm. Practically, our results demonstrate that advanced biofilm models should use a variable effective diffusivity which changes with time and location in the biofilm.« less

Application and further development of diffusion based 2D chemical imaging techniques in the rhizosphere

NASA Astrophysics Data System (ADS)

Hoefer, Christoph; Santner, Jakob; Borisov, Sergey; Kreuzeder, Andreas; Wenzel, Walter; Puschenreiter, Markus

2015-04-01

Two dimensional chemical imaging of root processes refers to novel in situ methods to investigate and map solutes at a high spatial resolution (sub-mm). The visualization of these solutes reveals new insights in soil biogeochemistry and root processes. We derive chemical images by using data from DGT-LA-ICP-MS (Diffusive Gradients in Thin Films and Laser Ablation Inductively Coupled Plasma Mass Spectrometry) and POS (Planar Optode Sensors). Both technologies have shown promising results when applied in aqueous environment but need to be refined and improved for imaging at the soil-plant interface. Co-localized mapping using combined DGT and POS technologies and the development of new gel combinations are in our focus. DGTs are smart and thin (<0.4 mm) hydrogels; containing a binding resin for the targeted analytes (e.g. trace metals, phosphate, sulphide or radionuclides). The measurement principle is passive and diffusion based. The present analytes are diffusing into the gel and are bound by the resin. Thereby, the resin acts as zero sink. After application, DGTs are retrieved, dried, and analysed using LA-ICP-MS. The data is then normalized by an internal standard (e.g. 13C), calibrated using in-house standards and chemical images of the target area are plotted using imaging software. POS are, similar to DGT, thin sensor foils containing a fluorophore coating depending on the target analyte. The measurement principle is based on excitation of the flourophore by a specific wavelength and emission of the fluorophore depending on the presence of the analyte. The emitted signal is captured using optical filters and a DSLR camera. While DGT analysis is destructive, POS measurements can be performed continuously during the application. Both semi-quantitative techniques allow an in situ application to visualize chemical processes directly at the soil-plant interface. Here, we present a summary of results from rhizotron experiments with different plants in metal contaminated and agricultural soils.

Demonstration of Technologies for Remote and in Situ Sensing of Atmospheric Methane Abundances - a Controlled Release Experiment

NASA Astrophysics Data System (ADS)

Aubrey, A. D.; Thorpe, A. K.; Christensen, L. E.; Dinardo, S.; Frankenberg, C.; Rahn, T. A.; Dubey, M.

2013-12-01

It is critical to constrain both natural and anthropogenic sources of methane to better predict the impact on global climate change. Critical technologies for this assessment include those that can detect methane point and concentrated diffuse sources over large spatial scales. Airborne spectrometers can potentially fill this gap for large scale remote sensing of methane while in situ sensors, both ground-based and mounted on aerial platforms, can monitor and quantify at small to medium spatial scales. The Jet Propulsion Laboratory (JPL) and collaborators recently conducted a field test located near Casper, WY, at the Rocky Mountain Oilfield Test Center (RMOTC). These tests were focused on demonstrating the performance of remote and in situ sensors for quantification of point-sourced methane. A series of three controlled release points were setup at RMOTC and over the course of six experiment days, the point source flux rates were varied from 50 LPM to 2400 LPM (liters per minute). During these releases, in situ sensors measured real-time methane concentration from field towers (downwind from the release point) and using a small Unmanned Aerial System (sUAS) to characterize spatiotemporal variability of the plume structure. Concurrent with these methane point source controlled releases, airborne sensor overflights were conducted using three aircraft. The NASA Carbon in Arctic Reservoirs Vulnerability Experiment (CARVE) participated with a payload consisting of a Fourier Transform Spectrometer (FTS) and an in situ methane sensor. Two imaging spectrometers provided assessment of optical and thermal infrared detection of methane plumes. The AVIRIS-next generation (AVIRIS-ng) sensor has been demonstrated for detection of atmospheric methane in the short wave infrared region, specifically using the absorption features at ~2.3 μm. Detection of methane in the thermal infrared region was evaluated by flying the Hyperspectral Thermal Emission Spectrometer (HyTES), retrievals which interrogate spectral features in the 7.5 to 8.5 μm region. Here we discuss preliminary results from the JPL activities during the RMOTC controlled release experiment, including capabilities of airborne sensors for total columnar atmospheric methane detection and comparison to results from ground measurements and dispersion models. Potential application areas for these remote sensing technologies include assessment of anthropogenic and natural methane sources over wide spatial scales that represent significant unconstrained factors to the global methane budget.

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

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.

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.

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.

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.

A Systematic Procedure to Describe Shale Gas Permeability Evolution during the Production Process

NASA Astrophysics Data System (ADS)

Jia, B.; Tsau, J. S.; Barati, R.

2017-12-01

Gas flow behavior in shales is complex due to the multi-physics nature of the process. Pore size reduces as the in-situ stress increases during the production process, which will reduce intrinsic permeability of the porous media. Slip flow/pore diffusion enhances gas apparent permeability, especially under low reservoir pressures. Adsorption not only increases original gas in place but also influences gas flow behavior because of the adsorption layer. Surface diffusion between free gas and adsorption phase enhances gas permeability. Pore size reduction and the adsorption layer both have complex impacts on gas apparent permeability and non-Darcy flow might be a major component in nanopores. Previously published literature is generally incomplete in terms of coupling of all these four physics with fluid flow during gas production. This work proposes a methodology to simultaneously take them into account to describe a permeability evolution process. Our results show that to fully describe shale gas permeability evolution during gas production, three sets of experimental data are needed initially: 1) intrinsic permeability under different in-situ stress, 2) adsorption isotherm under reservoir conditions and 3) surface diffusivity measurement by the pulse-decay method. Geomechanical effects, slip flow/pore diffusion, adsorption layer and surface diffusion all play roles affecting gas permeability. Neglecting any of them might lead to misleading results. The increasing in-situ stress during shale gas production is unfavorable to shale gas flow process. Slip flow/pore diffusion is important for gas permeability under low pressures in the tight porous media. They might overwhelm the geomechanical effect and enhance gas permeability at low pressures. Adsorption layer reduces the gas permeability by reducing the effective pore size, but the effect is limited. Surface diffusion increases gas permeability more under lower pressures. The total gas apparent permeability might keep increasing during the gas production process when the surface diffusivity is larger than a critical value. We believe that our workflow proposed in this study will help describe shale gas permeability evolution considering all the underlying physics altogether.

Impact of Moisture Content and Grain Size on Hydrocarbon Diffusion in Porous Media

NASA Astrophysics Data System (ADS)

McLain, A. A.; Ho, C. K.

2001-12-01

Diffusion of hydrocarbon vapors in porous media can play an important role in our ability to characterize subsurface contaminants such as trichloroethylene (TCE). For example, traditional monitoring methods often rely on direct sampling of contaminated soils or vapor. These samples may be influenced by the diffusion of vapors away from the contaminant source term, such as non-aqueous-phase TCE liquid. In addition, diffusion of hydrocarbon vapors can also impact the migration and dispersion of the contaminant in the subsurface. Therefore, understanding the diffusion rates and vapor transport processes of hydrocarbons in variably-saturated, heterogeneous porous media will assist in the characterization and detection of these subsurface contaminants. The purpose of this study was to investigate the impact of soil heterogeneity and water-moisture content on the diffusion processes for TCE. A one-dimensional column experiment was used to monitor the rates of vapor diffusion through sand. Experiments were performed with different average water-moisture contents and different grain sizes. On one end of the column, a reservoir cap is used to encase the TCE, providing a constant vapor boundary condition while sealing the end. The other end of the column contains a novel microchemical sensor. The sensor employs a polymer-absorption resistor (chemiresistor) that reversibly swells and increases in resistance when exposed to hydrocarbons. Once calibrated, the chemiresistors can be used to passively monitor vapor concentrations. This unique method allows the detection of in-situ vapor concentrations without disturbing the local environment. Results are presented in the form of vapor-concentration breakthrough curves as detected by the sensor. The shape of the breakthrough curve is dependent on several key parameters, including the length of the column and parameters (e.g., water-moisture content and grain-size) that affect the effective diffusion coefficient of TCE in air. Comparisons are made between theoretical and observed breakthrough curves to evaluate the diffusion of TCE and other relevant physical processes (e.g., air-water partitioning of TCE). The relative impact of water-moisture content and grain size on the diffusion of TCE vapor in porous media is also addressed. The authors thank Bob Hughes, who developed the chemiresistor sensors, and Chad Davis, who assisted with the calibrations. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy under Contract DE-AC04-94AL85000.

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.

The relationship between the surface composition and electrical properties of corrosion films formed on carbon steel in alkaline sour medium: an XPS and EIS study.

PubMed

Galicia, Policarpo; Batina, Nikola; González, Ignacio

2006-07-27

This work studies the evolution of 1018 carbon steel surfaces during 3-15 day immersion in alkaline sour medium 0.1 M (NH4)2S and 10 ppm CN(-) as (NaCN). During this period of time, surfaces were jointly characterized by electrochemical techniques in situ (electrochemical impedance spectroscopy, EIS) and spectroscopic techniques ex situ (X-ray photoelectron spectroscopy, XPS). The results obtained by these techniques allowed for a description of electrical and chemical properties of the films of corrosion products formed at the 1018 steel surface. There is an interconversion cycle of chemical species that form films of corrosion products whose conversion reactions favor two different types of diffusions inside the films: a chemical diffusion of iron cations and a typical diffusion of atomic hydrogen. These phenomena jointly control the passivity of the interface attacked by the corrosive medium.

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.

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.

Mixed region reactors for in situ treatment of DNAPL contaminated low permeability media

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

West, O.R.; Siegrist, R.L.

1996-08-01

Fine-textured soils and sediments contaminated by dense non-aqueous phase liquids (DNAPLs) present a significant environmental restoration challenge. An emerging approach to rapid in situ treatment within low permeability media involves the use of soil mixing to create mixed region reactors wherein biological or physical/chemical treatment processes can be employed. In cohesive soils, mixing breaks up the original soil structure and produces soil aggregates or clods separated by interaggregate void spaces. These void spaces create preferential flow paths for more efficient extraction of contaminants from the soil matrix or more rapid diffusion of treatment agents into the soil aggregates. This enhancementmore » technology has been most successfully used with vapor stripping. However, other technologies can also be coupled with soil mixing including chemical degradation, biodegradation and solidification. The application of this technology to DNAPL-contaminated low permeability media appears promising but requires further experiments and models that can simulate the movement of DNAPLs in mixed regions. 11 refs., 6 figs.« less

Effect of drug efflux transporters on placental transport of antiretroviral agent abacavir.

PubMed

Neumanova, Zuzana; Cerveny, Lukas; Greenwood, Susan L; Ceckova, Martina; Staud, Frantisek

2015-11-01

Abacavir is as a frequent part of combination antiretroviral therapy used in pregnant women. The aim of this study was to investigate, using in vitro, in situ and ex vivo experimental approaches, whether the transplacental pharmacokinetics of abacavir is affected by ATP-binding cassette (ABC) efflux transporters functionally expressed in the placenta: P-glycoprotein (ABCB1), breast cancer resistance protein (ABCG2), multidrug resistance-associated protein 2 (ABCC2) and multidrug resistance-associated protein 5 (ABCC5). In vitro transport assays revealed that abacavir is a substrate of human ABCB1 and ABCG2 transporters but not of ABCC2 or ABCC5. In addition, in situ experiments using dually perfused rat term placenta confirmed interactions of abacavir with placental Abcb1/Abcg2. In contrast, uptake studies in human placental villous fragments did not reveal any interaction of abacavir with efflux transporters suggesting a large contribution of passive diffusion and/or influx mechanisms to net transplacental abacavir transfer. Copyright © 2015 Elsevier Inc. All rights reserved.

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).

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.

Vertical diffusivity in the benthic boundary layer of the Oregon shelf from a deliberate tracer release experiment

NASA Astrophysics Data System (ADS)

Ferrón, S.; Ho, D. T.; Hales, B. R.

2010-12-01

A Fluorescein/SF6 deliberate tracer release experiment was conducted in benthic boundary layer (BBL) waters of the outer shelf of Oregon, as part of a multi-disciplinary research project that aims to study cross-shelf carbon transport and biogeochemical reaction rates within the BBL. The purpose of the tracers release was to examine physical transport processes, the rate of turbulent mixing and to provide a Lagrangian frame of reference for tracking other chemical species (pCO2, O2, CH4, DIC, DOC, POC, NO3-, NH4+, Fe). The tracers were injected on May 2009 during moderate upwelling favorable conditions with weak near-bottom currents, along a 4-km N-S line near the shelf streak at the 150 m isobath. Tracers distribution in the patch were tracked for over 5 days by tow-yo surveys using a winch-controlled pumping profiling vehicle that incorporated several in situ instruments such as CTD sensors, a 1200 kHz ADCP and a dye fluorometer for Fluorescein. Dissolved SF6 concentrations were analyzed on board from the underway water stream pumped from the towed vehicle by using an automated high-resolution chromatographic system equipped with an electron capture detector (ECD). The work presented here focuses on the estimation of the effective vertical diffusivity (Kz) in the BBL of the Oregon Shelf from the change in moment of the tracers’ vertical distribution, calculated using a 1D advection-diffusion model.

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.

Time-dependent deformation of gas shales - role of rock framework versus reservoir fluids

NASA Astrophysics Data System (ADS)

Hol, Sander; Zoback, Mark

2013-04-01

Hydraulic fracturing operations are generally performed to achieve a fast, drastic increase of permeability and production rates. Although modeling of the underlying short-term mechanical response has proven successful via conventional geomechanical approaches, predicting long-term behavior is still challenging as the formation interacts physically and chemically with the fluids present in-situ. Recent experimental work has shown that shale samples subjected to a change in effective stress deform in a time-dependent manner ("creep"). Although the magnitude and nature of this behavior is strongly related to the composition and texture of the sample, also the choice of fluid used in the experiments affects the total strain response - strongly adsorbing fluids result in more, recoverable creep. The processes underlying time-dependent deformation of shales under in-situ stresses, and the long-term impact on reservoir performance, are at present poorly understood. In this contribution, we report triaxial mechanical tests, and theoretical/thermodynamic modeling work with the aim to identify and describe the main mechanisms that control time-dependent deformation of gas shales. In particular, we focus on the role of the shale solid framework versus the type and pressure of the present pore fluid. Our experiments were mainly performed on Eagle Ford Shale samples. The samples were subjected to cycles of loading and unloading, first in the dry state, and then again after equilibrating them with (adsorbing) CO2 and (non-adsorbing) He at fluid pressures of 4 MPa. Stresses were chosen close to those persisting under in-situ conditions. The results of our tests demonstrate that likely two main types of deformation mechanisms operate that relate to a) the presence of microfractures as a dominating feature in the solid framework of the shale, and b) the adsorbing potential of fluids present in the nanoscale voids of the shale. To explain the role of adsorption in the observed compaction creep, we postulate a serial coupling between 1) stress-driven desorption of the fluid species, 2) diffusion of the desorbed species out of the solid, and 3) consequent shrinkage. We propose a model in which the total shrinkage of the solid (Step 3) that is measured as bulk compaction, is driven by a change in stress state (Step 1), and evolves in time controlled by the diffusion characteristics of the system (Step 2). Our experimental and modeling study shows that both the nature of the solid framework of the shale, as well as the type and pressure of pore fluids affect the long-term in-situ mechanical behavior of gas shale reservoirs.

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.

Spontaneous Reperfusion after In Situ Thromboembolic Stroke in Mice

PubMed Central

Cho, Tae-Hee; Bolbos, Radu; Langlois, Jean-Baptiste; Hermitte, Laure; Wiart, Marlène; Berthezène, Yves; Nighoghossian, Norbert

2012-01-01

Injection of thrombin into the middle cerebral artery (MCA) of mice has been proposed as a new model of thromboembolic stroke. The present study used sequential multiparametric Magnetic Resonance Imaging (MRI), including Magnetic Resonance Angiography (MRA), Diffusion-Weighted Imaging (DWI) and Perfusion-Weighted Imaging (PWI), to document MCA occlusion, PWI-DWI mismatch, and lesion development. In the first experiment, complete MCA occlusion and reproducible hypoperfusion were obtained in 85% of animals during the first hour after stroke onset. In the second experiment, 80% of animals showed partial to complete reperfusion during a three-hour follow-up. Spontaneous reperfusion thus contributed to the variability in ischemic volume in this model. The study confirmed the value of the model for evaluating new thrombolytic treatments, but calls for extended MRI follow-up at the acute stage in therapeutic studies. PMID:23166825

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.

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.

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.

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.

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.

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.

Gas sensing properties and in situ diffuse reflectance infrared Fourier transform spectroscopy study of trichloroethylene adsorption and reactions on SnO2 films

NASA Astrophysics Data System (ADS)

Zhang, Zhenxin; Huang, Kaijin; Yuan, Fangli; Xie, Changsheng

2014-05-01

The detection of trichloroethylene has attracted much attention because it has an important effect on human health. The sensitivity of the SnO2 flat-type coplanar gas sensor arrays to 100 ppm trichloroethylene in air was investigated. The adsorption and surface reactions of trichloroethylene were investigated at 100-200 °C by in-situ diffuse reflection Fourier transform infrared spectroscopy (DIRFTS) on SnO2 films. Molecularly adsorbed trichloroethylene, dichloroacetyl chloride (DCAC), phosgene, HCl, CO, H2O, CHCl3, Cl2 and CO2 surface species are formed during trichloroethylene adsorption at 100-200 °C. A possible mechanism of the reaction process is discussed.

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.

Combined Ocean and Atmospheric Lidar Profile Results during the Ship-Aircraft Bio-Optical Experiment.

NASA Astrophysics Data System (ADS)

Hair, J. W.; Hostetler, C. A.; Hu, Y.; Behrenfeld, M. J.; Butler, C. F.; Harper, D. B.; Hare, R. J.; Berkoff, T.; Cook, A. L.; Collins, J. E., Jr.; Stockley, N.; Twardowski, M.; Cetinic, I.; Ferrare, R. A.; Mack, T. L.

2016-02-01

First of its kind combined atmospheric and ocean profile data were collected by the recently upgraded NASA Langley Research Center's (LaRC) High Spectral Resolution Lidar (HSRL-1) during the 17 July - 7 August 2014 Ship-Aircraft Bio-Optical Research Experiment (SABOR). This mission sampled over a region that covered the Gulf of Maine, open-ocean near Bermuda, and coastal waters from Virginia to Rhode Island. The HSRL-1 and the Research Scanning Polarimeter from NASA Goddard Institute for Space Studies collected data onboard the NASA LaRC King Air aircraft and flight operations were closely coordinated with the Research Vessel Endeavor that made in situ ocean optical and biological measurements. The lidar measurements provided profiles of atmospheric backscatter and particulate depolarization at 532nm, 1064nm, and extinction (532nm) from approximately 9km altitude. In addition, for the first time HSRL subsurface ocean backscatter, depolarization, and diffuse attenuation data at 532nm were collected and compared to both the ship measurements and the Moderate Resolution Imaging Spectrometer (NASA MODIS-Aqua) satellite ocean retrievals. This presentation will include an overview of the instrument and measurement methodology, show examples from the campaign, and provide preliminary comparisons with the in situ optics and satellite retrievals.

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.

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.

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.

An in situ approach to study trace element partitioning in the laser heated diamond anvil cell

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

Petitgirard, S.; Mezouar, M.; Borchert, M.

2012-01-15

Data on partitioning behavior of elements between different phases at in situ conditions are crucial for the understanding of element mobility especially for geochemical studies. Here, we present results of in situ partitioning of trace elements (Zr, Pd, and Ru) between silicate and iron melts, up to 50 GPa and 4200 K, using a modified laser heated diamond anvil cell (DAC). This new experimental set up allows simultaneous collection of x-ray fluorescence (XRF) and x-ray diffraction (XRD) data as a function of time using the high pressure beamline ID27 (ESRF, France). The technique enables the simultaneous detection of sample meltingmore » based to the appearance of diffuse scattering in the XRD pattern, characteristic of the structure factor of liquids, and measurements of elemental partitioning of the sample using XRF, before, during and after laser heating in the DAC. We were able to detect elements concentrations as low as a few ppm level (2-5 ppm) on standard solutions. In situ measurements are complimented by mapping of the chemical partitions of the trace elements after laser heating on the quenched samples to constrain the partitioning data. Our first results indicate a strong partitioning of Pd and Ru into the metallic phase, while Zr remains clearly incompatible with iron. This novel approach extends the pressure and temperature range of partitioning experiments derived from quenched samples from the large volume presses and could bring new insight to the early history of Earth.« less

A statistical method for estimating wood thermal diffusivity and probe geometry using in situ heat response curves from sap flow measurements

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

Chen, Xingyuan; Miller, Gretchen R.; Rubin, Yoram

2012-09-13

The heat pulse method is widely used to measure water flux through plants; it works by inferring the velocity of water through a porous medium from the speed at which a heat pulse is propagated through the system. No systematic, non-destructive calibration procedure exists to determine the site-specific parameters necessary for calculating sap velocity, e.g., wood thermal diffusivity and probe spacing. Such parameter calibration is crucial to obtain the correct transpiration flux density from the sap flow measurements at the plant scale; and consequently, to up-scale tree-level water fluxes to canopy and landscape scales. The purpose of this study ismore » to present a statistical framework for estimating the wood thermal diffusivity and probe spacing simutaneously from in-situ heat response curves collected by the implanted probes of a heat ratio apparatus. Conditioned on the time traces of wood temperature following a heat pulse, the parameters are inferred using a Bayesian inversion technique, based on the Markov chain Monte Carlo sampling method. The primary advantage of the proposed methodology is that it does not require known probe spacing or any further intrusive sampling of sapwood. The Bayesian framework also enables direct quantification of uncertainty in estimated sap flow velocity. Experiments using synthetic data show that repeated tests using the same apparatus are essential to obtain reliable and accurate solutions. When applied to field conditions, these tests are conducted during different seasons and automated using the existing data logging system. The seasonality of wood thermal diffusivity is obtained as a by-product of the parameter estimation process, and it is shown to be affected by both moisture content and temperature. Empirical factors are often introduced to account for the influence of non-ideal probe geometry on the estimation of heat pulse velocity, and they are estimated in this study as well. The proposed methodology can be applied for the calibration of existing heat ratio sap flow systems at other sites. It is especially useful when an alternative transpiration calibration device, such as a lysimeter, is not available.« less

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.

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.

MA_MISS: Mars Multispectral Imager for Subsurface Studies

NASA Astrophysics Data System (ADS)

De Sanctis, M. C.; Coradini, A.; Ammannito, E.; Boccaccini, A.; Di Iorio, T.; Battistelli, E.; Capanni, A.

2012-04-01

A Drilling system, coupled with an in situ analysis package, is installed on the ExoMars Pasteur Rover to perform in situ investigations up to 2m in the Mars soil. Ma_Miss (Mars Multispectral Imager for Subsurface Studies) is a spectrometer devoted to observe the lateral wall of the borehole generated by the Drilling system. The instrument is fully integrated with the Drill and shares its structure and electronics. For the first time in Mars exploration experiments the water/geochemical environment will be investigated as function of depth in the shallow subsurface. Samples from the subsurface of Martian soil are unaltered by weathering process, oxidation and erosion. Subsurface access can be the key to look for signs of present and past environmental conditions, associated to the possibility for life (water, volatiles and weathering process). The analysis of uncontaminated samples by means of instrumented Drill and in situ observations is the solution for unambiguous interpretation of the original environment that leading to the formation of rocks. Ma_Miss experiment is perfectly suited to perform multispectral imaging of the drilled layers. Ma_Miss is a miniaturized near-infrared imaging spectrometer in the range 0.4-2.2 µm with 20nm spectral sampling. The task of illuminating the borehole wall and collecting the diffused light from the illuminated spot on the target requires a transparent window on the Drill tool, which shall prevent the dust contamination of the optical and mechanical elements inside. Hardness of sapphire is the closest to diamond one, thus avoiding the risk of scratches on its surface. The Sapphire window is cylindrical, and bounded such as to realize a continuous auger profile. Ma_Miss Optical Head performs the double task of illuminating the borehole wall with a spot around 1 mm diameter and of collecting the scattered light coming from a 0.1 mm diameter spot of the target. The signal from the Optical Head to the spectrometer is transferred through the different elements of the Drill by means of fiber optics and an optical rotary joint implemented in the roto-translation group of the Drill. Ma_Miss Optical Head has been tested in the breadboard to capture the diffused light from the observed target and transfer the signal to a laboratory spectrometer for analysis. The Optical Head of Ma_Miss has been tested after integration in ExoMars Drill. The drilling experiment has been carried out in realistic media (tuff, red brick). The test shows good performance of Optical Head illumination capability and of the window cleanliness during the drilling. Illumination spot is focused at the nominal distance of 0.2 mm from the sapphire window. During the ExoMars Pasteur Rover mission, the Ma_Miss experiment will allow collecting valuable data of the drilled stratigraphic column, will document "in-situ" the nature of the samples that will be delivered to the Pasteur Laboratory and will be able to identify hydrated minerals, sedimentary materials and different kind of diagnostic materials of Martian subsurface.

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

Shuttle Flight Experiment on USMP-4: In Situ Monitoring of Crystal Growth Using MEPHISTO

NASA Technical Reports Server (NTRS)

Abbaschian, Reza; deGroh, Henry C., III; Leonardi, E.; deVahlDavis, Graham; Coriell, Sam; Cambon, Gerard

2001-01-01

This reports on the MEPHISTO-4 experiment on the Space Shuttle Columbia, STS-87, November 19-December 5, 1997. Involved were NASA; the University of Florida at Gainesville; groups from France that developed and built the furnace; the National Institute of Standards and Technology; The University of New South Wales, Australia; and Purdue University. This was a solidification study in which three long rods of Bismuth- 1 at.% Tin were directionally solidified. The goals were to solidify in an environment free of natural convection; to determine the relationship among solidification growth velocity, growth mode, and temperature; and determine the diffusivity of Sn in Bi. The flight samples grew with a planar solid/liquid interface at velocities less than 3.4 gm/s, and cellular growth was present at velocities greater than 6.7 um/s; grain orientation influenced the planar to cellular transition. The temperature gradient in the liquid was 204 K/cm. The s/l interface was flat with slight concavity. Diffusion-dominated conditions were present during MEPHISTO-4. The Seebeck technique was used to determine the s/I interface temperature during growth, however, to date, analysis of the Seebeck results has not yielded a reliable measurement of the interface temperature. The partition coefficient for Bi alloyed with Sn was measured, k = 0.029.

Strontium-free rare earth perovskite ferrites with fast oxygen exchange kinetics: Experiment and theory

NASA Astrophysics Data System (ADS)

Berger, Christian; Bucher, Edith; Windischbacher, Andreas; Boese, A. Daniel; Sitte, Werner

2018-03-01

The Sr-free mixed ionic electronic conducting perovskites La0.8Ca0.2FeO3-δ (LCF82) and Pr0.8Ca0.2FeO3-δ (PCF82) were synthesized via a glycine-nitrate process. Crystal structure, phase purity, and lattice constants were determined by XRD and Rietveld analysis. The oxygen exchange kinetics and the electronic conductivity were obtained from in-situ dc-conductivity relaxation experiments at 600-800 °C and 1×10-3≤pO2/bar≤0.1. Both LCF82 and PCF82 show exceptionally fast chemical surface exchange coefficients and chemical diffusion coefficients of oxygen. The oxygen nonstochiometry of LCF82 and PCF82 was determined by precision thermogravimetry. A point defect model was used to calculate the thermodynamic factors of oxygen and to estimate self-diffusion coefficients and ionic conductivities. Density Functional Theory (DFT) calculations on the crystal structure, oxygen vacancy formation as well as oxygen migration energies are in excellent agreement with the experimental values. Due to their favourable properties both LCF82 and PCF82 are of interest for applications in solid oxide fuel cell cathodes, solid oxide electrolyser cell anodes, oxygen separation membranes, catalysts, or electrochemical sensors.

Laboratory measurements of HDO/H2O isotopic fractionation during ice deposition in simulated cirrus clouds.

PubMed

Lamb, Kara D; Clouser, Benjamin W; Bolot, Maximilien; Sarkozy, Laszlo; Ebert, Volker; Saathoff, Harald; Möhler, Ottmar; Moyer, Elisabeth J

2017-05-30

The stable isotopologues of water have been used in atmospheric and climate studies for over 50 years, because their strong temperature-dependent preferential condensation makes them useful diagnostics of the hydrological cycle. However, the degree of preferential condensation between vapor and ice has never been directly measured at temperatures below 233 K (-40 °C), conditions necessary to form cirrus clouds in the Earth's atmosphere, routinely observed in polar regions, and typical for the near-surface atmospheric layers of Mars. Models generally assume an extrapolation from the warmer experiments of Merlivat and Nief [Merlivat L, Nief G (1967) Tellus 19:122-127]. Nonequilibrium kinetic effects that should alter preferential partitioning have also not been well characterized experimentally. We present here direct measurements of HDO/H 2 O equilibrium fractionation between vapor and ice ([Formula: see text]) at cirrus-relevant temperatures, using in situ spectroscopic measurements of the evolving isotopic composition of water vapor during cirrus formation experiments in a cloud chamber. We rule out the recent proposed upward modification of [Formula: see text], and find values slightly lower than Merlivat and Nief. These experiments also allow us to make a quantitative validation of the kinetic modification expected to occur in supersaturated conditions in the ice-vapor system. In a subset of diffusion-limited experiments, we show that kinetic isotope effects are indeed consistent with published models, including allowing for small surface effects. These results are fundamental for inferring processes on Earth and other planets from water isotopic measurements. They also demonstrate the utility of dynamic in situ experiments for studying fractionation in geochemical systems.

Laboratory measurements of HDO/H2O isotopic fractionation during ice deposition in simulated cirrus clouds

PubMed Central

Lamb, Kara D.; Clouser, Benjamin W.; Bolot, Maximilien; Sarkozy, Laszlo; Ebert, Volker; Saathoff, Harald; Möhler, Ottmar; Moyer, Elisabeth J.

2017-01-01

The stable isotopologues of water have been used in atmospheric and climate studies for over 50 years, because their strong temperature-dependent preferential condensation makes them useful diagnostics of the hydrological cycle. However, the degree of preferential condensation between vapor and ice has never been directly measured at temperatures below 233 K (−40 °C), conditions necessary to form cirrus clouds in the Earth’s atmosphere, routinely observed in polar regions, and typical for the near-surface atmospheric layers of Mars. Models generally assume an extrapolation from the warmer experiments of Merlivat and Nief [Merlivat L, Nief G (1967) Tellus 19:122–127]. Nonequilibrium kinetic effects that should alter preferential partitioning have also not been well characterized experimentally. We present here direct measurements of HDO/H2O equilibrium fractionation between vapor and ice (αeq) at cirrus-relevant temperatures, using in situ spectroscopic measurements of the evolving isotopic composition of water vapor during cirrus formation experiments in a cloud chamber. We rule out the recent proposed upward modification of αeq, and find values slightly lower than Merlivat and Nief. These experiments also allow us to make a quantitative validation of the kinetic modification expected to occur in supersaturated conditions in the ice–vapor system. In a subset of diffusion-limited experiments, we show that kinetic isotope effects are indeed consistent with published models, including allowing for small surface effects. These results are fundamental for inferring processes on Earth and other planets from water isotopic measurements. They also demonstrate the utility of dynamic in situ experiments for studying fractionation in geochemical systems. PMID:28495968

Effect of Stepwise Pressure Change on Porosity Evolution during Directional Solidification in Small Cylindrical Channels

NASA Technical Reports Server (NTRS)

Grugel, R.N.; Lee, C.P.; Cox, M.C.; Blandford, B.T.; Anilkumar, A.V.

2008-01-01

Controlled directional solidification experiments were performed in capillary channels, using nitrogen-saturated succinonitrile, to examine the effect of an in-situ stepwise processing pressure increase on an isolated pore evolution. Two experiments were performed using different processing pressure input profiles. The results indicate that a processing pressure increase has a transient effect on pore growth geometry characterized by an initial phase of decreasing pore diameter, followed by a recovery phase of increasing pore diameter. The experimental results also show that processing pressure can be used as a control parameter to either increase or terminate porosity formation. A theoretical model is introduced which indicates that the pore formation process is limited by the diffusion of solute-gas through the melt, and that the observed response toa pressure increase is attributed to the re-equilibration of solute concentration in the melt associated with the increased melt pressure.

Microfluidic electrochemical device and process for chemical imaging and electrochemical analysis at the electrode-liquid interface in-situ

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

Yu, Xiao-Ying; Liu, Bingwen; Yang, Li

2016-03-01

A microfluidic electrochemical device and process are detailed that provide chemical imaging and electrochemical analysis under vacuum at the surface of the electrode-sample or electrode-liquid interface in-situ. The electrochemical device allows investigation of various surface layers including diffuse layers at selected depths populated with, e.g., adsorbed molecules in which chemical transformation in electrolyte solutions occurs.

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.

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.

Simulation of radiation damage in minerals by sequential ion irradiations

NASA Astrophysics Data System (ADS)

Nakasuga, W. M.; Li, W.; Ewing, R. C.

2015-12-01

Radiation effects due to α-decay of U and Th and spontaneous fission of 238U control the production and recovery of the radiation-induced structure of minerals, as well as the diffusion of elements through the mineral host. However, details of how the damage microstructure is produced and annealed remain unknown. Our recent ion beam experiments demonstrate that ionizing radiation from the α-particle recovers the damage structure. Thus, the damage structure is not only the result of the thermal hisotry of the sample, but also of the complex interaction between ionizing and ballistic damage mechanisms. By combining ion irradiations with transmission electron microscopy (TEM), we have simulated the damage produced by α-decay and fission. The α-particle induced annealing has been simulated by in situ TEM observation of consecutive ion-irradiations: i.) 1 MeV Kr2+ (simulating 70 keV α-recoils induced damage), ii.) followed by 400 keV He+ (simulating 4.5 MeV α-particle induced annealing). Thus, in addition to the well-established effects of thermal annealing, the α-particle annealing effects, as evidenced by partical recrystallization of the originally, fully-amorphous apatite upon the α-particle irriadations, should also be considered when evaluating diffusion and release of elements, such as He. In addition, the fission track annealing has been simulated by a new sample preparation method that allows for direct observation of radiation damage recovery at each point along the length of latent tracks created by 80 MeV Xe ions (a typical fission fragment). The initial, rapid reduction in etched track length during isothermal annealing is explained by the rapid annealing of those sections of the track with smaller diameters, as observed directly by in situ TEM. In summary, the atomic-scale investigation of radiation damage in minerals is critical to understanding of the influence of raidation damage on diffusion and kinetics that are fundamental to geochronology.

Fluid mechanical consequences of pendular activity, segmentation and pyloric outflow in the proximal duodenum of the rat and the guinea pig.

PubMed

de Loubens, Clément; Lentle, Roger G; Love, Richard J; Hulls, Corrin; Janssen, Patrick W M

2013-06-06

We conducted numerical experiments to study the influence of non-propagating longitudinal and circular contractions, i.e. pendular activity and segmentation, respectively, on flow and mixing in the proximal duodenum. A lattice-Boltzmann numerical method was developed to simulate the fluid mechanical consequences for each of 22 randomly selected sequences of high-definition video of real longitudinal and radial contractile activity in the isolated proximal duodenum of the rat and guinea pig. During pendular activity in the rat duodenum, the flow was characterized by regions of high shear rate. Mixing was so governed by shearing deformation of the fluid that increased the interface between adjacent domains and accelerated their inter-diffusion (for diffusion coefficients approx. less than 10(-8) m² s(-1)). When pendular activity was associated with a slow gastric outflow characteristic of post-prandial period, the dispersion was also improved, especially near the walls. Mixing was not promoted by isolated segmentative contractions in the guinea pig duodenum and not notably influenced by pylorus outflow. We concluded that pendular activity generates mixing of viscous fluids 'in situ' and accelerates the diffusive mass transfer, whereas segmentation may be more important in mixing particulate suspensions with high solid volume ratios.

A multi-probe thermophoretic soot sampling system for high-pressure diffusion flames

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

Vargas, Alex M.; Gülder, Ömer L.

Optical diagnostics and physical probing of the soot processes in high pressure combustion pose challenges that are not faced in atmospheric flames. One of the preferred methods of studying soot in atmospheric flames is in situ thermophoretic sampling followed by transmission electron microscopy imaging and analysis for soot sizing and morphology. The application of this method of sampling to high pressures has been held back by various operational and mechanical problems. In this work, we describe a rotating disk multi-probe thermophoretic soot sampling system, driven by a microstepping stepper motor, fitted into a high-pressure chamber capable of producing sooting laminarmore » diffusion flames up to 100 atm. Innovative aspects of the sampling system design include an easy and precise control of the sampling time down to 2.6 ms, avoidance of the drawbacks of the pneumatic drivers used in conventional thermophoretic sampling systems, and the capability to collect ten consecutive samples in a single experimental run. Proof of principle experiments were performed using this system in a laminar diffusion flame of methane, and primary soot diameter distributions at various pressures up to 10 atm were determined. High-speed images of the flame during thermophoretic sampling were recorded to assess the influence of probe intrusion on the flow field of the flame.« less

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

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.

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

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.

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.

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.

Enhanced In Situ Chemical Oxidation Using Surfactants and Shear Thinning Fluids

NASA Astrophysics Data System (ADS)

Hauswirth, S.; Sadeghi, S.; Cerda, C. C.; Espinoza, I.; Schultz, P. B.; Miller, C. T.

2017-12-01

In situ chemical oxidation (ISCO) is an attractive approach for the remediation of recalcitrant contaminants, due to the fact that target compounds are degraded in place, precluding the need for ex situ treatment or disposal. However, field applications of ISCO approaches have been plagued by "rebound" of contaminant concentrations in groundwater weeks to months after treatment. The cause of rebound at a given site may vary, but is typically associated with back-diffusion from finer grained, low permeability units or the presence of non-aqueous phase liquids (NAPLs) that are incompletely degraded during treatment. Modifications to traditional ISCO methods have been proposed to overcome these challenges, including the use of shear-thinning polymers to improve delivery of oxidants to low permeability units and the addition of surfactants to improve dissolution of contaminants from NAPLs. In this work, we investigate the application of these approaches to the oxidation of manufactured gas plant (MGP) tars—NAPLs composed primarily of polycyclic aromatic hydrocarbons (PAHs). We conducted experiments to determine the mutual impact of each chemical component on the physical and chemical properties of the overall system. Specifically, experiments were designed to: determine the kinetics and overall effectiveness of contaminant-oxidant reactions for multiple oxidant-activator combinations; screen several common surfactants in terms of their ability to increase MGP tar solubility and their compatibility with oxidant systems; measure the impact of oxidants and surfactants on the rheology of several common polymer additives; and assess the effect of surfactants and polymers on the consumption of oxidants/activators and on the kinetics of contaminant-oxidant reactions. The results of this work provide insight into the chemical and physical mechanisms associated with enhanced ISCO approaches and an improved basis with which to model and design ISCO applications at both the lab and field scales.

In situ measurement of solution concentrations and fluxes of sulfonamides and trimethoprim antibiotics in soils using o-DGT.

PubMed

Chen, Chang-Er; Chen, Wei; Ying, Guang-Guo; Jones, Kevin C; Zhang, Hao

2015-01-01

Techniques, such as Diffusive Gradients in Thin-films (DGT), which either minimally disturb the soil or perturb it in a controlled way are most likely to provide information relevant to toxicity. Herein, we report the first use of DGT for organics (o-DGT) in soil systems to gain insight into the mobility and lability of four antibiotics-sulfamethoxazole (SMX), sulfamethazine (SMZ), and sulfadimethoxine (SDM), trimethoprim (TMP) in soil. In experiments where the same known amount of antibiotics were spiked into the soil, which was then further modified with NaOH, NaCl or dissolved organic matter, directly measured soil solution concentrations (Csoln) of these antibiotics were in the order: SMX>SMZ≈SDM>TMP. The R values (ratio of concentrations measured by o-DGT and directly in solution) were 0.56, 0.41, 0.40 and 0.28, respectively, indicating that the removal of these antibiotics from the solution can be to some extent resupplied by release from the solid phase. The nonlinearity of the relationship between o-DGT fluxes and the reciprocal of diffusive layer thickness (Δg) also suggested that soil solution concentrations were only partially sustained by the solid phase. The potential fluxes of these antibiotics in this soil were 5.4, 3.6, 2.4, and 1.2 pg/cm(2)/s for SMX, SMZ, SDM, and TMP, respectively. o-DGT is a promising tool for understanding the fate and behaviour of polar organic chemicals in soil, and it potentially provides an in situ approach for assessing their bioavailability. Copyright © 2014 Elsevier B.V. All rights reserved.

Surface diffusion in homoepitaxial SrTiO3 thin films

NASA Astrophysics Data System (ADS)

Woo, Chang-Su; Chu, Kanghyun; Song, Jong-Hyun; Yang, Chan-Ho; Charm Lab Team; Nano Spintronics Lab Collaboration

The development of growth techniques such as molecular beam epitaxy (MBE) and pulsed laser deposition (PLD) has facilitated growths of complex oxide thin films at the atomic level .... Systematic studies on surface diffusion process of adatoms using theoretical and experimental methods allow us to understand growth mechanism enabling atomically flat thin film surface. In this presentation, we introduce the synthesis of homoepitaxial SrTiO3 thin films using a PLD equipped with reflection of high energy electron diffraction (RHEED). We determine the surface diffusion time as a function of growth temperature and extract the activation energy of diffusion on the surface by in-situ monitoring the RHEED intensity recovery during the film deposition. From the extracted experimental results, we discuss the microscopic mechanism of the diffusion process

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.

Solid-phase diffusion mechanism for GaAs nanowire growth.

PubMed

Persson, Ann I; Larsson, Magnus W; Stenström, Stig; Ohlsson, B Jonas; Samuelson, Lars; Wallenberg, L Reine

2004-10-01

Controllable production of nanometre-sized structures is an important field of research, and synthesis of one-dimensional objects, such as nanowires, is a rapidly expanding area with numerous applications, for example, in electronics, photonics, biology and medicine. Nanoscale electronic devices created inside nanowires, such as p-n junctions, were reported ten years ago. More recently, hetero-structure devices with clear quantum-mechanical behaviour have been reported, for example the double-barrier resonant tunnelling diode and the single-electron transistor. The generally accepted theory of semiconductor nanowire growth is the vapour-liquid-solid (VLS) growth mechanism, based on growth from a liquid metal seed particle. In this letter we suggest the existence of a growth regime quite different from VLS. We show that this new growth regime is based on a solid-phase diffusion mechanism of a single component through a gold seed particle, as shown by in situ heating experiments of GaAs nanowires in a transmission electron microscope, and supported by highly resolved chemical analysis and finite element calculations of the mass transport and composition profiles.

Comparative analysis of ex-situ and operando X-ray diffraction experiments for lithium insertion materials

NASA Astrophysics Data System (ADS)

Brant, William R.; Li, Dan; Gu, Qinfen; Schmid, Siegbert

2016-01-01

A comparative study of ex-situ and operando X-ray diffraction techniques using the fast lithium ion conductor Li0.18Sr0.66Ti0.5Nb0.5O3 is presented. Ex-situ analysis of synchrotron X-ray diffraction data suggests that a single phase material exists for all discharges to as low as 0.422 V. For samples discharged to 1 V or lower, i.e. with higher lithium content, it is possible to determine the lithium position from the X-ray data. However, operando X-ray diffraction from a coin cell reveals that a kinetically driven two phase region occurs during battery cycling below 1 V. Through monitoring the change in unit cell dimension during electrochemical cycling the dynamics of lithium insertion are explored. A reduction in the rate of unit cell expansion of 22(2)% part way through the first discharge and 13(1)% during the second discharge is observed. This reduction may be caused by a drop in lithium diffusion into the bulk material for higher lithium contents. A more significant change is a jump in the unit cell expansion by 60(2)% once the lithium content exceeds one lithium ion per vacant site. It is suggested that this jump is caused by damping of octahedral rotations, thus establishing a link between lithium content and octahedral rotations.

Feasibility study of modeling liver thermal damage using minimally invasive optical method adequate for in situ measurement.

PubMed

Zhao, Jinzhe; Zhao, Qi; Jiang, Yingxu; Li, Weitao; Yang, Yamin; Qian, Zhiyu; Liu, Jia

2018-06-01

Liver thermal ablation techniques have been widely used for the treatment of liver cancer. Kinetic model of damage propagation play an important role for ablation prediction and real-time efficacy assessment. However, practical methods for modeling liver thermal damage are rare. A minimally invasive optical method especially adequate for in situ liver thermal damage modeling is introduced in this paper. Porcine liver tissue was heated by water bath under different temperatures. During thermal treatment, diffuse reflectance spectrum of liver was measured by optical fiber and used to deduce reduced scattering coefficient (μ ' s ). Arrhenius parameters were obtained through non-isothermal heating approach with damage marker of μ ' s . Activation energy (E a ) and frequency factor (A) was deduced from these experiments. A pair of averaged value is 1.200 × 10 5  J mol -1 and 4.016 × 10 17  s -1 . The results were verified for their reasonableness and practicality. Therefore, it is feasible to modeling liver thermal damage based on minimally invasive measurement of optical property and in situ kinetic analysis of damage progress with Arrhenius model. These parameters and this method are beneficial for preoperative planning and real-time efficacy assessment of liver ablation therapy. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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.

Physical Properties of Liquid Fe-S Alloys at High Pressure

NASA Astrophysics Data System (ADS)

Antonangeli, D.; Morard, G.; Marret, A.; Prescher, C.; Boulard, E.; Mezouar, M.; Rivoldini, A.

2016-12-01

Sulfur is classically considered the dominant light element alloyed to iron in the core of small telluric planets such as Mercury and Mars. The expected pressure (P) and temperature (T) conditions are: P between 6 and 40 GPa and T between 1300 and 2300 K for Mercury's core and P between 24 and 42 GPa and T between 1800 and 2600 K for Mars'core. The presence of an internally generated magnetic field and the amplitude of its 88d libration support the liquid nature of a portion of Merury's core, and various independent lines of evident suggest that Mars's core has been liquid throughout its history. However, as only few experiments, mostly based on sink/float methods studied liquid Fe-S alloys, little is known about the physical properties at these P-T conditions, greatly limiting our capability to produce accurate planetary models. Here we present results of in-situ x-ray diffraction experiments on Fe-S liquids compressed in laser heated diamond anvil cell and of ex-situ electron microcopy analysis of the recovered samples. Our data allowed us to determine the evolution of the eutectic composition with pressure and to establish the eutectic melting curve up to 50 GPa. The x-ray diffuse signal from the liquid is analyzed to derive the density and compressibility of the Fe-S liquid alloys as a function of the S content.

Self-assembled formation and transformation of In/CdZnTe(110) nano-rings into camel-humps

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

Cohen-Taguri, G.; Ruzin, A.; Goldfarb, I.

2012-05-21

We used in situ scanning tunneling microscopy to monitor in real time the formation of nano-rings at the molecular beam epitaxially grown In/CdZnTe(110) surface, and Auger electron spectroscopy to explore the corresponding compositional changes. In-diffusion of In and segregation of Cd to the surface in course of annealing lead to a formation of elliptically distorted nano-rings, elongated along the fast [110] diffusion direction. Exacerbated diffusion anisotropy in the liquid state, at temperatures above the melting point of In, further distorts the nano-rings into a camel-hump shape.

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.

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

Diffusion of multi-isotopic chemical species in molten silicates

NASA Astrophysics Data System (ADS)

Watkins, James M.; Liang, Yan; Richter, Frank; Ryerson, Frederick J.; DePaolo, Donald J.

2014-08-01

Diffusion experiments in a simplified Na2O-CaO-SiO2 liquid system are used to develop a general formulation for the fractionation of Ca isotopes during liquid-phase diffusion. Although chemical diffusion is a well-studied process, the mathematical description of the effects of diffusion on the separate isotopes of a chemical element is surprisingly underdeveloped and uncertain. Kinetic theory predicts a mass dependence on isotopic mobility, but it is unknown how this translates into a mass dependence on effective binary diffusion coefficients, or more generally, the chemical diffusion coefficients that are housed in a multicomponent diffusion matrix. Our experiments are designed to measure Ca mobility, effective binary diffusion coefficients, the multicomponent diffusion matrix, and the effects of chemical diffusion on Ca isotopes in a liquid of single composition. We carried out two chemical diffusion experiments and one self-diffusion experiment, all at 1250 °C and 0.7 GPa and using a bulk composition for which other information is available from the literature. The self-diffusion experiment is used to determine the mobility of Ca in the absence of diffusive fluxes of other liquid components. The chemical diffusion experiments are designed to determine the effect on Ca isotope fractionation of changing the counter-diffusing component from fast-diffusing Na2O to slow-diffusing SiO2. When Na2O is the main counter-diffusing species, CaO diffusion is fast and larger Ca isotopic effects are generated. When SiO2 is the main counter-diffusing species, CaO diffusion is slow and smaller Ca isotopic effects are observed. In both experiments, the liquid is initially isotopically homogeneous, and during the experiment Ca isotopes become fractionated by diffusion. The results are used as a test of a new general expression for the diffusion of isotopes in a multicomponent liquid system that accounts for both self diffusion and the effects of counter-diffusing species. Our results show that (1) diffusive isotopic fractionations depend on the direction of diffusion in composition space, (2) diffusive isotopic fractionations scale with effective binary diffusion coefficient, as previously noted by Watkins et al. (2011), (3) self-diffusion is not decoupled from chemical diffusion, (4) self diffusion can be faster than or slower than chemical diffusion and (5) off-diagonal terms in the chemical diffusion matrix have isotopic mass-dependence. The results imply that relatively large isotopic fractionations can be generated by multicomponent diffusion even in the absence of large concentration gradients of the diffusing element. The new formulations for isotope diffusion can be tested with further experimentation and provide an improved framework for interpreting mass-dependent isotopic variations in natural liquids.

Estimating Hydraulic Conductivities in a Fractured Shale Formation from Pressure Pulse Testing and 3d Modeling

NASA Astrophysics Data System (ADS)

Courbet, C.; DICK, P.; Lefevre, M.; Wittebroodt, C.; Matray, J.; Barnichon, J.

2013-12-01

In the framework of its research on the deep disposal of radioactive waste in shale formations, the French Institute for Radiological Protection and Nuclear Safety (IRSN) has developed a large array of in situ programs concerning the confining properties of shales in their underground research laboratory at Tournemire (SW France). One of its aims is to evaluate the occurrence and processes controlling radionuclide migration through the host rock, from the disposal system to the biosphere. Past research programs carried out at Tournemire covered mechanical, hydro-mechanical and physico-chemical properties of the Tournemire shale as well as water chemistry and long-term behaviour of the host rock. Studies show that fluid circulations in the undisturbed matrix are very slow (hydraulic conductivity of 10-14 to 10-15 m.s-1). However, recent work related to the occurrence of small scale fractures and clay-rich fault gouges indicate that fluid circulations may have been significantly modified in the vicinity of such features. To assess the transport properties associated with such faults, IRSN designed a series of in situ and laboratory experiments to evaluate the contribution of both diffusive and advective process on water and solute flux through a clay-rich fault zone (fault core and damaged zone) and in an undisturbed shale formation. As part of these studies, Modular Mini-Packer System (MMPS) hydraulic testing was conducted in multiple boreholes to characterize hydraulic conductivities within the formation. Pressure data collected during the hydraulic tests were analyzed using the nSIGHTS (n-dimensional Statistical Inverse Graphical Hydraulic Test Simulator) code to estimate hydraulic conductivity and formation pressures of the tested intervals. Preliminary results indicate hydraulic conductivities of 5.10-12 m.s-1 in the fault core and damaged zone and 10-14 m.s-1 in the adjacent undisturbed shale. Furthermore, when compared with neutron porosity data from borehole logging, porosity varies by a factor of 2.5 whilst hydraulic conductivity varies by 2 to 3 orders of magnitude. In addition, a 3D numerical reconstruction of the internal structure of the fault zone inferred from borehole imagery has been built to estimate the permeability tensor variations. First results indicate that hydraulic conductivity values calculated for this structure are 2 to 3 orders of magnitude above those measured in situ. Such high values are due to the imaging method that only takes in to account open fractures of simple geometry (sine waves). Even though improvements are needed to handle more complex geometry, outcomes are promising as the fault damaged zone clearly appears as the highest permeability zone, where stress analysis show that the actual stress state may favor tensile reopening of fractures. Using shale samples cored from the different internal structures of the fault zone, we aim now to characterize the advection and diffusion using laboratory petrophysical tests combined with radial and through-diffusion experiments.

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.

Investigating redox processes under diffusive and advective flow conditions using a coupled omics and synchrotron approach

NASA Astrophysics Data System (ADS)

Kemner, K. M.; Boyanov, M.; Flynn, T. M.; O'Loughlin, E. J.; Antonopoulos, D. A.; Kelly, S.; Skinner, K.; Mishra, B.; Brooks, S. C.; Watson, D. B.; Wu, W. M.

2015-12-01

FeIII- and SO42--reducing microorganisms and the mineral phases they produce have profound implications for many processes in aquatic and terrestrial systems. In addition, many of these microbially-catalysed geochemical transformations are highly dependent upon introduction of reactants via advective and diffusive hydrological transport. We have characterized microbial communities from a set of static microcosms to test the effect of ethanol diffusion and sulfate concentration on UVI-contaminated sediment. The spatial distribution, valence states, and speciation of both U and Fe were monitored in situ throughout the experiment by synchrotron x-ray absorption spectroscopy, in parallel with solution measurements of pH and the concentrations of sulfate, ethanol, and organic acids. After reaction initiation, a ~1-cm thick layer of sediment near the sediment-water (S-W) interface became visibly dark. Fe XANES spectra of the layer were consistent with the formation of FeS. Over the 4 year duration of the experiment, U LIII-edge XANES indicated reduction of U, first in the dark layer and then throughout the sediment. Next, the microcosms were disassembled and samples were taken from the overlying water and different sediment regions. We extracted DNA and characterized the microbial community by sequencing 16S rRNA gene amplicons with the Illumina MiSeq platform and found that the community evolved from its originally homogeneous composition, becoming significantly spatially heterogeneous. We have also developed an x-ray accessible column to probe elemental transformations as they occur along the flow path in a porous medium with the purpose of refining reactive transport models (RTMs) that describe coupled physical and biogeochemical processes in environmental systems. The elemental distribution dynamics and the RTMs of the redox driven processes within them will be presented.

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.

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.

Characterization of a clay-rich rock through development and installation of specific hydrogeological and diffusion test equipment in deep boreholes

NASA Astrophysics Data System (ADS)

Delay, Jacques; Distinguin, Marc; Dewonck, Sarah

Andra (Agence Nationale pour la Gestion des Déchets Radioactifs - National Radioactive Waste Management Agency) has developed specific tools and methodologies to evaluate and understand the main transport mechanisms of solute species in an argillaceous rock in the framework of the scientific program of the Meuse/Haute-Marne Underground Research Laboratory. This paper focuses on three specific equipments already installed in boreholes for the determination of convection and diffusion parameters in a very low permeability environment. The first one is a specific borehole completion for head and permeability measurements with an integrated wireless telemetry device. In 1995, Andra devised a probe equipped with a pressure sensor to monitor the long-term evolution of electro-magnetically transmitted pore pressures. The data gathered by this first device, and a second one installed in 2001, have shown the occurrence of overpressures in very low permeability formations. The second device is derived from the multipacker system used for monitoring the drainage of the Oxfordian limestone due to the sinking of the shaft above the Callovo-Oxfordian. It is used for obtaining from a single borehole, a pressure profile of the argillaceous formation and its encasing units. To date, the major information obtained with these two borehole equipments is the existence of a 25-35 m anomalous excess hydraulic head in the 130 m thick Callovo-Oxfordian argillaceous formation. Head values in the argillaceous rock exceed those in the overlying Oxfordian limestone by 25-35 m, and those in the underlying Dogger by over 45 m. The third equipment described in the paper, is derived from the experiment carried out at the Mont Terri rock laboratory since 1996 for the characterization of diffusion and retention processes. The system is adapted for a borehole drilled from the surface. The objectives of this experiment are as follows: Verification of the predominant role played by molecular diffusion compared with convection; Acquisition of data required to extrapolate and /or interpolate chemical retention and diffusion parameters. The diffusion test performed from the borehole makes it possible to test in situ a small number of tracers (HTO, 36Cl, 134Cs) at a scale of 10 cm for the non sorbing tracers.

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.

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.

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.

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.

In Situ Atomic Scale Visualization Of Surface Kinetics Driven Dynamics Of Oxide Growth On A Ni–Cr Surface

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

Luo, Langli; Zou, Lianfeng; Schreiber, Daniel K.

2016-01-20

We report in situ atomic-scale visualization of the dynamical three-dimensional (3D) growth of NiO during initial oxidation of Ni-10at%Cr using environmental transmission electron microscopy (ETEM). Despite the thermodynamic preference for Cr2O3 formation, cubic NiO oxides nucleated and grew epitaxially as the dominating oxide phase on the Ni-Cr (100) surface during initial oxidation. The growth of NiO islands proceeds through step-by-step adatom mechanism in 3D, which is sustained by surface diffusion of Ni and O atoms. Although the shapes of oxide islands are controlled by strain energy between oxide and alloy substrate, local surface kinetic variations can lead to the changemore » of surface planes of oxide islands. These results demonstrate that surface diffusion dominates initial oxidation of Ni-Cr in these test conditions.« less

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.

Development of a sorption rate technique for single zeolite crystals using an electrodynamic balance

NASA Astrophysics Data System (ADS)

Welegala, Mark Joseph

Conventional means for evaluating intracrystalline diffusion in zeolites are complicated by extracrystalline mass transport resistances, crystallite size distribution, sorption heat effects, and finite instrument response times. A potentially direct means of overcoming these problems is to study sorption uptake on a single crystal suspended within a flowing gas stream in an electrodynamic balance (EDB). The objectives of this research were to design, build and investigate the viability of using such a device for obtaining diffusion coefficients from simple sorbate/zeolite systems, by computing the sorption uptake curve from the levitation voltage as a function of time. The initial electronic cell design was strongly influenced by flow mixing considerations. Accordingly, the conventional bihyperboloid electrode configuration was discarded in favor of novel four-ring (4R), and later two-ring/two-screen (2R/2S) designs with cylindrical interior geometries. A detailed numerical model based on the Method of Discrete Charges (MDC) was developed and used to aid in the design and operational understanding of these cells. Several 2R/2S designs were built and tested, including teflon/mica composite and ceramic cells capable of withstanding up to 750oF, for in situ activation of the zeolites. The diffusion of carbon dioxide in zeolite A was selected for testing due to the large differential weight change (10-20%) which occurs at ambient conditions and the availability of reliable experimental diffusion results (Yucel and Ruthven, 1980a). In addition to the carbon dioxide sorbate, water on zeolite 4A and a system relatively immune to atmospheric contamination, CO2 on activated carbon were also studied. Laboratory 4A crystals of up to 45 μm were grown using Charnell's method. These large solid particles were captured using a dry charging technique, and held during elevated temperature dehydration. Preliminary experimentation introduced externally dried crystals to the cell chamber in 0.5-3 minutes. Only minimal desorption results with carbon dioxide and later, adsorption for water vapor, were obtained. Further experiments revealed that crystal contamination from laboratory air can be considerable in less than one minute, thereby preadsorbing airborne water vapor. The experimental methodology was changed to include in situ heating. Subsequent attempts to circumvent laser heating of the particle had limited success. Particle loss, (due to excessive charge loss) and cell material degradation limited the process to null point temperatures of approximately 260oC, which is insufficient for complete zeolite dehydration. Early, it was demonstrated that gas compositions could be switched while flowing without losing the particle. However, the resulting concentration transient imposes an ultimate limitation on the technique for application to rapidly diffusing systems. Also, the fact that the technique is gravimetric requires that the diffusing species must be appreciably adsorbed at ambient conditions. Thus the single crystal sorption apparatus based on the electrodynamic containment device would appear to have use primarily for strongly adsorbed and slowly diffusing species. (Abstract shortened by UMI.)

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

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

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.

Mechanical Properties and Tribological Behavior of In Situ NbC/Fe Surface Composites

NASA Astrophysics Data System (ADS)

Cai, Xiaolong; Zhong, Lisheng; Xu, Yunhua

2017-01-01

The mechanical properties and tribological behavior of the niobium carbide (NbC)-reinforced gray cast iron surface composites prepared by in situ synthesis have been investigated. Composites are comprised of a thin compound layer and followed by a deep diffusion zone on the surface of gray cast iron. The graded distributions of the hardness and elastic modulus along the depth direction of the cross section of composites form in the ranges of 6.5-20.1 and 159.3-411.2 GPa, respectively. Meanwhile, dry wear tests for composites were implemented on pin-on-disk equipment at sliding speed of 14.7 × 10-2 m/s and under 5 or 20 N, respectively. The result indicates that tribological performances of composites are considerably dependent on the volume fraction and the grain size of the NbC as well as the mechanical properties of the matrices in different areas. The surface compound layer presents the lowest coefficient of friction and wear rate, and exhibits the highest wear resistance, in comparison with diffusion zone and substrate. Furthermore, the worn morphologies observed reveal the dominant wear mechanism is abrasive wear feature in compound layer and diffusion zone.

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.

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

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

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.

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-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

Radionuclide Transport in Fracture-Granite Interface Zones

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

Hu, Q; Mori, A

In situ radionuclide migration experiments, followed by excavation and sample characterization, were conducted in a water-conducting shear zone at the Grimsel Test Site (GTS) in Switzerland to study diffusion paths of radionuclides in fractured granite. In this work, we employed a micro-scale mapping technique that interfaces laser ablation sampling with inductively coupled plasma-mass spectrometry (LA/ICP-MS) to measure the fine-scale (micron-range) distribution of actinides ({sup 234}U, {sup 235}U, and {sup 237}Np) in the fracture-granite interface zones. Long-lived {sup 234}U, {sup 235}U, and {sup 237}Np were detected in flow channels, as well as in the adjacent rock matrix, using the sensitive, feature-basedmore » mapping of the LA/ICP-MS technique. The injected sorbing actinides are mainly located within the advective flowing fractures and the immediately adjacent regions. The water-conducting fracture studied in this work is bounded on one side by mylonite and the other by granitic matrix regions. These actinides did not penetrate into the mylonite side as much as the relatively higher-porosity granite matrix, most likely due to the low porosity, hydraulic conductivity, and diffusivity of the fracture wall (a thickness of about 0.4 mm separates the mylonite region from the fracture) and the mylonite region itself. Overall, the maximum penetration depth detected with this technique for the more diffusive {sup 237}Np over the field experimental time scale of about 60 days was about 10 mm in the granitic matrix, illustrating the importance of matrix diffusion in retarding radionuclide transport from the advective fractures. Laboratory tests and numerical modeling of radionuclide diffusion into granitic matrix was conducted to complement and help interpret the field results. Measured apparent diffusivity of multiple tracers in granite provided consistent predictions for radionuclide transport in the fractured granitic rock.« less

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 Fiber Optic Probe for Monitoring Protein Aggregation, Nucleation, and Crystallization

NASA Technical Reports Server (NTRS)

Ansari, Rafat R.; Suh, Kwang I.; Arabshahi, Alireza; Wilson, William W.; Bray, Terry L.; DeLucas, Lawrence J.

1996-01-01

Protein crystals are experimentally grown in hanging drops in microgravity experiments on-board the Space Shuttle orbiter. The technique of dynamic light scattering (DLS) can be used to monitor crystal growth process in hanging droplets (approx. 30 (L)) in microgravity experiments, but elaborate instrumentation and optical alignment problems have made in-situ applications difficult. In this paper we demonstrate that such experiments are now feasible. We apply a newly developed fiber optic probe to various earth and space (micro- gravity) bound protein crystallization system configurations to test its capability. These include conventional batch (cuvette or capillary) systems, hanging drop method in a six-pack hanging drop vapor diffusion apparatus (HDVDA), a modified HDVDA for temperature- induced nucleation and aggregation studies, and a newly envisioned dynamically controlled vapor diffusion system (DCVDS) configuration. Our compact system exploits the principles of DLS and offers a fast (within a few seconds) means of quantitatively and non-invasively monitoring the various growth stages of protein crystallization. In addition to DLS capability, the probe can also be used for performing single-angle static light scattering measurements. It utilizes extremely low levels of laser power (approx. few (W)) without a need of having any optical alignment and vibration isolation. The compact probe is also equipped with a miniaturized microscope for visualization of macroscopic protein crystals. This new optical diagnostic system opens up enormous opportunity for exploring new ways to grow good quality crystals suitable for x-ray crystallographic analysis and may help develop a concrete scientific basis for understanding the process of crystallization.

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.

Dissociation of Laboratory-Synthesized Methane Hydrate in Coarse-Grained Sediments by Slow Depressurization

NASA Astrophysics Data System (ADS)

Phillips, S. C.; You, K.; Borgfeldt, T.; Meyer, D.; Dong, T.; Flemings, P. B.

2016-12-01

We performed four dissociation experiments in which experimentally-formed methane hydrate was dissociated via slow, stepwise depressurization, revealing in situ salinity conditions. Overall, these results suggest the occurrence of local pore water freshening around dissociating hydrate in which bulk equilibrium behavior is limited by salt diffusion. Depressurization was performed at a constant confining temperature over 1 to 3 weeks by releasing small volumes of methane gas from the top of a vertically-oriented sample into an inverted graduated cylinder. We identify three distinct regimes of depressurization based on pressure drop behavior: (1) release of free gas down to initial hydrate dissociation at 3.3 MPa in NaBr or 4.64 MPa in NaCl, (2) dissociation of methane hydrate characterized by a slow, logarithmic increase in pressure after each gas release and (3) residual free gas release. Initial hydrate dissociation in NaCl brine at 4.64 MPa corresponds to the phase boundary for hydrate in 9.6 wt% NaCl. In the NaCl experiment, pressure increases of 0.16 MPa while the sample was shut in over 3 days likely correspond to a recovery in salinity of 0.7 wt. %. Salt ions likely diffuse from brine ahead of the hydrate front, based on a length scale for diffusion of NaCl of 6.3 cm for 3 days. In this experiment dissociation at bulk equilibrium is expected to decline from 4.54 to 4.04 MPa; however actual dissociation during 73 gas releases over 15 days, results in a pressure drop from 4.64 to 3.25 MPa. Hydrate samples were formed by injection of methane gas at 1 ºC and 12.24 MPa within a cylinder packed with medium-grained quartz sand and initially saturated in a 7 wt% NaBr or NaCl solution. In two experiments in which the system was thoroughly leak tested, total methane consumed during formation and recovered during depressurization match within 7% indicating this approach to be relatively accurate for determining total methane in experimental or pressure core samples.

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

Direct variational data assimilation algorithm for atmospheric chemistry data with transport and transformation model

NASA Astrophysics Data System (ADS)

Penenko, Alexey; Penenko, Vladimir; Nuterman, Roman; Baklanov, Alexander; Mahura, Alexander

2015-11-01

Atmospheric chemistry dynamics is studied with convection-diffusion-reaction model. The numerical Data Assimilation algorithm presented is based on the additive-averaged splitting schemes. It carries out ''fine-grained'' variational data assimilation on the separate splitting stages with respect to spatial dimensions and processes i.e. the same measurement data is assimilated to different parts of the split model. This design has efficient implementation due to the direct data assimilation algorithms of the transport process along coordinate lines. Results of numerical experiments with chemical data assimilation algorithm of in situ concentration measurements on real data scenario have been presented. In order to construct the scenario, meteorological data has been taken from EnviroHIRLAM model output, initial conditions from MOZART model output and measurements from Airbase database.

Movement and fate of atrazine and bromide in central Kansas croplands

USGS Publications Warehouse

Sophocleous, M.; Townsend, M.A.; Whittemore, Donald O.

1990-01-01

Two flooding experiments were conducted at two sites with different soils to study the transport and fate of the commonly used herbicide atrazine and inorganic chemicals in the Great Bend Prairie croplands of south-central Kansas. The instantaneous profile method supplemented by the use of an organic (atrazine) and an inorganic (bromide) tracer chemical was used to characterize in situ the hydraulic and chemical properties of the appropriately instrumented field sites. Atrazine readily degraded to hydroxyatrazine and biodegradation by-products and was not detected deeper in the soil profile and underlying shallow aquifer. The classical processes of chemical movement based on porous media-equilibrium-diffuse flow did not fit the data well at either site. Incompletely mixed, slug flow appeared to predominate at one of the sites and preferential flow at the other. The slug movement caused 'piston-type' displacement of more saline solutions in the soil profile to the shallow water table. Recommendations for conducting related field studies based on our sampling experience are given. ?? 1990.

Seismic and aseismic fault slip in response to fluid injection observed during field experiments at meter scale

NASA Astrophysics Data System (ADS)

Cappa, F.; Guglielmi, Y.; De Barros, L.; Wynants-Morel, N.; Duboeuf, L.

2017-12-01

During fluid injection, the observations of an enlarging cloud of seismicity are generally explained by a direct response to the pore pressure diffusion in a permeable fractured rock. However, fluid injection can also induce large aseismic deformations which provide an alternative mechanism for triggering and driving seismicity. Despite the importance of these two mechanisms during fluid injection, there are few studies on the effects of fluid pressure on the partitioning between seismic and aseismic motions under controlled field experiments. Here, we describe in-situ meter-scale experiments measuring synchronously the fluid pressure, the fault motions and the seismicity directly in a fault zone stimulated by controlled fluid injection at 280 m depth in carbonate rocks. The experiments were conducted in a gallery of an underground laboratory in south of France (LSBB, http://lsbb.eu). Thanks to the proximal monitoring at high-frequency, our data show that the fluid overpressure mainly induces a dilatant aseismic slip (several tens of microns up to a millimeter) at the injection. A sparse seismicity (-4 < Mw < -3) is observed several meters away from the injection, in a part of the fault zone where the fluid overpressure is null or very low. Using hydromechanical modeling with friction laws, we simulated an experiment and investigated the relative contribution of the fluid pressure diffusion and stress transfer on the seismic and aseismic fault behavior. The model reproduces the hydromechanical data measured at injection, and show that the aseismic slip induced by fluid injection propagates outside the pressurized zone where accumulated shear stress develops, and potentially triggers seismicity. Our models also show that the permeability enhancement and friction evolution are essential to explain the fault slip behavior. Our experimental results are consistent with large-scale observations of fault motions at geothermal sites (Wei et al., 2015; Cornet, 2016), and suggest that controlled field experiments at meter-scale are important for better assessing the role of fluid pressure in natural and human-induced earthquakes.

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.

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.

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

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.

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.

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.

Growth of carbon nanotubes (CNTs) on metallic underlayers by diffusion plasma-enhanced chemical vapour deposition (DPECVD)

NASA Astrophysics Data System (ADS)

Kim, S. M.; Gangloff, L.

2009-10-01

Here, we demonstrate the low-temperature (480-612 °C) synthesis of carbon nanotubes (CNTs) on different metallic underlayers (i.e., NiV, Ir, Ag, Pt, W, and Ta) using diffusion (dc) plasma-enhanced (~20 W, -600 V) chemical vapour deposition (DPECVD). The catalyst used is bi-layered Fe/Al and the feedstock used is a mixture of C 2H 2 and NH 3 (1:4). The crucial component is the diffusion of radical ions and hydrogen generated such as H 2/H +/H 2+/NH 3+/CH 2+/C 2H 2+ (which are confirmed by in-situ mass spectroscopy) from the nozzle, where it is inserted for most effective plasma diffusion between a substrate and a gas distributor.

Electrokinetic Enhanced Permanganate Delivery for Low Permeability Soil Remediation

NASA Astrophysics Data System (ADS)

Chowdhury, A. I.; Gerhard, J.; Reynolds, D. A.; Sleep, B. E.; O'Carroll, D. M.

2016-12-01

Contaminant mass sequestered in low permeability zones (LPZ) in the subsurface has become a significant concern due to back diffusion of contaminants, leading to contaminant rebound following treatment of the high permeability strata. In-situ remediation technologies such as in-situ chemical oxidation (ISCO) are promising, however, successful delivery of oxidants into silts and clays remains a challenge. Electrokinetics (EK) has been proposed as a technique that can overcome this challenge by delivering oxidants into low permeability soils. This study demonstrates the ability of EK to facilitate permanganate delivery into silt for treatment of trichloroethene (TCE). A two-dimensional sandbox was packed with alternate vertical layers of coarse sand and silt contaminated with high concentrations of aqueous phase TCE. Nine experiments were conducted to compare EK-enhanced in-situ chemical oxidation (EK-ISCO) to ISCO alone or EK alone. Frequent groundwater sampling at multiple locations combined with image analysis provided detailed mapping of TCE, permanganate, and manganese dioxide mass distributions. EK-ISCO successfully delivered the permanganate throughout the silt cross-section while ISCO without EK resulted in permanganate delivery only to the edges of the silt layer. EK-ISCO resulted in a 4.4 order-of-magnitude (OoM) reduction in TCE concentrations in the coarse sand compared to a 3.5 OoM reduction for ISCO alone. This study suggests that electrokinetics coupled with ISCO can achieve enhanced remediation of lower permeability strata, where remediation technologies for successful contaminant mass removal would otherwise be limited.

In situ fluidization for peat bed rupture, and preliminary economic analysis.

PubMed

Niven, R K; Khalili, N

2002-11-01

This study concerns in situ fluidization (ISF), a new remediation method with potential application to the remediation of NAPL and heavy metal contaminants, by their release from the fluidized zone generated by a water jet. The present study examines the effect of ISF on layers of peat, of significance owing to its role as an important NAPL and metal contaminant trap. Once trapped, such contaminants are not readily accessible by most remedial methods, due to the low permeability and diffusivity of the peat. A simple tank experiment is used to demonstrate rupture of a peat layer by ISF, with removal of the peat as elutriated fines and segregated peat chunks. The application of ISF in the field is then examined by three field trials in uncontaminated sands, in both saturated and unsaturated conditions. Fluidized depths of up to 1.9 m in the saturated zone (with refusal on a peat layer) and 2.5 m in the unsaturated zone (no refusal) were attained, using a 1.9-m-long, 50 mm diameter jet operated at 5-13 1 s(-1). Pulses of dark turbidity and shell fragments in the effluent indicated the rupture of peat and shelly layers. The experiments demonstrate the hydraulic viability of ISF in the field, and its ability to remove peat-based contaminants. The issues of appropriate jet design and water generation during ISF are discussed, followed by a preliminary economic analysis of ISF relative to existing remediation methods.

Structural and kinetic studies of metal hydride hydrogen storage materials using thin film deposition and characterization techniques

NASA Astrophysics Data System (ADS)

Kelly, Stephen Thomas

Hydrogen makes an attractive energy carrier for many reasons. It is an abundant chemical fuel that can be produced from a wide variety of sources and stored for very long periods of time. When used in a fuel cell, hydrogen emits only water at the point of use, making it very attractive for mobile applications such as in an automobile. Metal hydrides are promising candidates for on-board reversible hydrogen storage in mobile applications due to their very high volumetric storage capacities---in most cases exceeding even that of liquid hydrogen. The United States Department of Energy (DOE) has set fuel system targets for an automotive hydrogen storage system, but as of yet no single material meets all the requirements. In particular, slow reaction kinetics and/or inappropriate thermodynamics plague many metal hydride hydrogen storage materials. In order to engineer a practical material that meets the DOE targets, we need a detailed understanding of the kinetic and thermodynamic properties of these materials during the phase change. In this work I employed sputter deposited thin films as a platform to study materials with highly controlled chemistry, microstructure and catalyst placement using thin film characterization techniques such as in situ x-ray diffraction (XRD) and neutron reflectivity. I observed kinetic limitations in the destabilized Mg2Si system due to the slow diffusion of the host Mg and Si atoms while forming separate MgH2 and Si phases. Conversely, I observed that the presence of Al in the Mg/Al system inhibits hydrogen diffusion while the host Mg and Al atoms interdiffuse readily, allowing the material to fall into a kinetic and/or thermodynamic trap by forming intermetallic compounds such as Mg17Al 12. By using in situ XRD to analyze epitaxial Mg films grown on (001) oriented Al2O3 substrates I observed hydride growth consistent with a model of a planar hydride layer growing into an existing metal layer. Subsequent film cycling changes the hydrogen absorption and desorption kinetics and degrades the material texture. Cycling the films to greater hydrogen loading accelerates the changes to the kinetics and material texture. In addition to in situ XRD experiments, in situ neutron reflectivity experiments on epitaxial Mg films exposed to hydrogen gas reveal details about the microstructural development of the growing hydride layer as the film absorbs and releases hydrogen. Small (10 wt%) additions of Ti to epitaxial Mg films during growth result in metastable solid solution films of Ti in Mg that deposit epitaxially on (001) Al2O3 substrates with epitaxy similar to the pure Mg films. These metastable alloy films absorb hydrogen faster than pure Mg films under identical conditions. Subsequent film cycling results in altered reaction kinetics and a transition to a different kinetic mechanism during desorption than for pure Mg films.

Biomass-based magnetic fluorescent nanoparticles: One-step scalable synthesis, application as drug carriers and mechanism study.

PubMed

Li, Lei; Wang, Feijun; Shao, Ziqiang

2018-03-15

A biomass-based magnetic fluorescent nanoparticle (MFNPs) was successively in situ synthesized via a one-step high-gravity approach, which constructed by a magnetic core of Fe 3 O 4 nanoparticles, the fluorescent marker of carbon dots (CDs), and shells of chitosan (CS). The obtained MFNPs had a 10 nm average diameter and narrow particle size distribution, low cytotoxicity, superior fluorescent emission and superparamagnetic properties. The encapsulating and release 5-fluorouracil experiments confirmed that the introduction of CS/CDs effectively improved the drug loading capacity. Mechanism and kinetic studies proved that: (i) the monolayer adsorption was the main sorption mode under the studied conditions; (ii) the whole adsorption process was controlled by intra-liquid diffusion mass transfer and governed by chemisorption; and (iii) the release process was controlled by Fickian diffusion. These results demonstrated this method to one-step continuously produce MFNPs and the construction of non-toxic nanostructure possessed great superiority in currently Nano-delivery systems, which would show high application value in targeted drug delivery, magnetic fluid hyperthermia treatment, magnetic resonance imaging (MRI), in vitro testing and relative research. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

A Controllable Earthquake Rupture Experiment on the Homestake Fault

NASA Astrophysics Data System (ADS)

Germanovich, L. N.; Murdoch, L. C.; Garagash, D.; Reches, Z.; Martel, S. J.; Gwaba, D.; Elsworth, D.; Lowell, R. P.; Onstott, T. C.

2010-12-01

Fault-slip is typically simulated in the laboratory at the cm-to-dm scale. Laboratory results are then up-scaled by orders of magnitude to understand faulting and earthquakes processes. We suggest an experimental approach to reactivate faults in-situ at scales ~10-100 m using thermal techniques and fluid injection to modify in situ stresses and the fault strength to the point where the rock fails. Mines where the modified in-situ stresses are sufficient to drive faulting, present an opportunity to conduct such experiments. During our recent field work in the former Homestake gold mine in the northern Black Hills, South Dakota, we found a large fault present on multiple mine levels. The fault is subparallel to the local foliation in the Poorman formation, a Proterozoic metamorphic rock deformed into regional-scale folds with axes plunging ~40° to the SSE. The fault extends at least 1.5 km along strike and dip, with a center ~1.5 km deep. It strikes ~320-340° N, dips ~45-70° NE, and is recognized by a ~0.3-0.5 m thick distinct gouge that contains crushed host rock and black material that appears to be graphite. Although we could not find clear evidence for fault displacement, secondary features suggest that it is a normal fault. The size and distinct structure of this fault make it a promising target for in-situ experimentation of fault strength, hydrological properties, and slip nucleation processes. Most earthquakes are thought to be the result of unstable slip on existing faults, Activation of the Homestake fault in response to the controlled fluid injection and thermally changing background stresses is likely to be localized on a crack-like patch. Slow patch propagation, moderated by the injection rate and the rate of change of the background stresses, may become unstable, leading to the nucleation of a small earthquake (dynamic) rupture. This controlled instability is intimately related to the dependence of the fault strength on the slip process and has been analyzed for the Homestake fault conditions. Scale analyses indicate that this transition occurs for the nucleation patch size ~1 m. This represents a fundamental limitation for laboratory experiments, where the induced dynamic patch could be tractable, and necessitates larger scale field tests ~10-100 m. The ongoing dewatering is expected to affect displacements in the fault vicinity. This poroelastic effect can be used to better characterize the fault. Nucleation, propagation, and arrest of dynamic fault slip is governed by fluid overpressure source, diffusion, and the magnitude of the background loading in relation to the peak and residual strength in the fault zone at the ambient pore pressure level. More information on in-situ stresses than currently available is required to evaluate the fault state. Yet, initial modeling suggests that a suitable place for such an experiment is where the Homestake fault intersects the 4850-ft mine level or at greater depths.

Self diffusion of alkaline-Earth in Ca-Mg-aluminosilicate melts: Experimental improvements on the determination of the self-diffusion coefficients

NASA Technical Reports Server (NTRS)

Paillat, O.; Wasserburg, G. J.

1993-01-01

Experimental studies of self-diffusion isotopes in silicate melts often have quite large uncertainties when comparing one study to another. We designed an experiment in order to improve the precision of the results by simultaneously studying several elements (Mg, Ca, Sr, Ba) during the same experiment thereby greatly reducing the relative experimental uncertainties. Results show that the uncertainties on the diffusion coefficients can be reduced to 10 percent, allowing a more reliable comparison of differences of self-diffusion coefficients of the elements. This type of experiment permits us to study precisely and simultaneously several elements with no restriction on any element. We also designed an experiment to investigate the possible effects of multicomponent diffusion during Mg self-diffusion experiments by comparing cases where the concentrations of the elements and the isotopic compositions are different. The results suggest that there are differences between the effective means of transport. This approach should allow us to investigate the importance of multicomponent diffusion in silicate melts.

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 Field Measurement of Leaf Water Potential Using Thermocouple Psychrometers 1

PubMed Central

Savage, Michael J.; Wiebe, Herman H.; Cass, Alfred

1983-01-01

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. PMID:16663267

Hand-held synchronous scan spectrometer for in situ and immediate detection of live/dead bacteria ratio

NASA Astrophysics Data System (ADS)

Li, Runze; Goswami, Umang; Walck, Matthew; Khan, Kasfia; Chen, Jie; Cesario, Thomas C.; Rentzepis, Peter M.

2017-11-01

The design, construction, and operation of a hand-held synchronously scanned, excitation-emission, double monochromator spectrometer is described. Data show that it is possible to record and display within minutes the fluorescence spectra and ratio of live/dead bacteria in situ. Excitation emission matrix contour plots display clearly bacteria fluorescence spectra before and after UV inactivation, respectively. The separation of the fluorescence band maxima of molecular components, such as tryptophan, tyrosine, and DNA, may be distinguished in the diffused fluorescence spectra of bacteria and mixtures.

Hand-held synchronous scan spectrometer for in situ and immediate detection of live/dead bacteria ratio.

PubMed

Li, Runze; Goswami, Umang; Walck, Matthew; Khan, Kasfia; Chen, Jie; Cesario, Thomas C; Rentzepis, Peter M

2017-11-01

The design, construction, and operation of a hand-held synchronously scanned, excitation-emission, double monochromator spectrometer is described. Data show that it is possible to record and display within minutes the fluorescence spectra and ratio of live/dead bacteria in situ. Excitation emission matrix contour plots display clearly bacteria fluorescence spectra before and after UV inactivation, respectively. The separation of the fluorescence band maxima of molecular components, such as tryptophan, tyrosine, and DNA, may be distinguished in the diffused fluorescence spectra of bacteria and mixtures.

Additive manufacturing of liquid/gas diffusion layers for low-cost and high-efficiency hydrogen production

DOE PAGES

Mo, Jingke; Zhang, Feng -Yuan; Dehoff, Ryan R.; ...

2016-01-14

The electron beam melting (EBM) additive manufacturing technology was used to fabricate titanium liquid/gas diffusion media with high-corrosion resistances and well-controllable multifunctional parameters, including two-phase transport and excellent electric/thermal conductivities, has been first demonstrated. Their applications in proton exchange membrane eletrolyzer cells have been explored in-situ in a cell and characterized ex-situ with SEM and XRD. Compared with the conventional woven liquid/gas diffusion layers (LGDLs), much better performance with EBM fabricated LGDLs is obtained due to their significant reduction of ohmic loss. The EBM technology components exhibited several distinguished advantages in fabricating gas diffusion layer: well-controllable pore morphology and structure,more » rapid prototyping, fast manufacturing, highly customizing and economic. In addition, by taking advantage of additive manufacturing, it possible to fabricate complicated three-dimensional designs of virtually any shape from a digital model into one single solid object faster, cheaper and easier, especially for titanium. More importantly, this development will provide LGDLs with control of pore size, pore shape, pore distribution, and therefore porosity and permeability, which will be very valuable to develop modeling and to validate simulations of electrolyzers with optimal and repeatable performance. Further, it will lead to a manufacturing solution to greatly simplify the PEMEC/fuel cell components and to couple the LGDLs with other parts, since they can be easily integrated together with this advanced manufacturing process« less

Numerical modeling of a long-term in situ chemical osmosis experiment in the Pierre Shale, South Dakota

USGS Publications Warehouse

Garavito, A.M.; Kooi, H.; Neuzil, C.E.

2006-01-01

We have numerically modeled evolving fluid pressures and concentrations from a nine-year in situ osmosis experiment in the Pierre Shale, South Dakota. These data were obtained and recently interpreted by one of us (C.E.N.) as indicating a potentially significant role for chemical osmosis in media like the Pierre Shale. That analysis considered only the final pressure differentials among boreholes that were assumed to represent osmotic equilibrium. For this study, the system evolution was modeled using a recently developed transient model for membrane transport. The model simulates hydraulically and chemically driven fluid and solute transport. The results yield an estimate of the thickness of the water film between the clay platelets b of 40 A??, which corresponds to an osmotic efficiency ?? of 0.21 for the ambient pore water salinity of 3.5 g/l TDS. These values largely confirm the results of the earlier equilibrium analysis. However, the new model analysis provides additional constraints suggesting that intrinsic permeability k = 1.4 ?? 10-19 m2, specific storage Ss = 1.7 ?? 10-5 m-1, and diffusion coefficient D* = 6 ?? 10-11 m2/s. The k value is larger than certain independent estimates which range from 10-21 to 10-20; it may indicate opening of microcracks during the experiments. The fact that the complex transient pressure and concentration behavior for the individual wells could be reproduced quite accurately, and the inferred parameter values appear to be realistic for the Pierre Shale, suggests that the new model is a useful tool for modeling transient coupled flows in groundwater systems. ?? 2005 Elsevier Ltd. All rights reserved.

Interface test series: An in situ study of factors affecting the containment of hydraulic fractures

NASA Astrophysics Data System (ADS)

Warpinski, N. R.; Finley, S. J.; Vollendorf, W. C.; Obrien, M.; Eshom, E.

1982-02-01

In situ experiments, which are accessible for direct observation by mineback, were conducted to determine the effect that material-property interfaces and in situ stress differences have on hydraulic fracture propagation and the resultant overall geometry. These experiments show conclusively that a difference in elastic modulus at a geologic interface has little or no effect on crack growth and, therefore, is not a feature which would promote containment of fractures within a specified reservoir zone. However, differences in the in situ stress between adjacent layers is shown to have a considerable influence on fracture propagation. Experiments were conducted in a low modulus ash-fall tuff which contained two layers of high minimum principal in situ stress and which was overlain by a formation with at least a factor of 5 increase in elastic modulus. Fractures were observed to terminate in regions of high minimum principal in situ stress in nearly every case.

In Situ Remediation of Polychlorinated Bephenyls Using Palladium Coated Iron or Magnesium

NASA Technical Reports Server (NTRS)

Geiger, Cherie L.

2003-01-01

The remediation of polychlorinated biphenyls (PCBs) and other chlorinated synthetic aromatic compounds are of great concern due to their toxicity and persistence in the environment. When released into the environment, PCBs are sorbed to particulate matter that can then disperse over large areas. Although the US Environmental Protection Agency (EPA) has banned the manufacture of PCBs since 1979, they are still present in the environment posing possible adverse health affects to both humans and animals. Thus, it is of utmost importance to develop a method that remediates PCB-contaminated soil, sediments, and water. The objective of our research was to develop an in-situ PCB remediation technique that is applicable for the treatment of soils and sediments. Previous research conducted at the University of Central Florida (UCF) proved the feasibility of using an emulsified system to dehalogenate a dense non-aqueous phase liquid (DNAPL) source, such as TCE, in the subsurface by means of an in-situ injection. The generation of a hydrophobic emulsion system drew the DNAPL TCE, through the oil membrane where it diffused to the iron particle and underwent degradation. TCE continued to enter, diffuse, degrade and exit the droplet maintaining a concentration gradient across the membrane, thus maintaining the driving force of the reaction.

Nanocrystalline SiC and Ti 3SiC 2 Alloys for Reactor Materials: Diffusion of Fission Product Surrogates

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

Henager, Charles H.; Jiang, Weilin

2014-11-01

MAX phases, such as titanium silicon carbide (Ti 3SiC 2), have a unique combination of both metallic and ceramic properties, which make them attractive for potential nuclear applications. Ti 3SiC 2 has been suggested in the literature as a possible fuel cladding material. Prior to the application, it is necessary to investigate diffusivities of fission products in the ternary compound at elevated temperatures. This study attempts to obtain relevant data and make an initial assessment for Ti 3SiC 2. Ion implantation was used to introduce fission product surrogates (Ag and Cs) and a noble metal (Au) in Ti 3SiC 2,more » SiC, and a dual-phase nanocomposite of Ti 3SiC 2/SiC synthesized at PNNL. Thermal annealing and in-situ Rutherford backscattering spectrometry (RBS) were employed to study the diffusivity of the various implanted species in the materials. In-situ RBS study of Ti 3SiC 2 implanted with Au ions at various temperatures was also performed. The experimental results indicate that the implanted Ag in SiC is immobile up to the highest temperature (1273 K) applied in this study; in contrast, significant out-diffusion of both Ag and Au in MAX phase Ti 3SiC 2 occurs during ion implantation at 873 K. Cs in Ti 3SiC 2 is found to diffuse during post-irradiation annealing at 973 K, and noticeable Cs release from the sample is observed. This study may suggest caution in using Ti 3SiC 2 as a fuel cladding material for advanced nuclear reactors operating at very high temperatures. Further studies of the related materials are recommended.« 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

Novel thin/tunable gas diffusion electrodes with ultra-low catalyst loading for hydrogen evolution reactions in proton exchange membrane electrolyzer cells

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

Kang, Zhenye; Yang, Gaoqiang; Mo, Jingke

2018-05-01

Proton exchange membrane electrolyzer cells (PEMECs) have received great attention for hydrogen/oxygen production due to their high efficiencies even at low-temperature operation. Because of the high cost of noble platinum-group metal (PGM) catalysts (Ir, Ru, Pt, etc.) that are widely used in water splitting, a PEMEC with low catalyst loadings and high catalyst utilizations is strongly desired for its wide commercialization. In this study, the ultrafast and multiscale hydrogen evolution reaction (HER) phenomena in an operating PEMEC is in-situ observed for the first time. The visualization results reveal that the HER and hydrogen bubble nucleation mainly occur on catalyst layersmore » at the rim of the pores of the thin/tunable liquid/gas diffusion layers (TT-LGDLs). This indicates that the catalyst material of the conventional catalyst-coated membrane (CCM) that is located in the middle area of the LGDL pore is underutilized/inactive. Based on this discovery, a novel thin and tunable gas diffusion electrode (GDE) with a Pt catalyst thickness of 15 nm and a total thickness of about 25 um has been proposed and developed by taking advantage of advanced micro/nano manufacturing. The novel thin GDEs are comprehensively characterized both ex-situ and in-situ, and exhibit excellent PEMEC performance. More importantly, they achieve catalyst mass activity of up to 58 times higher than conventional CCM at 1.6 V under the operating conditions of 80 degrees C and 1 atm. This study demonstrates a promising concept for PEMEC electrode development, and provides a direction of future catalyst designs and fabrications for electrochemical devices.« less

Novel thin/tunable gas diffusion electrodes with ultra-low catalyst loading for hydrogen evolution reactions in proton exchange membrane electrolyzer cells

DOE PAGES

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

2018-03-09

Proton exchange membrane electrolyzer cells (PEMECs) have received great attention for hydrogen/oxygen production due to their high efficiencies even at low-temperature operation. Because of the high cost of noble platinum-group metal (PGM) catalysts (Ir, Ru, Pt, etc.) that are widely used in water splitting, a PEMEC with low catalyst loadings and high catalyst utilizations is strongly desired for its wide commercialization. In this study, the ultrafast and multiscale hydrogen evolution reaction (HER) phenomena in an operating PEMEC is in-situ observed for the first time. The visualization results reveal that the HER and hydrogen bubble nucleation mainly occur on catalyst layersmore » at the rim of the pores of the thin/tunable liquid/gas diffusion layers (TT-LGDLs). This indicates that the catalyst material of the conventional catalyst-coated membrane (CCM) that is located in the middle area of the LGDL pore is underutilized/inactive. Based on this discovery, a novel thin and tunable gas diffusion electrode (GDE) with a Pt catalyst thickness of 15 nm and a total thickness of about 25 um has been proposed and developed by taking advantage of advanced micro/nano manufacturing. The novel thin GDEs are comprehensively characterized both ex-situ and in-situ, and exhibit excellent PEMEC performance. More importantly, they achieve catalyst mass activity of up to 58 times higher than conventional CCM at 1.6 V under the operating conditions of 80 degrees C and 1 atm. This study demonstrates a promising concept for PEMEC electrode development, and provides a direction of future catalyst designs and fabrications for electrochemical devices.« less

Novel thin/tunable gas diffusion electrodes with ultra-low catalyst loading for hydrogen evolution reactions in proton exchange membrane electrolyzer cells

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

Kang, Zhenye; Yang, Gaoqiang; Mo, Jingke

Proton exchange membrane electrolyzer cells (PEMECs) have received great attention for hydrogen/oxygen production due to their high efficiencies even at low-temperature operation. Because of the high cost of noble platinum-group metal (PGM) catalysts (Ir, Ru, Pt, etc.) that are widely used in water splitting, a PEMEC with low catalyst loadings and high catalyst utilizations is strongly desired for its wide commercialization. In this study, the ultrafast and multiscale hydrogen evolution reaction (HER) phenomena in an operating PEMEC is in-situ observed for the first time. The visualization results reveal that the HER and hydrogen bubble nucleation mainly occur on catalyst layersmore » at the rim of the pores of the thin/tunable liquid/gas diffusion layers (TT-LGDLs). This indicates that the catalyst material of the conventional catalyst-coated membrane (CCM) that is located in the middle area of the LGDL pore is underutilized/inactive. Based on this discovery, a novel thin and tunable gas diffusion electrode (GDE) with a Pt catalyst thickness of 15 nm and a total thickness of about 25 um has been proposed and developed by taking advantage of advanced micro/nano manufacturing. The novel thin GDEs are comprehensively characterized both ex-situ and in-situ, and exhibit excellent PEMEC performance. More importantly, they achieve catalyst mass activity of up to 58 times higher than conventional CCM at 1.6 V under the operating conditions of 80 degrees C and 1 atm. This study demonstrates a promising concept for PEMEC electrode development, and provides a direction of future catalyst designs and fabrications for electrochemical devices.« less

Modelling the diffusion-available pore space of an unaltered granitic rock matrix using a micro-DFN approach

NASA Astrophysics Data System (ADS)

Svensson, Urban; Löfgren, Martin; Trinchero, Paolo; Selroos, Jan-Olof

2018-04-01

In sparsely fractured rock, the ubiquitous heterogeneity of the matrix, which has been observed in different laboratory and in situ experiments, has been shown to have a significant influence on retardation mechanisms that are of importance for the safety of deep geological repositories for nuclear waste. Here, we propose a conceptualisation of a typical heterogeneous granitic rock matrix based on micro-Discrete Fracture Networks (micro-DFN). Different sets of fractures are used to represent grain-boundary pores as well as micro fractures that transect different mineral grains. The micro-DFN model offers a great flexibility in the way inter- and intra-granular space is represented as the different parameters that characterise each fracture set can be fine tuned to represent samples of different characteristics. Here, the parameters of the model have been calibrated against experimental observations from granitic rock samples taken at Forsmark (Sweden) and different variant cases have been used to illustrate how the model can be tied to rock samples with different attributes. Numerical through-diffusion simulations have been carried out to infer the bulk properties of the model as well as to compare the computed mass flux with the experimental data from an analogous laboratory experiment. The general good agreement between the model results and the experimental observations shows that the model presented here is a reliable tool for the understanding of retardation mechanisms occurring at the mm-scale in the matrix.

Diffusion tensor optical coherence tomography

NASA Astrophysics Data System (ADS)

Marks, Daniel L.; Blackmon, Richard L.; Oldenburg, Amy L.

2018-01-01

In situ measurements of diffusive particle transport provide insight into tissue architecture, drug delivery, and cellular function. Analogous to diffusion-tensor magnetic resonance imaging (DT-MRI), where the anisotropic diffusion of water molecules is mapped on the millimeter scale to elucidate the fibrous structure of tissue, here we propose diffusion-tensor optical coherence tomography (DT-OCT) for measuring directional diffusivity and flow of optically scattering particles within tissue. Because DT-OCT is sensitive to the sub-resolution motion of Brownian particles as they are constrained by tissue macromolecules, it has the potential to quantify nanoporous anisotropic tissue structure at micrometer resolution as relevant to extracellular matrices, neurons, and capillaries. Here we derive the principles of DT-OCT, relating the detected optical signal from a minimum of six probe beams with the six unique diffusion tensor and three flow vector components. The optimal geometry of the probe beams is determined given a finite numerical aperture, and a high-speed hardware implementation is proposed. Finally, Monte Carlo simulations are employed to assess the ability of the proposed DT-OCT system to quantify anisotropic diffusion of nanoparticles in a collagen matrix, an extracellular constituent that is known to become highly aligned during tumor development.

The melting curve of Ni to 1 Mbar

NASA Astrophysics Data System (ADS)

Lord, Oliver T.; Wood, Ian G.; Dobson, David P.; Vočadlo, Lidunka; Wang, Weiwei; Thomson, Andrew R.; Wann, Elizabeth T. H.; Morard, Guillaume; Mezouar, Mohamed; Walter, Michael J.

2014-12-01

The melting curve of Ni has been determined to 125 GPa using laser-heated diamond anvil cell (LH-DAC) experiments in which two melting criteria were used: firstly, the appearance of liquid diffuse scattering (LDS) during in situ X-ray diffraction (XRD) and secondly, plateaux in temperature vs. laser power functions in both in situ and off-line experiments. Our new melting curve, defined by a Simon-Glatzel fit to the data where TM (K) = [ (PM/18.78 ± 10.20 + 1) ]1/2.42 ± 0.66 × 1726, is in good agreement with the majority of the theoretical studies on Ni melting and matches closely the available shock wave melting data. It is however dramatically steeper than the previous off-line LH-DAC studies in which determination of melting was based on the visual observation of motion aided by the laser speckle method. We estimate the melting point (TM) of Ni at the inner-core boundary (ICB) pressure of 330 GPa to be TM = 5800 ± 700 K (2 σ), within error of the value for Fe of TM = 6230 ± 500 K determined in a recent in situ LH-DAC study by similar methods to those employed here. This similarity suggests that the alloying of 5-10 wt.% Ni with the Fe-rich core alloy is unlikely to have any significant effect on the temperature of the ICB, though this is dependent on the details of the topology of the Fe-Ni binary phase diagram at core pressures. Our melting temperature for Ni at 330 GPa is ∼2500 K higher than that found in previous experimental studies employing the laser speckle method. We find that those earlier melting curves coincide with the onset of rapid sub-solidus recrystallization, suggesting that visual observations of motion may have misinterpreted dynamic recrystallization as convective motion of a melt. This finding has significant implications for our understanding of the high-pressure melting behaviour of a number of other transition metals.

Clonal reticulohistiocytosis of the skin and bone marrow associated with systemic mastocytosis and acute myeloid leukaemia.

PubMed

Fusco, Nicola; Bonometti, Arturo; Augello, Claudia; Fabris, Sonia; Boiocchi, Leonardo; Fiori, Stefano; Morotti, Denise; Fracchiolla, Nicola; Berti, Emilio; Gianelli, Umberto

2017-05-01

The aims of this study were to define whether diffuse cutaneous reticulohistiocytosis could be underpinned by somatic genetic alterations and represent a precursor of more aggressive forms of disease. A 59-year-old man with diffuse cutaneous reticulohistiocytosis experienced bone marrow localization of the disease, with associated systemic mastocytosis and acute myeloid leukaemia. Cytogenetic analyses of the bone marrow aspirate revealed the presence of a derivative chromosome giving rise to a partial trisomy of chromosome 1q and a partial monosomy of chromosome 9q. Therefore, we characterized the cutaneous lesions before and after chemotherapy by using an integrative approach combining histopathology, electron microscopy, and fluorescence in-situ hybridization. Histologically, the skin lesions belonged to the spectrum of diffuse cutaneous reticulohistiocytoses, as confirmed by immunohistochemistry and ultrastructural analyses. Fluorescence in-situ hybridization in the skin nodules confirmed the presence of the genetic alterations previously detected in the bone marrow. Here, we provide circumstantial evidence to suggest that at least a subset of cutaneous reticulohistiocytoses harbour clonal molecular alterations. Furthermore, we confirm that these lesions have the potential to arise in the setting of concurrent haematological disorders. In this hypothesis-generating study, two possible tumorigenesis models are proposed. © 2017 John Wiley & Sons Ltd.

Comparison of conventional and internally cured concrete bridge decks in Utah : Mountain View corridor project.

DOT National Transportation Integrated Search

2014-12-01

The objectives of this research were to 1) monitor in-situ moisture and diffusivity for both conventional concrete : and concrete containing pre-wetted lightweight fine aggregate (LWFA), 2) compare deck performance in terms of : early-age cracking, c...

Isotope fractionation by multicomponent diffusion (Invited)

NASA Astrophysics Data System (ADS)

Watkins, J. M.; Liang, Y.; Richter, F. M.; Ryerson, F. J.; DePaolo, D. J.

2013-12-01

Isotope fractionation by multicomponent diffusion The isotopic composition of mineral phases can be used to probe the temperatures and rates of mineral formation as well as the degree of post-mineralization alteration. The ability to interpret stable isotope variations is limited by our knowledge of three key parameters and their relative importance in determining the composition of a mineral grain and its surroundings: (1) thermodynamic (equilibrium) partitioning, (2) mass-dependent diffusivities, and (3) mass-dependent reaction rate coefficients. Understanding the mechanisms of diffusion and reaction in geological liquids, and how these mass transport processes discriminate between isotopes, represents an important problem that is receiving considerable attention in the geosciences. Our focus in this presentation will be isotope fractionation by chemical diffusion. Previous studies have documented that diffusive isotope effects vary depending on the cation as well as the liquid composition, but the ability to predict diffusive isotope effects from theory is limited; for example, it is unclear whether the magnitude of diffusive isotopic fractionations might also vary with the direction of diffusion in composition space. To test this hypothesis and to further guide the theoretical treatment of isotope diffusion, two chemical diffusion experiments and one self diffusion experiment were conducted at 1250°C and 0.7 GPa. In one experiment (A-B), CaO and Na2O counter-diffuse rapidly in the presence of a small SiO2 gradient. In the other experiment (D-E), CaO and SiO2 counter-diffuse more slowly in a small Na2O gradient. In both chemical diffusion experiments, Ca isotopes become fractionated by chemical diffusion but by different amounts, documenting for the first time that the magnitude of isotope fractionation by diffusion depends on the direction of diffusion in composition space. The magnitude of Ca isotope fractionation that develops is positively correlated with the rate of CaO diffusion; in A-B, the total variation is 2.5‰ whereas in D-E it is only 1.3‰. The diffusion of isotopes in a multicomponent system is modeled using a new expression for the isotope-specific diffusive flux that includes self diffusion terms in addition to the multicomponent chemical diffusion matrix. Kinetic theory predicts a mass dependence on isotopic mobility, i.e., self diffusivity, but it is unknown whether or how the mass dependence on self diffusivity translates into a mass dependence on chemical diffusion coefficients. The new experimental results allow us to assess several empirical expressions relating the self diffusivity and its mass dependence to the elements of the diffusion matrix and their mass dependence. Several plausible theoretical treatments can fit the data equally well. We are currently at the stage where experiments are guiding the theoretical treatment of the isotope fractionation by diffusion problem, underscoring the importance of experiments for aiding interpretations of isotopic variations in nature.

Quantitative apparent diffusion coefficient as a noninvasive imaging biomarker for the differentiation of invasive breast cancer and ductal carcinoma in situ.

PubMed

Bickel, Hubert; Pinker-Domenig, Katja; Bogner, Wolfgang; Spick, Claudio; Bagó-Horváth, Zsuzsanna; Weber, Michael; Helbich, Thomas; Baltzer, Pascal

2015-02-01

The objective of this study was to evaluate whether apparent diffusion coefficient (ADC) obtained through diffusion-weighted imaging magnetic resonance imaging at 3 T can be used as an imaging biomarker to differentiate invasive breast cancer from noninvasive ductal carcinoma in situ (DCIS). One hundred seventy-six histopathologically verified primary malignant breast tumors were retrospectively evaluated in 170 patients. All patients had undergone a standardized 3-T magnetic resonance imaging protocol, containing a diffusion-weighted sequence with 2 b values and a series of dynamic contrast-enhanced T1-weighted sequences. Apparent diffusion coefficient was measured manually by a reader blinded to the histopathological results. The ADC values were correlated with histopathological results. Mean ADC values were compared between invasive cancers and DCIS as well as between different tumor grades. Receiver operating characteristics curves were used to calculate diagnostic performance. There were 155 invasive cancers and 21 noninvasive DCIS. Mean (SD) values differed significantly between the invasive cancers (0.9 [0.15] ×10 mm/s) and the DCIS (1.24 [0.23] ×10 mm/s, P < 0.001). Area under the receiver operating characteristics curve was 0.895 (95% confidence interval [CI], 0.840-0.936). A threshold of 1.01 ×10 mm/s or less allowed an identification of invasive cancers with a sensitivity of 78.06% (95% CI, 70.7%-84.3%) and a specificity of 90.5% (95% CI, 69.6%-98.8%). No significant ADC differences were found among different tumor grades (P > 0.05). Apparent diffusion coefficient could be used as an imaging biomarker for the diagnosis of breast cancer. It seems to be a valuable noninvasive quantitative biomarker to assess breast cancer invasiveness. Thus, ADC measurements provide the potential to reduce overdiagnosis and subsequent overtreatment.

Surface faceting and elemental diffusion behaviour at atomic scale for alloy nanoparticles during in situ annealing

PubMed Central

Chi, Miaofang; Wang, Chao; Lei, Yinkai; Wang, Guofeng; Li, Dongguo; More, Karren L.; Lupini, Andrew; Allard, Lawrence F.; Markovic, Nenad M.; Stamenkovic, Vojislav R.

2015-01-01

The catalytic performance of nanoparticles is primarily determined by the precise nature of the surface and near-surface atomic configurations, which can be tailored by post-synthesis annealing effectively and straightforwardly. Understanding the complete dynamic response of surface structure and chemistry to thermal treatments at the atomic scale is imperative for the rational design of catalyst nanoparticles. Here, by tracking the same individual Pt3Co nanoparticles during in situ annealing in a scanning transmission electron microscope, we directly discern five distinct stages of surface elemental rearrangements in Pt3Co nanoparticles at the atomic scale: initial random (alloy) elemental distribution; surface platinum-skin-layer formation; nucleation of structurally ordered domains; ordered framework development and, finally, initiation of amorphization. Furthermore, a comprehensive interplay among phase evolution, surface faceting and elemental inter-diffusion is revealed, and supported by atomistic simulations. This work may pave the way towards designing catalysts through post-synthesis annealing for optimized catalytic performance. PMID:26576477

Surface faceting and elemental diffusion behaviour at atomic scale for alloy nanoparticles during in situ annealing

DOE PAGES

Chi, Miaofang; Wang, Chao; Lei, Yinkai; ...

2015-11-18

The catalytic performance of nanoparticles is primarily determined by the precise nature of the surface and near-surface atomic configurations, which can be tailored by post-synthesis annealing effectively and straightforwardly. Understanding the complete dynamic response of surface structure and chemistry to thermal treatments at the atomic scale is imperative for the rational design of catalyst nanoparticles. Here, by tracking the same individual Pt 3Co nanoparticles during in situ annealing in a scanning transmission electron microscope, we directly discern five distinct stages of surface elemental rearrangements in Pt 3Co nanoparticles at the atomic scale: initial random (alloy) elemental distribution; surface platinum-skin-layer formation;more » nucleation of structurally ordered domains; ordered framework development and, finally, initiation of amorphization. Furthermore, a comprehensive interplay among phase evolution, surface faceting and elemental inter-diffusion is revealed, and supported by atomistic simulations. In conlcusion, this work may pave the way towards designing catalysts through post-synthesis annealing for optimized catalytic performance.« less

Tunneling-Magnetoresistance Ratio Comparison of MgO-Based Perpendicular-Magnetic-Tunneling-Junction Spin Valve Between Top and Bottom Co2Fe6B2 Free Layer Structure.

PubMed

Lee, Du-Yeong; Lee, Seung-Eun; Shim, Tae-Hun; Park, Jea-Gun

2016-12-01

For the perpendicular-magnetic-tunneling-junction (p-MTJ) spin valve with a nanoscale-thick bottom Co2Fe6B2 free layer ex situ annealed at 400 °C, which has been used as a common p-MTJ structure, the Pt atoms of the Pt buffer layer diffused into the MgO tunneling barrier. This transformed the MgO tunneling barrier from a body-centered cubic (b.c.c) crystallized layer into a mixture of b.c.c, face-centered cubic, and amorphous layers and rapidly decreased the tunneling-magnetoresistance (TMR) ratio. The p-MTJ spin valve with a nanoscale-thick top Co2Fe6B2 free layer could prevent the Pt atoms diffusing into the MgO tunneling barrier during ex situ annealing at 400 °C because of non-necessity of a Pt buffer layer, demonstrating the TMR ratio of ~143 %.

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

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.

MMS Encounters with Reconnection Diffusion Regions in the Earth's Magnetotail

NASA Astrophysics Data System (ADS)

Torbert, R. B.; Burch, J. L.; Argall, M. R.; Farrugia, C. J.; Alm, L.; Dors, I.; Payne, D.; Rogers, A. J.; Strangeway, R. J.; Phan, T.; Ergun, R.; Goodrich, K.; Lindqvist, P. A.; Khotyaintsev, Y. V.; Giles, B. L.; Rager, A. C.; Gershman, D. J.; Kletzing, C.

2017-12-01

The Magnetospheric Multiscale (MMS) fleet of four spacecraft traversed the Earth's magnetotail in May through August of 2017 with an apogee of 25 Re, and encountered diffusion regions characteristic of symmetric reconnection. This presentation will describe in-situ measurements of large electric fields, strong electron cross-tail and Hall currents, and electron velocity distributions (frequently crescent-shaped) that are commonly observed in these regions. Positive electromagnetic energy conversion is also typical. The characteristics of symmetric reconnection observations will be contrasted with those of asymmetric reconnection that MMS observed previously at the dayside magnetopause.

Observations of Ion Diffusion Regions in the Geomagnetic Tail

NASA Astrophysics Data System (ADS)

Rogers, A. J.; Farrugia, C. J.; Torbert, R. B.; Argall, M. R.; Strangeway, R. J.; Ergun, R.

2017-12-01

We present analysis of two Ion Diffusion Regions (IDRs) in the geomagnetic tail, as observed by the Magnetospheric Multiscale Mission (MMS). Analysis of each event is centered around discussion of parameters commonly associated with IDRs such as enhanced electric field magnitude, guiding center expansion parameter, and ion velocity. Characteristic values for these parameters are determined, as well as other common attributes of IDRs, and used to develop a searching algorithm to automate identification of possible IDRs for closer inspection. Preliminary results of applying this algorithm to in situ MMS observations are also presented

Fragmentation, rings and coarsening: structure and transformations of nanocrystal aggregate networks on a liquid surface

NASA Astrophysics Data System (ADS)

Yang, Bo; Scheidtmann, Jens; Mayer, Joachim; Wuttig, Matthias; Michely, Thomas

2002-01-01

Deposition of Ag on a silicon oil surface leads to the formation of nm-sized Ag crystals floating on the oil surface. These nanocrystals mutually attract each other, forming strongly branched nanocrystal aggregates and continuous aggregate networks. Transformation processes of such nanocrystal aggregate networks are imaged in situ by optical microscopy. The observations are explained on the basis of a simple model involving diffusion of nanocrystals along aggregate edges and the rupture of branches resulting from branch width fluctuations due to edge diffusion.

Student-Led Presentations "in Situ": The Challenges to Presenting on the Edge of a Volcano

ERIC Educational Resources Information Center

Marvell, Alan

2008-01-01

Student-led seminars are commonplace within higher education but few are allowed the opportunity of being delivered in situ. Presentations in situ widen the experience of students and develop a range of transferable skills, encouraging a greater sense of place and facilitating reflective learning. This case study describes the experiences of a…

Hydrodynamically induced fluid transfer and non-convective double-diffusion in microgravity sliding solvent diffusion cells

NASA Technical Reports Server (NTRS)

Pollmann, Konrad W.; Stodieck, Louis S.; Luttges, Marvin W.

1994-01-01

Microgravity can provide a diffusion-dominated environment for double-diffusion and diffusion-reaction experiments otherwise disrupted by buoyant convection or sedimentation. In sliding solvent diffusion cells, a diffusion interface between two liquid columns is achieved by aligning two offset sliding wells. Fluid in contact with the sliding lid of the cavities is subjected to an applied shear stress. The momentum change by the start/stop action of the well creates an additional hydrodynamical force. In microgravity, these viscous and inertial forces are sufficiently large to deform the diffusion interface and induce hydrodynamic transfer between the wells. A series of KC-135 parabolic flight experiments were conducted to characterize these effects and establish baseline data for microgravity diffusion experiments. Flow visualizations show the diffusion interface to be deformed in a sinusoidal fashion following well alignment. After the wells were separated again in a second sliding movement, the total induced liquid transfer was determined and normalized by the well aspect ratio. The normalized transfer decreased linearly with Reynolds number from 3.3 to 4.0% (w/v) for Re = 0.4 (Stokes flow) to a minimum of 1.0% for Re = 23 to 30. Reynolds numbers that provide minimum induced transfers are characterized by an interface that is highly deformed and unsuitable for diffusion measurements. Flat diffusion interfaces acceptable for diffusion measurements are obtained with Reynolds numbers on the order of 7 to 10. Microgravity experiments aboard a sounding rocket flight verified counterdiffusion of different solutes to be diffusion dominated. Ground control experiments showed enhanced mixing by double-diffusive convection. Careful selection of experimental parameters improves initial conditions and minimizes induced transfer rates.

Effects of molecular weight on the diffusion coefficient of aquatic dissolved organic matter and humic substances.

PubMed

Balch, J; Guéguen, C

2015-01-01

In situ measurements of labile metal species using diffusive gradients in thin films (DGT) passive samplers are based on the diffusion rates of individual species. Although most studies have dealt with chemically isolated humic substances, the diffusion of dissolved organic matter (DOM) across the hydrogel is not well understood. In this study, the diffusion coefficient (D) and molecular weight (MW) of 11 aquatic DOM and 4 humic substances (HS) were determined. Natural, unaltered aquatic DOM was capable of diffusing across the diffusive gel membrane with D values ranging from 2.48×10(-6) to 5.31×10(-6) cm(2) s(-1). Humic substances had diffusion coefficient values ranging from 3.48×10(-6) to 6.05×10(-6) cm(2) s(-1), congruent with previous studies. Molecular weight of aquatic DOM and HS samples (∼500-1750 Da) measured using asymmetrical flow field-flow fractionation (AF4) strongly influenced D, with larger molecular weight DOM having lower D values. No noticeable changes in DOM size properties were observed during the diffusion process, suggesting that DOM remains intact following diffusion across the diffusive gel. The influence of molecular weight on DOM mobility will assist in further understanding and development of the DGT technique and the uptake and mobility of contaminants associated with DOM in aquatic environments. Copyright © 2014 Elsevier Ltd. All rights reserved.

Enhanced functional connectivity properties of human brains during in-situ nature experience

PubMed Central

2016-01-01

In this study, we investigated the impacts of in-situ nature and urban exposure on human brain activities and their dynamics. We randomly assigned 32 healthy right-handed college students (mean age = 20.6 years, SD = 1.6; 16 males) to a 20 min in-situ sitting exposure in either a nature (n = 16) or urban environment (n = 16) and measured their Electroencephalography (EEG) signals. Analyses revealed that a brief in-situ restorative nature experience may induce more efficient and stronger brain connectivity with enhanced small-world properties compared with a stressful urban experience. The enhanced small-world properties were found to be correlated with “coherent” experience measured by Perceived Restorativeness Scale (PRS). Exposure to nature also induces stronger long-term correlated activity across different brain regions with a right lateralization. These findings may advance our understanding of the functional activities during in-situ environmental exposures and imply that a nature or nature-like environment may potentially benefit cognitive processes and mental well-being. PMID:27547533

Permeability, storage and hydraulic diffusivity controlled by earthquakes

NASA Astrophysics Data System (ADS)

Brodsky, E. E.; Fulton, P. M.; Xue, L.

2016-12-01

Earthquakes can increase permeability in fractured rocks. In the farfield, such permeability increases are attributed to seismic waves and can last for months after the initial earthquake. Laboratory studies suggest that unclogging of fractures by the transient flow driven by seismic waves is a viable mechanism. These dynamic permeability increases may contribute to permeability enhancement in the seismic clouds accompanying hydraulic fracking. Permeability enhancement by seismic waves could potentially be engineered and the experiments suggest the process will be most effective at a preferred frequency. We have recently observed similar processes inside active fault zones after major earthquakes. A borehole observatory in the fault that generated the M9.0 2011 Tohoku earthquake reveals a sequence of temperature pulses during the secondary aftershock sequence of an M7.3 aftershock. The pulses are attributed to fluid advection by a flow through a zone of transiently increased permeability. Directly after the M7.3 earthquake, the newly damaged fault zone is highly susceptible to further permeability enhancement, but ultimately heals within a month and becomes no longer as sensitive. The observation suggests that the newly damaged fault zone is more prone to fluid pulsing than would be expected based on the long-term permeability structure. Even longer term healing is seen inside the fault zone of the 2008 M7.9 Wenchuan earthquake. The competition between damage and healing (or clogging and unclogging) results in dynamically controlled permeability, storage and hydraulic diffusivity. Recent measurements of in situ fault zone architecture at the 1-10 meter scale suggest that active fault zones often have hydraulic diffusivities near 10-2 m2/s. This uniformity is true even within the damage zone of the San Andreas fault where permeability and storage increases balance each other to achieve this value of diffusivity over a 400 m wide region. We speculate that fault zones may evolve to a preferred diffusivity in a dynamic equilibrium.

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.

Diffusional limits to the consumption of atmospheric methane by soils

USGS Publications Warehouse

Striegl, Robert G.

1993-01-01

Net transport of atmospheric gases into and out of soil systems is primarily controlled by diffusion along gas partial pressure gradients. Gas fluxes between soil and the atmosphere can therefore be estimated by a generalization of the equation for ordinary gaseous diffusion in porous unsaturated media. Consumption of CH4 by methylotrophic bacteria in the top several centimeters of soil causes the uptake of atmospheric CH4 by aerated soils. The capacity of the methylotrophs to consume CH4 commonly exceeds the potential of CH4 to diffuse from the atmosphere to the consumers. The maximum rate of uptake of atmospheric CH4 by soil is, therefore, limited by diffusion and can be calculated from soil physical properties and the CH4 concentration gradient. The CH4 concentration versus depth profile is theoretically described by the equation for gaseous diffusion with homogeneous chemical reaction in porous unsaturated media. This allows for calculation of the in situ rate of CH4 consumption within specified depth intervals.

Multicomponent diffusion in basaltic melts at 1350 °C

NASA Astrophysics Data System (ADS)

Guo, Chenghuan; Zhang, Youxue

2018-05-01

Nine successful diffusion couple experiments were conducted in an 8-component SiO2-TiO2-Al2O3-FeO-MgO-CaO-Na2O-K2O system at ∼1350 °C and at 1 GPa, to study multicomponent diffusion in basaltic melts. At least 3 traverses were measured to obtain diffusion profiles for each experiment. Multicomponent diffusion matrix at 1350 °C was obtained by simultaneously fitting diffusion profiles of diffusion couple experiments. Furthermore, in order to better constrain the diffusion matrix and reconcile mineral dissolution data, mineral dissolution experiments in the literature and diffusion couple experiments from this study, were fit together. All features of diffusion profiles in both diffusion couple and mineral dissolution experiments were well reproduced by the diffusion matrix. Diffusion mechanism is inferred from eigenvectors of the diffusion matrix, and it shows that the diffusive exchange between network-formers SiO2 and Al2O3 is the slowest, the exchange of SiO2 with other oxide components is the second slowest with an eigenvalue that is only ∼10% larger, then the exchange between divalent oxide components and all the other oxide components is the third slowest with an eigenvalue that is twice the smallest eigenvalue, then the exchange of FeO + K2O with all the other oxide components is the fourth slowest with an eigenvalue that is 5 times the smallest eigenvalue, then the exchange of MgO with FeO + CaO is the third fastest with an eigenvalue that is 6.3 times the smallest eigenvalue, then the exchange of CaO + K2O with all the other oxide components is the second fastest with an eigenvalue that is 7.5 times the smallest eigenvalue, and the exchange of Na2O with all other oxide components is the fastest with an eigenvalue that is 31 times the smallest eigenvalue. The slowest and fastest eigenvectors are consistent with those for simpler systems in most literature. The obtained diffusion matrix was successfully applied to predict diffusion profiles during mineral dissolution in basaltic melts.

Understanding catalyst behavior during in situ heating through simultaneous secondary and transmitted electron imaging

DOE PAGES

Howe, Jane Y.; Allard, Jr., Lawrence Frederick; Demers, Hendrix; ...

2014-11-14

In situ heating study via a simultaneous secondary electron (SE) and transmitted electron (TE) microscopy is extremely insightful because information from the surface (SE) and bulk (TE) can be readily obtained. The leached Au/Fe 2O 3 catalyst has voids on the surface of Fe 2O 3. Upon heating to 500 °C, voids shrank and disappeared, while internal Au species diffused to the surface to form new nanoparticles. Heating in vacuum reduced Fe 2O 3 to Fe 3O 4. Heating at 700 °C caused coalescence and growth of Au particles and formation of faceted Fe 3O 4 surfaces. We achieved 1.1more » nm resolution in SE imaging during in situ heating.« less

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

Improvement of laser molecular beam epitaxy grown SrTiO3 thin film properties by temperature gradient modulation growth

NASA Astrophysics Data System (ADS)

Li, Jin Long; Hao, J. H.; Li, Y. R.

2007-09-01

Oxygen diffusion at the SrTiO3/Si interface was analyzed. A method called temperature gradient modulation growth was introduced to control oxygen diffusion at the interface of SrTiO3/Si. Nanoscale multilayers were grown at different temperatures at the initial growing stage of films. Continuous growth of SrTiO3 films was followed to deposit on the grown sacrificial layers. The interface and crystallinity of SrTiO3/Si were investigated by in situ reflection high energy electron diffraction and x-ray diffraction measurements. It has been shown that the modulated multilayers may help suppress the interfacial diffusion, and therefore improve SrTiO3 thin film properties.

Effect of Azospirillum brasilense and Burkholderia unamae Bacteria on Maize Photosynthetic Activity Evaluated Using the Photoacoustic Technique

NASA Astrophysics Data System (ADS)

Gordillo-Delgado, F.; Marín, E.; Calderón, A.

2016-09-01

In this work, the photosynthetic process of maize plants ( Zea mays), which were grown using seeds inoculated with plant growth promoting bacteria Azospirillum brasilense and Burkholderia unamae, was monitored. Photothermal and photobaric signals obtained by a time-resolved photoacoustic measurement configuration were used for measuring the oxygen evolution rate in situ. A frequency-resolved configuration of the method was utilized to determine the oxygen diffusion coefficient and the thermal diffusivity of the maize leaves. The latter parameters, which can be used as indicators of the photosynthetic activity of maize, are found to vary according to the plant-microbe interaction. Treatment with plant growth promoting bacteria induced a decrease in the oxygen diffusion coefficient of about 20 %.

Diffusion Study on Dissolved Hydrogen toward Effective Bioremediation of Chlorinated Ethenes in Aquitards

NASA Astrophysics Data System (ADS)

Yoshikawa, M.; Zhang, M.; Takeuchi, M.; Komai, T.

2010-12-01

In Japan, the demand for in-situ remediation of contaminated sediments is expected to increase in the future due to the recent amendment of Soil Contamination Countermeasures Act. The Japanese law requires remediating not only contaminated groundwater but also contaminated sediments including those in aquitards. In-situ remediation of contaminated aquitards has been a challenging issue and bioremediation is considered to be one of the effective techniques. In microbial degradation of chrolinated ethenes such as tetrachloroethene and trichloroethene under anaerobic environments, dissolved hydrogen plays an important role. The dechlorinating microbes utilize hydrogen and chlorinated ethenes as an electron donor and an electron accepter, respectively. The size of hydrogen molecule is extremely small and the diffusion rate of dissolved hydrogen in an aquitard would be the key factor that controls the process of microbial dechlorination. However, the diffusion behavior of dissolved hydrogen in subsurface sediments remains unclear. The purposes of this study are to develop a practically utilizable test apparatus, carry out a series of dissolved hydrogen diffusion tests on representative samples, and illustrate the applicability of bioremediation in aquitards. A completely leak-free apparatus was developed by using aluminum alloy and gas tight rubber. This apparatus is capable of testing specimens with a diameter as large as 100 mm by a length from 5 mm to 10 mm, depending on the maximum grain size within a test specimen. Preliminary tests have been performed with glass beads as an ideal material, commercially available kaolin clay, and core samples taken from a polluted site containing clay minerals. The effective diffusion coefficients of these samples were all on the order of 10E-10 m2/s, though their coefficients of permeability varied between the orders of 10E-2 and 10E-7 cm/s. These results showed that there was no obvious relationship between the effective diffusion coefficient of hydrogen and coefficient of permeability. This observation indicates that dissolved hydrogen also diffuses through hydraulically-tight soil particles and bioremediation of chlorinated ethenes in aquitards would be possible from the aspect of electron donor supply.

Shock Melting of Iron Silicide as Determined by In Situ X-ray Diffraction.

NASA Astrophysics Data System (ADS)

Newman, M.; Kraus, R. G.; Wicks, J. K.; Smith, R.; Duffy, T. S.

2016-12-01

The equation of state of core alloys at pressures and temperatures near the solid-liquid coexistence curve is important for understanding the dynamics at the inner core boundary of the Earth and super-Earths. Here, we present a series of laser driven shock experiments on textured polycrystalline Fe-15Si. These experiments were conducted at the Omega and Omega EP laser facilities. Particle velocities in the Fe-15Si samples were measured using a line VISAR and were used to infer the thermodynamic state of the shocked samples. In situ x-ray diffraction measurements were used to probe the melting transition and investigate the potential decomposition of Fe-15Si in to hcp and B2 structures. This work examines the kinetic effects of decomposition due to the short time scale of dynamic compression experiments. In addition, the thermodynamic data collected in these experiments adds to a limited body of information regarding the equation of state of Fe-15Si, which is a candidate for the composition in Earth's outer core. Our experimental results show a highly textured solid phase upon shock compression to pressures ranging from 170 to 300 GPa. Below 320 GPa, we observe diffraction peaks consistent with decomposition of the D03 starting material in to an hcp and a cubic (potentially B2) structure. Upon shock compression above 320 GPa, the intense and textured solid diffraction peaks give way to diffuse scattering and loss of texture, consistent with melting along the Hugoniot. When comparing these results to that of pure iron, we can ascertain that addition of 15 wt% silicon increases the equilibrium melting temperature significantly, or that the addition of silicon significantly increases the metastability of the solid phase, relative to the liquid. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Detection of soil microorganism in situ by combined gas chromatography mass spectrometry

NASA Technical Reports Server (NTRS)

Alexander, M.; Duxbury, J. M.; Francis, A. J.; Adamson, J.

1972-01-01

Experimental tests were made to determine whether analysis of volatile metabolic products, formed in situ, is a viable procedure for an extraterrestrial life detection system. Laboratory experiments, carried out under anaerobic conditions with addition of carbon source, extended to include a variety of soils and additional substrates. In situ experiments were conducted without amendment using a vacuum sampling system.

Coadsorbate-Induced Reversal of Solid-Liquid Interface Dynamics.

PubMed

Rahn, Björn; Wen, Rui; Deuchler, Lukas; Stremme, Johannes; Franke, Andreas; Pehlke, Eckhard; Magnussen, Olaf M

2018-05-22

Coadsorbed anions are well-known to influence surface reactivity and dynamics at solid-liquid interfaces. Here we demonstrate that the chemical nature of these spectator species can entirely determine the microscopic dynamic behavior. Quantitative in situ video-STM data on the surface diffusion of adsorbed sulfur atoms on Cu(100) electrodes in aqueous solution covered by bromide and chloride spectators, respectively, reveal in both cases a strong exponential potential dependence, but with opposite sign. This reversal is highly surprising in view of the isostructural adsorbate arrangement in the two systems. Detailed DFT studies suggest an anion-induced difference in the sulfur diffusion mechanism, specifically an exchange diffusion on the Br-covered surface. Experimental evidence for the latter is provided by the observation of Cu vacancy formation in the Br system, which can be rationalized by a side reaction of the sulfur exchange diffusion. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Compilation of Global Bio-Optical in Situ Data for Ocean-Colour Satellite Applications

NASA Technical Reports Server (NTRS)

Valente, Andre; Sathyendranath, Shubha; Brotus, Vanda; Groom, Steve; Grant, Michael; Taberner, Malcolm; Antoine, David; Arnone, Robert; Balch, William M.; Barker, Kathryn;

In situ nuclear magnetic resonance microimaging of live biofilms in a microchannel

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

Renslow, R. S.; Marshall, M. J.; Tucker, A. E.

Nuclear magnetic resonance (NMR) microimaging and spectroscopy was used to interrogate fluids of biological importance (e.g., water, buffer, medium solution) and live biofilms in a microchannel compatible for analyses at ambient pressure and under vacuum. Studies using buffer, growth medium, and actively growing Shewanella oneidensis biofilms were used to demonstrate in situ NMR microimaging measurement capabilities including velocity mapping, diffusion coefficient mapping, relaxometry, localized spectroscopy, and 2D and 3D imaging within a microchannel suitable for different analytical platforms. This technique is promising for diverse applications of correlative imaging using a portable microfluidic platform.

In situ nondestructive imaging of functional pigments in Micro-Tom tomato fruits by multi spectral imaging based on Wiener estimation method

NASA Astrophysics Data System (ADS)

Nishidate, Izumi; Ooe, Shintaro; Todoroki, Shinsuke; Asamizu, Erika

2013-05-01

To evaluate the functional pigments in the tomato fruits nondestructively, we propose a method based on the multispectral diffuse reflectance images estimated by the Wiener estimation for a digital RGB image. Each pixel of the multispectral image is converted to the absorbance spectrum and then analyzed by the multiple regression analysis to visualize the contents of chlorophyll a, lycopene and β-carotene. The result confirms the feasibility of the method for in situ imaging of chlorophyll a, β-carotene and lycopene in the tomato fruits.

In situ monitored in-pile creep testing of zirconium alloys

NASA Astrophysics Data System (ADS)

Kozar, R. W.; Jaworski, A. W.; Webb, T. W.; Smith, R. W.

2014-01-01

The experiments described herein were designed to investigate the detailed irradiation creep behavior of zirconium based alloys in the HALDEN Reactor spectrum. The HALDEN Test Reactor has the unique capability to control both applied stress and temperature independently and externally for each specimen while the specimen is in-reactor and under fast neutron flux. The ability to monitor in situ the creep rates following a stress and temperature change made possible the characterization of creep behavior over a wide stress-strain-rate-temperature design space for two model experimental heats, Zircaloy-2 and Zircaloy-2 + 1 wt%Nb, with only 12 test specimens in a 100-day in-pile creep test program. Zircaloy-2 specimens with and without 1 wt% Nb additions were tested at irradiation temperatures of 561 K and 616 K and stresses ranging from 69 MPa to 455 MPa. Various steady state creep models were evaluated against the experimental results. The irradiation creep model proposed by Nichols that separates creep behavior into low, intermediate, and high stress regimes was the best model for predicting steady-state creep rates. Dislocation-based primary creep, rather than diffusion-based transient irradiation creep, was identified as the mechanism controlling deformation during the transitional period of evolving creep rate following a step change to different test conditions.

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.

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

Optimizing Binding Energies of Key Intermediates for CO 2 Hydrogenation to Methanol over Oxide-Supported Copper

DOE PAGES

None, None

2016-08-29

Rational optimization of catalytic performance has been one of the major challenges in catalysis. We report a bottom-up study on the ability of TiO 2 and ZrO 2 to optimize the CO 2 conversion to methanol on Cu, using combined density functional theory (DFT) calculations, kinetic Monte Carlo (KMC) simulations, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements, and steady-state flow reactor tests. Furthermore, the theoretical results from DFT and KMC agree with in situ DRIFTS measurements, showing that both TiO 2 and ZrO 2 help to promote methanol synthesis on Cu via carboxyl intermediates and the reversemore » water–gas-shift (RWGS) pathway; the formate intermediates, on the other hand, likely act as a spectator eventually. The origin of the superior promoting effect of ZrO 2 is associated with the fine-tuning capability of reduced Zr 3+ at the interface, being able to bind the key reaction intermediates, e.g. *CO 2, *CO, *HCO, and *H 2CO, moderately to facilitate methanol formation. Our study demonstrates the importance of synergy between theory and experiments to elucidate the complex reaction mechanisms of CO 2 hydrogenation for the realization of a better catalyst by design.« less

Apparent diffusion coefficient value of diffusion-weighted imaging for differential diagnosis of ductal carcinoma in situ and infiltrating ductal carcinoma.

PubMed

Ding, Jian-Rong; Wang, Dong-Nv; Pan, Jing-Li

2016-01-01

The present meta-analysis investigated the clinical value of apparent diffusion coefficient (ADC) values in diffusion-weighted imaging (DWI) for differential diagnosis of ductal carcinoma in situ (DCIS) and infiltrating ductal carcinoma (IDC). Electronic databases searches were employed to identify relevant scientific literature, and the search results were screened to selected high-quality studies for this meta-analysis. Methodological quality of the enrolled studies was evaluated by quality evaluation of diagnostic accuracy studies (QUADAS). Summary odds ratios (ORs) and its corresponding 95% confidence interval (95% CI) were calculated for DCIS versus IDC category of ADC value using Z test. Our meta-analysis contained a combined total of 1,097 subjects (928 patients with IDC and 169 patients with DCIS) from 9 relevant high-quality cohort studies. Pooled ORs demonstrated that ADC value in IDC patients was significantly lower than DCIS patients. Subgroup analysis stratified by ethnicity indicated a higher ADC value in DCIS patients compared to IDC, in Asian population, but not in Caucasians. Magnetic resonance imaging (MRI) machine type-stratified analysis revealed that the ADC value of DWI obtained from both non- General Electric Company (GE) 1.5T and GE 1.5T machines were highly reliable in the differential diagnosis of DCIS and IDC. Our meta-analysis provides evidence that ADC values in DWI accurately conveys the differences in tumor architecture between IDC and DCIS, which has high clinical value in differentiatal diagnosis of IDC and DCIS. This may lead to improved BC prediction and treatment.

The metal-insulator transition in a phase-separated manganite studied by in situ STS

NASA Astrophysics Data System (ADS)

Snijders, P. C.; Gao, M.; Guo, H.; Ward, T. Z.; Gao, H.-J.; Shen, J.; Gai, Z.

2012-02-01

Electronic phase separation (EPS) is a key feature at the heart of the wide variety of electronic and magnetic properties in complex oxides. One consequence of EPS is that electronic transport experiments in bulk materials or 2D films mostly probe the low resistivity electronic phases due to the percolative path of the current. We study oxygen deficient La5/8-xPrxCa3/8M nO3 (LPCMO) thin films using both in situ scanning tunneling spectroscopy (STS) and ex situ transport experiments. The oxygen deficiency is known to decrease the metal-insulator transition (MIT) temperature or even completely suppress the MIT in conventional transport experiments. We show that in situ STS is able to detect the MIT even in systems where conventional transport experiments do not show an MIT at zero magnetic field.

Comparison of field and laboratory VNIR spectroscopy for profile soil property estimation

USDA-ARS?s Scientific Manuscript database

In-field, in-situ data collection with soil sensors has potential to improve the efficiency and accuracy of soil property estimates. Optical diffuse reflectance spectroscopy (DRS) has been used to estimate important soil properties, such as soil carbon, nitrogen, water content, and texture. Most pre...

Methods to Estimate Solar Radiation Dosimetry in Coral Reefs Using Remote Sensed, Modeled, and in Situ Data.

EPA Science Inventory

Solar irradiance has been increasingly recognized as an important determinant of bleaching in coral reefs, but measurements of solar radiation exposure within coral reefs have been relatively limited. Solar irradiance and diffuse down welling attenuation coefficients (Kd, m-1) we...

EFFICIENCY OF CAPPING CONTAMINATED SEDIMENTS IN SITU: 2. MATHEMATICS OF DIFFUSION-ADSORPTION IN THE CAPPING LAYER. (R825513C009)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Material Science Experiments on Mir

NASA Technical Reports Server (NTRS)

Kroes, Roger L.

1999-01-01

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

A review of the LATEX project: mesoscale to submesoscale processes in a coastal environment

NASA Astrophysics Data System (ADS)

Petrenko, Anne A.; Doglioli, Andrea M.; Nencioli, Francesco; Kersalé, Marion; Hu, Ziyuan; d'Ovidio, Francesco

2017-04-01

The main objective of the LAgrangian Transport EXperiment (LATEX) project was to study the influence of coastal mesoscale and submesoscale physical processes on circulation dynamics, cross-shelf exchanges, and biogeochemistry in the western continental shelf of the Gulf of Lion, Northwestern Mediterranean Sea. LATEX was a five-year multidisciplinary project based on the combined analysis of numerical model simulations and multi-platform field experiments. The model component included a ten-year realistic 3D numerical simulation, with a 1 km horizontal resolution over the gulf, nested in a coarser 3 km resolution model. The in situ component involved four cruises, including a large-scale multidisciplinary campaign with two research vessels in 2010. This review concentrates on the physics results of LATEX, addressing three main subjects: (1) the investigation of the mesoscale to submesoscale processes. The eddies are elliptic, baroclinic, and anticyclonic; the strong thermal and saline front is density compensated. Their generation processes are studied; (2) the development of sampling strategies for their direct observations. LATEX has implemented an adaptive strategy Lagrangian tool, with a reference software available on the web, to perform offshore campaigns in a Lagrangian framework; (3) the quantification of horizontal mixing and cross-shelf exchanges. Lateral diffusivity coefficients, calculated in various ways including a novel technique, are in the range classically encountered for their associated scales. Cross-shelf fluxes have been calculated, after retrieving the near-inertial oscillation contribution. Further perspectives are discussed, especially for the ongoing challenge of studying submesoscale features remotely and from in situ data.

Indomethacin-5-fluorouracil-methyl ester dry emulsion: a potential oral delivery system for 5-fluorouracil.

PubMed

Wang, Jing; Hu, Yanchen; Li, Ling; Jiang, Tongying; Wang, Siling; Mo, Fengkui

2010-06-01

To produce a combined effect of indomethacin (IDM) and 5-fluorouracil (5FU) for cancer therapy, the side effects of IDM on the gastrointestinal (GI) tract were reduced and the oral adsorption of 5FU was improved. Indomethacin-5-fluorouracil-methyl ester (IFM) dry emulsion was prepared and evaluated as a potential oral delivery system for 5FU. IFM was synthesized by formation of an ester between IDM and 5FU intermediate and then characterized by structure, melting point, solubility, apparent partition coefficient, and incubation with GI tract contents and plasma. Gum acacia and sodium carboxymethyl cellulose (CMC-Na) were applied as the adsorbent and solid carrier to prepare IFM dry emulsion. IFM dry emulsion was then characterized by reconstitution in water and in situ intestinal perfusion experiment. Physicochemical properties of the new synthesized compound confirmed the formation of IFM. Incubation of IFM in the contents of the GI tract and plasma revealed that IFM was not relatively stable in GI contents during the time period of transit through the GI tract, whereas it was very unstable in plasma and released 5FU rapidly. The IFM dry emulsion could be easily reconstituted in water, and the mean particle size was 2.416 microm. The absorption rate constant (K) for IFM with concentration of 2, 5, and 10 microg/mL in the in situ perfusion experiment were 0.473, 0.423, and 0.433/h, respectively, demonstrating passive diffusion of IFM across the biological membranes. This study indicates that the IFM dry emulsion may represent a potentially useful oral delivery system for 5FU.

Influence of liquid structure on diffusive isotope separation in molten silicates and aqueous solutions

NASA Astrophysics Data System (ADS)

Watkins, James M.; DePaolo, Donald J.; Ryerson, Frederick J.; Peterson, Brook T.

2011-06-01

Molecular diffusion in natural volcanic liquids discriminates between isotopes of major ions (e.g., Fe, Mg, Ca, and Li). Although isotope separation by diffusion is expected on theoretical grounds, the dependence on mass is highly variable for different elements and in different media. Silicate liquid diffusion experiments using simple liquid compositions were carried out to further probe the compositional dependence of diffusive isotopic discrimination and its relationship to liquid structure. Two diffusion couples consisting of the mineral constituents anorthite (CaAl 2Si 2O 8; denoted AN), albite (NaAlSi 3O 8; denoted AB), and diopside (CaMgSi 2O 6; denoted DI) were held at 1450 °C for 2 h and then quenched to ambient pressure and temperature. Major-element as well as Ca and Mg isotope profiles were measured on the recovered quenched glasses. In both experiments, Ca diffuses rapidly with respect to Si. In the AB-AN experiment, D Ca/ D Si ≈ 20 and the efficiency of isotope separation for Ca is much greater than in natural liquid experiments where D Ca/ D Si ≈ 1. In the AB-DI experiment, D Ca/ D Si ≈ 6 and the efficiency of isotope separation is between that of the natural liquid experiments and the AB-AN experiment. In the AB-DI experiment, D Mg/ D Si ≈ 1 and the efficiency of isotope separation for Mg is smaller than it is for Ca yet similar to that observed for Mg in natural liquids. The results from the experiments reported here, in combination with results from natural volcanic liquids, show clearly that the efficiency of diffusive separation of Ca isotopes is systematically related to the solvent-normalized diffusivity - the ratio of the diffusivity of the cation ( D Ca) to the diffusivity of silicon ( D Si). The results on Ca isotopes are consistent with available data on Fe, Li, and Mg isotopes in silicate liquids, when considered in terms of the parameter D cation/ D Si. Cations diffusing in aqueous solutions display a similar relationship between isotopic separation efficiency and Dcation/D, although the efficiencies are smaller than in silicate liquids. Our empirical relationship provides a tool for predicting the magnitude of diffusive isotopic effects in many geologic environments and a basis for a more comprehensive theory of isotope separation in liquid solutions. We present a conceptual model for the relationship between diffusivity and liquid structure that is consistent with available data.

In situ study of Li-ions diffusion and deformation in Li-rich cathode materials by using scanning probe microscopy techniques

NASA Astrophysics Data System (ADS)

Zeng, Kaiyang; Li, Tao; Tian, Tian

2017-08-01

In this paper, the scanning probe microscopy (SPM) based techniques, namely, conductive-AFM, electrochemical strain microscopy (ESM) and AM-FM (amplitude modulation-frequency modulation) techniques, are used to in situ characterize the changes in topography, conductivity and elastic properties of Li-rich layered oxide cathode (Li1.2Mn0.54Ni0.13Co0.13O2) materials, in the form of nanoparticles, when subject to the external electric field. Nanoparticles are the basic building blocks for composite cathode in a Li-ion rechargeable battery. Characterization of the structure and electrochemical properties of the nanoparticles is very important to understand the performance and reliability of the battery materials and devices. In this study, the conductivity, deformation and mechanical properties of the Li-rich oxide nanoparticles under different polarities of biases are studied using the above-mentioned SPM techniques. This information can be correlated with the Li+-ion diffusion and migration in the particles under external electrical field. The results also confirm that the SPM techniques are ideal tools to study the changes in various properties of electrode materials at nano- to micro-scales during or after the ‘simulated’ battery operation conditions. These techniques can also be used to in situ characterize the electrochemical performances of other energy storage materials, especially in the form of the nanoparticles.

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.

In situ TEM probing of crystallization form-dependent sodiation behavior in ZnO nanowires for sodium-ion batteries

DOE PAGES

Xu, Feng; Li, Zhengrui; Wu, Lijun; ...

2016-09-13

Development of sodium-ion battery (SIB) electrode materials currently lags behind electrodes in commercial lithium-ion batteries (LIBs). However, in the long term, development of SIB components is a valuable goal. Their similar, but not identical, chemistries require careful identification of the underlying sodiation mechanism in SIBs. Here in this study, we utilize in situ transmission electron microscopy to explore quite different sodiation behaviors even in similar electrode materials through real-time visualization of microstructure and phase evolution. Upon electrochemical sodiation, single-crystalline ZnO nanowires (sc-ZNWs) are found to undergo a step-by-step electrochemical displacement reaction, forming crystalline NaZn 13 nanograins dispersed in a Namore » 2O matrix. This process is characterized by a slowly propagating reaction front and the formation of heterogeneous interfaces inside the ZNWs due to non-uniform sodiation amorphization. In contrast, poly-crystalline ZNWs (pc-ZNWs) exhibited an ultrafast sodiation process, which can partly be ascribed to the availability of unobstructed ionic transport pathways among ZnO nanograins. Thus the reaction front and heterogeneous interfaces disappear. The in situ TEM results, supported by calculation of the ion diffusion coefficient, provide breakthrough insights into the dependence of ion diffusion kinetics on crystallization form. This points toward a goal of optimizing the microstructure of electrode materials in order to develop high performance SIBs.« less

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

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.

In vitro and in situ degradation of alkali treated sorghum wet distillers grains alone or in combination with corn stalks to increase their nutritive value

USDA-ARS?s Scientific Manuscript database

This experiment was conducted to evaluate the effect of alkali treatment on in vitro and in situ digestibility of fiber sources. An in vitro and in situ experiment were conducted to determine the effects of treating sorghum WDG with solubles (SWDG) and corn stalks (CS) with calcium hydroxide on in ...

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.

Structure determination of an integral membrane protein at room temperature from crystals in situ

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

Axford, Danny; Foadi, James; Imperial College London, London SW7 2AZ

2015-05-14

The X-ray structure determination of an integral membrane protein using synchrotron diffraction data measured in situ at room temperature is demonstrated. The structure determination of an integral membrane protein using synchrotron X-ray diffraction data collected at room temperature directly in vapour-diffusion crystallization plates (in situ) is demonstrated. Exposing the crystals in situ eliminates manual sample handling and, since it is performed at room temperature, removes the complication of cryoprotection and potential structural anomalies induced by sample cryocooling. Essential to the method is the ability to limit radiation damage by recording a small amount of data per sample from many samplesmore » and subsequently assembling the resulting data sets using specialized software. The validity of this procedure is established by the structure determination of Haemophilus influenza TehA at 2.3 Å resolution. The method presented offers an effective protocol for the fast and efficient determination of membrane-protein structures at room temperature using third-generation synchrotron beamlines.« less

In situ Scanning Electron Microscopy of Silicon Anode Reactions in Lithium-Ion Batteries during Charge/Discharge Processes

PubMed Central

Chen, Chih-Yao; Sano, Teruki; Tsuda, Tetsuya; Ui, Koichi; Oshima, Yoshifumi; Yamagata, Masaki; Ishikawa, Masashi; Haruta, Masakazu; Doi, Takayuki; Inaba, Minoru; Kuwabata, Susumu

2016-01-01

A comprehensive understanding of the charge/discharge behaviour of high-capacity anode active materials, e.g., Si and Li, is essential for the design and development of next-generation high-performance Li-based batteries. Here, we demonstrate the in situ scanning electron microscopy (in situ SEM) of Si anodes in a configuration analogous to actual lithium-ion batteries (LIBs) with an ionic liquid (IL) that is expected to be a functional LIB electrolyte in the future. We discovered that variations in the morphology of Si active materials during charge/discharge processes is strongly dependent on their size and shape. Even the diffusion of atomic Li into Si materials can be visualized using a back-scattering electron imaging technique. The electrode reactions were successfully recorded as video clips. This in situ SEM technique can simultaneously provide useful data on, for example, morphological variations and elemental distributions, as well as electrochemical data. PMID:27782200

The ability to use remote polarization studies of Earth from space in the national economy (Project of the onboard filter panoramic polarimeter)

NASA Astrophysics Data System (ADS)

Nevodovskyi, P. V.; Vidmachenko, A. P.; Geraimchuk, M. D.; Ivahiv, O. V.

2016-10-01

Remote polarization studies are a very powerful method of solving of astronomical tasks with the study of the physical properties of the planets and their atmospheres. It allows research of objects as in situ, so in vitro, and has many other advantages. To use this method has already been developed and are continuing the development of many various special instruments called polarimeters. The essence of the space experiment consists in the fact to using the polarimeter installed on board a micro satellite, systematically, during each of its revolutions around the Earth, to monitor a polarization components of a diffusely reflected by atmosphere solar radiation in different, previously stipulated wavelengths. There are a lot of the optical schemes, which are used in devices of measuring and monitoring of parameters of polarized radiation, including those into space experiments of probing of the Earth's atmosphere from orbit of satellites. In this paper we analyze the potential for use of filter-polarimeter to measure the Stokes vector components.

An in-situ Mobile pH Calibrator for application with HOV and ROV platform in deep sea environments

NASA Astrophysics Data System (ADS)

Tan, C.; Ding, K.; Seyfried, W. E., Jr.

2014-12-01

Recently, a novel in-situ sensor calibration instrument, Mobile pH Calibrator (MpHC), was developed for application with HOV Alvin. It was specifically designed to conduct in-situ pH measurement in deep sea hydrothermal diffuse fluids with in-situ calibration function. In general, the sensor calibrator involves three integrated electrodes (pH, dissolved H2 and H2S) and a temperature sensor, all of which are installed in a cell with a volume of ~ 1 ml. A PEEK check valve cartridge is installed at the inlet end of the cell to guide the flow path during the measurement and calibration processes. Two PEEK tubes are connected at outlet end of the cell for drawing out hydrothermal fluid and delivering pH buffer fluids. During its measurement operation, the pump draws in hydrothermal fluid, which then passes through the check valve directly into the sensing cell. When in calibration mode, the pump delivers pH buffers into the cell, while automatically closing the check valve to the outside environment. This probe has two advantages compared to our previous unit used during KNOX18RR MAR cruise in 2008 and MARS cabled observatory deployment in 2012. First, in the former design, a 5 cm solenoid valve was equipped with the probe. This enlarged size prevented its application in specific point or small area. In this version, the probe has only a dimension of 1.6 cm for an easy access to hydrothermal biological environments. Secondly, the maximum temperature condition of the earlier system was limited by the solenoid valve precluding operation in excess of 50 ºC. The new design avoids this problem, which improves its temperature tolerance. The upper limit of temperature condition is now up to 100oC, therefore enabling broader application in hydrothermal diffuse flow system on the seafloor. During SVC cruise (AT26-12) in the Gulf of Mexico this year, the MpHC was successfully tested with Alvin dives at the depth up to 2600 m for measuring pH with in-situ calibration in seafloor cold seep environment. The measurement and calibration were also conducted in hydrothermal diffuse flow at temperature condition exceeding 70 ºC with Alvin dives during a recent cruise AT26-17 in ASHES vent field and Main Endeavour Field on Juan de Fuca Ridge. Data from these seagoing deployments will be presented, with emphasis on both technical and scientific aplications.

The diffusion of water in haploanesite

NASA Astrophysics Data System (ADS)

Ni, H.; Zhang, Y.

2008-12-01

Diffusive transport of water in silicate melts is a key process in magma dynamics and volcanic eruptions, including bubble growth. Previous studies demonstrate that in additional to temperature, water content and pressure, melt composition also plays an important role in determining water diffusivity. We carried out high temperature (1311-1512°C) diffusion-couple experiments and intermediate temperature (470- 600°C) dehydration experiments to investigate H2O diffusion in a melt of haploandesitic composition. The diffusion couple is composed of an anhydrous (with <0.1 wt.% H2O) and a hydrous (with 2 wt.% H2O) haploandesitic glass. A platinum capsule is used to contain the couple and then it is welded shut. Diffusion runs are carried out in a 12.7-mm piston-cylinder apparatus at 1 GPa and superliquidus temperatures of 1584-1785 K. Infrared microscopy is applied on quenched glass to measure the profile of total H2O concentration (H2Ot). The profile shape is best fit by an error function, indicating an H2O diffusivity virtually independent of H2O concentration, consistent with the results of Behrens et al. (2004) on an Fe-bearing andesite. Dehydration experiments are performed at 743-873 K in a rapid-quench cold-seal vessel, with a heated hydrous glass losing water to 0.1 GPa Ar atmosphere. Measured diffusion profiles, however, show that water diffusivity is dependent on water content. Experimental data can be explained by H2Om being the dominating diffusant or a total H2O diffusivity proportional to total H2O content. The distinction between the high-temperature experiments where H2Ot diffusivity is apparently independent of H2Ot content, and the intermediate-temperature experiments where H2Ot diffusivity depends on H2Ot can be rationalized if OH diffusion has a higher activation energy than molecular H2O diffusion, and their comparable diffusivities at high T gradually diverge as temperature is lowered. At below 1 wt.% H2O, water diffusivity increases from rhyolite to dacite to andesite at >1300°C, and this sequence is reversed at <600°C.

Applications of a time-dependent polar ionosphere model for radio modification experiments

NASA Astrophysics Data System (ADS)

Fallen, Christopher Thomas

A time-dependent self-consistent ionosphere model (SLIM) has been developed to study the response of the polar ionosphere to radio modification experiments, similar to those conducted at the High-Frequency Active Auroral Research Program (HAARP) facility in Gakona, Alaska. SCIM solves the ion continuity and momentum equations, coupled with average electron and ion gas energy equations; it is validated by reproducing the diurnal variation of the daytime ionosphere critical frequency, as measured with an ionosonde. Powerful high-frequency (HF) electromagnetic waves can drive naturally occurring electrostatic plasma waves, enhancing the ionospheric reflectivity to ultra-high frequency (UHF) radar near the HF-interaction region as well as heating the electron gas. Measurements made during active experiments are compared with model calculations to clarify fundamental altitude-dependent physical processes governing the vertical composition and temperature of the polar ionosphere. The modular UHF ionosphere radar (MUIR), co-located with HAARP, measured HF-enhanced ion-line (HFIL) reflection height and observed that it ascended above its original altitude after the ionosphere had been HF-heated for several minutes. The HFIL ascent is found to follow from HF-induced depletion of plasma surrounding the F-region peak density layer, due to temperature-enhanced transport of atomic oxygen ions along the geomagnetic field line. The lower F-region and topside ionosphere also respond to HF heating. Model results show that electron temperature increases will lead to suppression of molecular ion recombination rates in the lower F region and enhancements of ambipolar diffusion in the topside ionosphere, resulting in a net enhancement of slant total electron content (TEC); these results have been confirmed by experiment. Additional evidence for the model-predicted topside ionosphere density enhancements via ambipolar diffusion is provided by in-situ measurements of ion density and vertical velocity over HAARP made by a Defense Meteorological Satellite Program (DMSP) satellite.

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

In-Situ Tuff Water Migration/Heater Experiment: posttest thermal analysis

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

Eaton, R.R.; Johnstone, J.K.; Nunziato, J.W.

This report describes posttest laboratory experiments and thermal computations for the In-Situ Tuff Water Migration/Heater Experiment that was conducted in Grouse Canyon Welded Tuff in G-Tunnel, Nevada Test Site. Posttest laboratory experiments were designed to determine the accuracy of the temperatures measured by the rockwall thermocouples during the in-situ test. The posttest laboratory experiments showed that the measured in-situ rockwall temperatures were 10 to 20{sup 0}C higher than the true rockwall temperatures. The posttest computational results, obtained with the thermal conduction code COYOTE, were compared with the experimentally obtained data and with calculated pretest results. Daily heater output power fluctuationsmore » (+-4%) caused by input power line variations and the sensitivity of temperature to heater output power required care in selecting the average heater output power values used in the code. The posttest calculated results compare reasonably well with the experimental data. 10 references, 14 figures, 5 tables.« less

An Investigation into the Effects of Interface Stress and Interfacial Arrangement on Temperature Dependent Thermal Properties of a Biological and a Biomimetic Material

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

Tomar, Vikas

2015-01-12

A significant effort in the biomimetic materials research is on developing materials that can mimic and function in the same way as biological tissues, on bio-inspired electronic circuits, on bio-inspired flight structures, on bio-mimetic materials processing, and on structural biomimetic materials, etc. Most structural biological and biomimetic material properties are affected by two primary factors: (1) interfacial interactions between an organic and an inorganic phase usually in the form of interactions between an inorganic mineral phase and organic protein network; and (2) structural arrangement of the constituents. Examples are exoskeleton structures such as spicule, nacre, and crustacean exoskeletons. A significantmore » effort is being directed towards making synthetic biomimetic materials based on a manipulation of the above two primary factors. The proposed research is based on a hypothesis that in synthetic materials with biomimetic morphology thermal conductivity, k, (how fast heat is carried away) and thermal diffusivity, D, (how fast a material’s temperature rises: proportional to the ratio of k and heat capacity) can be engineered to be either significantly low or significantly high based on a combination of chosen interface orientation and interfacial arrangement in comparison to conventional material microstructures with the same phases and phase volume fractions. METHOD DEVELOPMENT 1. We have established a combined Raman spectroscopy and nanomechanical loading based experimental framework to perform environment (liquid vs. air vs. vacuum) dependent and temperature dependent (~1000 degree-C) in-situ thermal diffusivity measurements in biomaterials at nanoscale to micron scale along with the corresponding analytical theoretic calculations. (Zhang and Tomar, 2013) 2. We have also established a new classical molecular simulation based framework to measure thermal diffusivity in biomolecular interfaces. We are writing a publication currently (Qu and Tomar, 2013) to report the framework and findings in tropocollagen-hydroxyapatite based idealized biomaterial interfaces. PHYSICAL FINDINGS 1. Analyses using experiments have revealed that in the case of bone thermal conductivity and thermal diffusivity at micron scale shows significant dependence on compressive stress and temperature. Overall, there is a decrease with respect to increase in temperature and increase with respect to increase in compressive stress. Bio-molecular simulations on idealized tropocollagen-hydroxyapatite interfaces confirm such findings. However, simulations also reveal that thermal diffusivity and thermal conductivity can be significantly tailored by interfacial orientation. More importantly, in inorganic materials, interfaces contribute to reduce thermal conductivity and diffusivity. However, analyses here reveal that both can be increased despite presence of a lot of interfaces. 2. Based on significant role played by interfaces in affecting bone thermal properties, a crustacean-exoskeleton system is examined for thermal diffusivity using the newly developed setup. Special emphasis here is on this system since such arrangement is found to be common in fresh water shrimp as well as in some deep water organisms surviving in environment extremes. Experiments reveal that in such system thermal diffusivity is highly tailorable. 3. Overall, experiments and models have established that in biomaterial interfaces a counterintuitive role of interfaces in mediating thermal conduction as a function of stress and temperature is possible in contrast to inorganic materials where interfaces almost always lead to reduction of thermal conductivity as a function of such factors. More investigations are underway to reveal physical origins of such counter-physical characteristics. Such principles can be significantly useful in developing new and innovative bioenergy and inorganic energy systems where heat dissipation significantly affects system performance.« less

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.

Diffuse lamellar keratitis after laser in situ keratomileusis with the Moria LSK-One and Carriazo-Barraquer microkeratomes.

PubMed

Thammano, Pavika; Rana, Azhar N; Talamo, Jonathan H

2003-10-01

To assess risk factors for and incidence of diffuse lamellar keratitis (DLK) and to investigate whether microkeratome design is associated with the incidence of DLK. The Laser Eye Consultants of Boston, Boston and Waltham, Massachusetts, USA. In a retrospective nonrandomized comparative study, 1122 consecutive primary laser in situ keratomileusis (LASIK) treatments (584 patients) were analyzed to determine the incidence of DLK using 2 different microkeratome designs (Moria LSK-One [LSK] and Moria Carriazo-Barraquer [C-B]). The incidence of DLK was as determined by clinical signs. The overall incidence of DLK was 2.23%. The incidence in the LSK and C-B groups was 1.09% and 4.38%, respectively, with a statistically significant difference in incidence between the 2 groups (P<.01). Epithelial irregularities increased the risk for DLK. There was no significant statistical difference in sex, age, operating room location, type of laser, or time of day the surgery was performed between the 2 groups or between eyes that had DLK and eyes without DLK. The incidence of DLK using the C-B microkeratome fell significantly after May 2000, when new cleaning methods for this device were introduced. Different microkeratomes and how they are maintained may influence the incidence of DLK. Diffuse lamellar keratitis is more common after LASIK in a setting of epithelial irregularities, whether or not an actual epithelial defect is created.

Shape-dependent hydrogen-storage properties in Pd nanocrystals: which does hydrogen prefer, octahedron (111) or cube (100)?

PubMed

Li, Guangqin; Kobayashi, Hirokazu; Dekura, Shun; Ikeda, Ryuichi; Kubota, Yoshiki; Kato, Kenichi; Takata, Masaki; Yamamoto, Tomokazu; Matsumura, Syo; Kitagawa, Hiroshi

2014-07-23

Pd octahedrons and cubes enclosed by {111} and {100} facets, respectively, have been synthesized for investigation of the shape effect on hydrogen-absorption properties. Hydrogen-storage properties were investigated using in situ powder X-ray diffraction, in situ solid-state (2)H NMR and hydrogen pressure-composition isotherm measurements. With these measurements, it was found that the exposed facets do not affect hydrogen-storage capacity; however, they significantly affect the absorption speed, with octahedral nanocrystals showing the faster response. The heat of adsorption of hydrogen and the hydrogen diffusion pathway were suggested to be dominant factors for hydrogen-absorption speed. Furthermore, in situ solid-state (2)H NMR detected for the first time the state of (2)H in a solid-solution (Pd + H) phase of Pd nanocrystals at rt.

In-situ x-ray studies of compositional control during synthesis of LaGaO 3 by radio frequency-magnetron sputtering

DOE PAGES

Highland, Matthew J.; Fong, Dillon D.; Ju, Guangxu; ...

2015-08-28

In-situ synchrotron x-ray scattering has been used to monitor and control the synthesis of LaGaO 3 epitaxial thin films by 90° off-axis RF-magnetron sputtering. We compared films deposited from a single LaGaO 3 source with those prepared by alternating deposition from separate La 2O 3 and Ga 2O 3 sources. The conditions for growth of stoichiometric films were determined by real-time monitoring of secondary phase formation as well as from features in the diffuse scatter from island formation during synthesis. Our results provide atomic-scale insight into the mechanisms taking place during reactive epitaxial growth and demonstrate how in-situ techniques canmore » be utilized to achieve stoichiometric control in ultrathin films.« less

Formulation of thermoresponsive and buccal adhesive in situ gel for treatment of oral thrush containing poorly water soluble drug bifonazole.

PubMed

Patel, Dimendra; Patel, Dipti; Prajapati, Jatin; Patel, Umang; Patel, Vijay

2012-03-01

The aim of the present work is to formulate and evaluate in situ oral topical gels of poorly water soluble drug Bifonazole based on temperature induced systems for the treatment of oral candidiasis. Bifonazole is poorly water soluble and low permeable drug means it's belongs to BCS Class IV. Due to its poor water solubility, it necessary to enhance solubility in water by make complex with Beta- Cyclodextrin (Drug to βCyclo Dextrine ratio is 1:1). After in situ gel preparation done by using Poloxamer (10% and 15%w/w) along with carbopol 934 (0.2 to 1.0% w/w) and Bifonazole - β CD complex (1%w/w). The formulations were evaluated for physiochemical parameter, gelation Temperature, viscosity, gel strength, content uniformity mucoadhesive force, Diffusion Study.

Formulation of thermoresponsive and buccal adhesive in situ gel for treatment of oral thrush containing poorly water soluble drug bifonazole

PubMed Central

Patel, Dimendra; Patel, Dipti; Prajapati, Jatin; Patel, Umang; Patel, Vijay

2012-01-01

The aim of the present work is to formulate and evaluate in situ oral topical gels of poorly water soluble drug Bifonazole based on temperature induced systems for the treatment of oral candidiasis. Bifonazole is poorly water soluble and low permeable drug means it's belongs to BCS Class IV. Due to its poor water solubility, it necessary to enhance solubility in water by make complex with Beta- Cyclodextrin (Drug to βCyclo Dextrine ratio is 1:1). After in situ gel preparation done by using Poloxamer (10% and 15%w/w) along with carbopol 934 (0.2 to 1.0% w/w) and Bifonazole – β CD complex (1%w/w). The formulations were evaluated for physiochemical parameter, gelation Temperature, viscosity, gel strength, content uniformity mucoadhesive force, Diffusion Study. PMID:23066185

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.

Optimized Mixing in Microchannels with Integrated Microactuators

NASA Astrophysics Data System (ADS)

Folk, Christopher Richard

Microscale valves and pumps have been designed and fabricated for integration into a microfluidic circuit. Furthermore, a micromixer for this circuit has been designed and optimized. N-isopropylacrylamide (NIPA) gels have been fabricated and actuated directly with heat and indirectly by laser. A new method for photopatterning these gels based on photoinitiation has been used to fabricate hydrogel valves down to 50 mum in diameter. Hydrogel valves have been fabricated in situ in a microfluidic network. The valves open in 27 seconds and close via diffusion of water into the gel in 128 seconds, which is faster than other optically-driven polymers used for large displacements. In this research, azobis-isobutyronitrile (AIBN) is incorporated into a variety of polydimethylsiloxane (PDMS) pump chambers. The AIBN is heated via integrated resistive heaters and decomposes to release nitrogen gas. The nitrogen gas provides impulse power to a PDMS diaphragm to displace the fluid. The pump devices have been built and characterized. Lastly, in this work, we describe the use of combined fluid dynamic and diffusion modeling to simulate a micromixer based on the elements above. The micromixer is optimized via Design of Experiments to produce an optimized geometry for mixing. The optimization is validated via comparison to previous work through the Strouhal number.

Capable Infection of Hepatitis B Virus in Diffuse Large B-cell Lymphoma

PubMed Central

Wang, Yanchun; Wang, Huijie; Pan, Shaokun; Hu, Tao; Shen, Jiabin; Zheng, Hui; Xie, Suhong; Xie, Youhua; Lu, Renquan; Guo, Lin

2018-01-01

Background: Diffuse large B-cell lymphoma (DLBCL) is the most common pathological type of non-Hodgkin lymphoma (NHL). It is strongly correlated to the host immunity and infection status. Aim: This study tested the hypothesis that hepatitis B virus (HBV) infection is also associated with DLBCL. Methods: Clinical analysis of the correlation between DLBCL and HBV infection, detection of HBV in situ of DLBCL tissue, and biological experiments that determined whether HBV infects B lymphocytes were conducted. Results: Our long-term clinical data showed that the positive rate of serum HBV was significantly increased in DLBCL patients (23.6%) compared to that in the general Chinese population (7.2%, P<0.001), especially in advanced stage lymphoma patients (P=0.003). In addition, HBV could infect B lymphocytes in vitro and the HBV antigen and nucleic acid could be detected intracellularly. Hepatitis B x protein (HBx) was also strongly expressed in tissues from DLBCL patients that were serum HBV surface antigen (HBsAg) positive. These patients responded less well to therapy with an odds ratio (OR) of 3.04. Conclusions: HBV can infect B lymphocytes. It might be related to the development of DLBCL and may also impact the efficacy of treatment. PMID:29760795

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.

Room temperature synthesis of Cu₂O nanospheres: optical properties and thermal behavior.

PubMed

Nunes, Daniela; Santos, Lídia; Duarte, Paulo; Pimentel, Ana; Pinto, Joana V; Barquinha, Pedro; Carvalho, Patrícia A; Fortunato, Elvira; Martins, Rodrigo

2015-02-01

The present work reports a simple and easy wet chemistry synthesis of cuprous oxide (Cu2O) nanospheres at room temperature without surfactants and using different precursors. Structural characterization was carried out by X-ray diffraction, transmission electron microscopy, and scanning electron microscopy coupled with focused ion beam and energy-dispersive X-ray spectroscopy. The optical band gaps were determined from diffuse reflectance spectroscopy. The photoluminescence behavior of the as-synthesized nanospheres showed significant differences depending on the precursors used. The Cu2O nanospheres were constituted by aggregates of nanocrystals, in which an on/off emission behavior of each individual nanocrystal was identified during transmission electron microscopy observations. The thermal behavior of the Cu2O nanospheres was investigated with in situ X-ray diffraction and differential scanning calorimetry experiments. Remarkable structural differences were observed for the nanospheres annealed in air, which turned into hollow spherical structures surrounded by outsized nanocrystals.

Kinetics and characterization of radiation-induced grafting of styrene on fluoropolymers

NASA Astrophysics Data System (ADS)

Guilmeau, I.; Esnouf, S.; Betz, N.; Le Moël, A.

1997-08-01

Grafting of styrene solution onto poly(ethylene-co-tetrafluoroethylene) (ETFE) was carried out by the pre-irradiation method. ETFE films were irradiated by 1.5 MeV electron beams in air. The influence of grafting temperature (50 to 80°C) has been investigated. It was found that the saturation grafting yield and the initial rate follow an Arrhenius law. The volume grafting yields were measured by FTIR spectroscopy in transmission and by weighing and the 'surface' grafting yields by FTIR-ATR. The results showed that grafting reaction is not monomer diffusion controlled in 30 μm film, nevertheless heterogeneities are revealed. By in-situ ESR, the decay of peroxy radicals was recorded under various heating and grafting conditions. These experiments suggest that the peroxy radicals react rapidly with monomer, but do not initiate the grafting process. The propagating radicals were not detectable, which may indicate that polystyrene chains are very long.

In situ observations of the scale-size of plasma turbulence in the asteroid belt /1.6-3 astronomical units/

NASA Technical Reports Server (NTRS)

Intriligator, D. S.

1975-01-01

Pioneer 10 observations from the Ames Research Center Plasma Analyzer experiment between 1 and 3 AU in 1972 have been used to estimate the power spectra of the streaming speed of solar wind protons. A power-law spectrum is obtained in the 10,000 to 0.001 Hz frequency range which is similar to that obtained for the solar wind proton number density and streaming speed at 1 AU in 1965 December and 1966 January. The power spectra indicate that significant turbulence on the scale of about 1,000,000 km or more is present throughout this range of heliocentric distances, implying the importance of the role of large-scale turbulence between 1 and 3 AU. The power spectra also present qualitatively information concerning the cosmic-ray diffusion tensor at these extended distances.

Adsorption/electrosorption of catechol and resorcinol onto high area activated carbon cloth.

PubMed

Bayram, Edip; Hoda, Numan; Ayranci, Erol

2009-09-15

Removal of catechol and resorcinol from aqueous solutions by adsorption and electrosorption onto high area activated carbon cloth (ACC) was investigated. Kinetics of both adsorption and electrosorption were followed by in-situ UV-spectroscopic method and the data were treated according to pseudo-first-order, pseudo-second-order and intraparticle diffusion models. It was found that the adsorption and electrosorption of these compounds onto ACC follows pseudo-second-order model. pH changes during adsorption and electrosorption were followed and discussed with regard to the interaction between ACC and adsorbate molecules, utilizing the pH(pzc) value of ACC. An electrodesorption experiment was conducted to explore the possibility of regeneration of ACC. Adsorption isotherms were derived at 25 degrees C on the basis of batch analysis. The fits of experimental isotherm data to the well-known Freundlich, Langmuir and Tempkin models were examined.

Diagnosing the Internal Architecture of Zeolite Ferrierite

PubMed Central

Schmidt, Joel E.; Hendriks, Frank C.; Lutz, Martin; Post, L. Christiaan; Fu, Donglong

2017-01-01

Abstract Large crystals of zeolite ferrierite (FER) are important model systems for spatially resolved catalysis and diffusion studies, though there is considerable variation in crystal habit depending on the chemical composition and employed synthesis conditions. A synergistic combination of techniques has been applied, including single crystal X‐ray diffraction, high‐temperature in situ confocal fluorescence microscopy, fluorescent probe molecules, wide‐field microscopy and atomic force microscopy to unravel the internal architecture of three distinct FER zeolites. Pyrolyzed template species can be used as markers for the 8‐membered ring direction as they are trapped in the terraced roof of the FER crystals. This happens as the materials grow in a layer‐by‐layer, defect‐free manner normal to the large crystal surface, and leads to a facile method to diagnose the pore system orientation, which avoids tedious single crystal X‐ray diffraction experiments. PMID:28809081

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

Automatic Tuning Matching Cycler (ATMC) in situ NMR spectroscopy as a novel approach for real-time investigations of Li- and Na-ion batteries

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

Pecher, Oliver; Bayley, Paul M.; Liu, Hao

We have developed and explored the use of a new Automatic Tuning Matching Cycler (ATMC) in situ NMR probe system to track the formation of intermediate phases and investigate electrolyte decomposition during electrochemical cycling of Li- and Na-ion batteries (LIBs and NIBs). The new approach addresses many of the issues arising during in situ NMR, e.g., significantly different shifts of the multi-component samples, changing sample conditions (such as the magnetic susceptibility and conductivity) during cycling, signal broadening due to paramagnetism as well as interferences between the NMR and external cycler circuit that might impair the experiments. We provide practical insightmore » into how to conduct ATMC in situ NMR experiments and discuss applications of the methodology to LiFePO4 (LFP) and Na3V2(PO4)2F3 cathodes as well as Na metal anodes. Automatic frequency sweep 7Li in situ NMR reveals significant changes of the strongly paramagnetic broadened LFP line shape in agreement with the structural changes due to delithiation. Additionally, 31P in situ NMR shows a full separation of the electrolyte and cathode NMR signals and is a key feature for a deeper understanding of the processes occurring during charge/discharge on the local atomic scale of NMR. 31P in situ NMR with “on-the-fly” re-calibrated, varying carrier frequencies on Na3V2(PO4)2F3 as a cathode in a NIB enabled the detection of different P signals within a huge frequency range of 4000 ppm. The experiments show a significant shift and changes in the number as well as intensities of 31P signals during desodiation/sodiation of the cathode. The in situ experiments reveal changes of local P environments that in part have not been seen in ex situ NMR investigations. Furthermore, we applied ATMC 23Na in situ NMR on symmetrical Na–Na cells during galvanostatic plating. An automatic adjustment of the NMR carrier frequency during the in situ experiment ensured on-resonance conditions for the Na metal and electrolyte peak, respectively. Thus, interleaved measurements with different optimal NMR set-ups for the metal and electrolyte, respectively, became possible. This allowed the formation of different Na metal species as well as a quantification of electrolyte consumption during the electrochemical experiment to be monitored. The new approach is likely to benefit a further understanding of Na-ion battery chemistries.« less

Automatic Tuning Matching Cycler (ATMC) in situ NMR spectroscopy as a novel approach for real-time investigations of Li- and Na-ion batteries

NASA Astrophysics Data System (ADS)

Pecher, Oliver; Bayley, Paul M.; Liu, Hao; Liu, Zigeng; Trease, Nicole M.; Grey, Clare P.

2016-04-01

We have developed and explored the use of a new Automatic Tuning Matching Cycler (ATMC) in situ NMR probe system to track the formation of intermediate phases and investigate electrolyte decomposition during electrochemical cycling of Li- and Na-ion batteries (LIBs and NIBs). The new approach addresses many of the issues arising during in situ NMR, e.g., significantly different shifts of the multi-component samples, changing sample conditions (such as the magnetic susceptibility and conductivity) during cycling, signal broadening due to paramagnetism as well as interferences between the NMR and external cycler circuit that might impair the experiments. We provide practical insight into how to conduct ATMC in situ NMR experiments and discuss applications of the methodology to LiFePO4 (LFP) and Na3V2(PO4)2F3 cathodes as well as Na metal anodes. Automatic frequency sweep 7Li in situ NMR reveals significant changes of the strongly paramagnetic broadened LFP line shape in agreement with the structural changes due to delithiation. Additionally, 31P in situ NMR shows a full separation of the electrolyte and cathode NMR signals and is a key feature for a deeper understanding of the processes occurring during charge/discharge on the local atomic scale of NMR. 31P in situ NMR with "on-the-fly" re-calibrated, varying carrier frequencies on Na3V2(PO4)2F3 as a cathode in a NIB enabled the detection of different P signals within a huge frequency range of 4000 ppm. The experiments show a significant shift and changes in the number as well as intensities of 31P signals during desodiation/sodiation of the cathode. The in situ experiments reveal changes of local P environments that in part have not been seen in ex situ NMR investigations. Furthermore, we applied ATMC 23Na in situ NMR on symmetrical Na-Na cells during galvanostatic plating. An automatic adjustment of the NMR carrier frequency during the in situ experiment ensured on-resonance conditions for the Na metal and electrolyte peak, respectively. Thus, interleaved measurements with different optimal NMR set-ups for the metal and electrolyte, respectively, became possible. This allowed the formation of different Na metal species as well as a quantification of electrolyte consumption during the electrochemical experiment to be monitored. The new approach is likely to benefit a further understanding of Na-ion battery chemistries.

NiAl Oxidation Reaction Processes Studied In Situ Using MEMS-Based Closed-Cell Gas Reaction Transmission Electron Microscopy

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

Unocic, Kinga A.; Shin, Dongwon; Unocic, Raymond R.

The nanoscale oxidation mechanisms and kinetics of a model β-NiAl system were investigated using in situ closed-cell gas reaction scanning transmission electron microscopy (STEM). Here, we directly visualize the dynamic structural and chemical changes that occur during high-temperature oxidation at a high spatial resolution of 50.3Ni–49.7Al (at.%) nanoparticles under static air conditions at 730 Torr with heating up to 750 °C at 5 °C/s. A MEMS-based gas cell system, with microfabricated heater devices and a gas delivery system, was used to reveal site-specific oxidation initiation sites. Through time-resolved annular dark-field STEM imaging, we tracked the nanoscale oxidation kinetics of Almore » 2O 3. After oxidation at 750 °C, nucleation of voids at the Ni/Al 2O 3 interface was observed along a NiAl grain boundary, followed by the formation of faceted NiO crystals. Small faceted cubic crystals of NiO were formed at the initial stage of oxidation at high PO 2 due to the outward self-diffusion of Ni 2+ ions, followed by the formation of a mixture of metastable and stable α-Al 2O 3 at the oxide/metal interface that is attributed to a PO 2 decrease with oxidation time, which agreed with thermodynamic modeling calculations. Furthermore, the results from these in situ oxidation experiments in the β-NiAl system are in agreement with the established oxidation mechanisms; however, with in situ closed-cell gas microscopy it is now feasible to investigate nanoscale oxidation mechanisms and kinetics in real time and at high spatial resolution and can be broadly applied to understand the basic high-temperature oxidation mechanisms for a wide range of alloy compositions.« less

NiAl Oxidation Reaction Processes Studied In Situ Using MEMS-Based Closed-Cell Gas Reaction Transmission Electron Microscopy

DOE PAGES

Unocic, Kinga A.; Shin, Dongwon; Unocic, Raymond R.; ...

2017-02-07

The nanoscale oxidation mechanisms and kinetics of a model β-NiAl system were investigated using in situ closed-cell gas reaction scanning transmission electron microscopy (STEM). Here, we directly visualize the dynamic structural and chemical changes that occur during high-temperature oxidation at a high spatial resolution of 50.3Ni–49.7Al (at.%) nanoparticles under static air conditions at 730 Torr with heating up to 750 °C at 5 °C/s. A MEMS-based gas cell system, with microfabricated heater devices and a gas delivery system, was used to reveal site-specific oxidation initiation sites. Through time-resolved annular dark-field STEM imaging, we tracked the nanoscale oxidation kinetics of Almore » 2O 3. After oxidation at 750 °C, nucleation of voids at the Ni/Al 2O 3 interface was observed along a NiAl grain boundary, followed by the formation of faceted NiO crystals. Small faceted cubic crystals of NiO were formed at the initial stage of oxidation at high PO 2 due to the outward self-diffusion of Ni 2+ ions, followed by the formation of a mixture of metastable and stable α-Al 2O 3 at the oxide/metal interface that is attributed to a PO 2 decrease with oxidation time, which agreed with thermodynamic modeling calculations. Furthermore, the results from these in situ oxidation experiments in the β-NiAl system are in agreement with the established oxidation mechanisms; however, with in situ closed-cell gas microscopy it is now feasible to investigate nanoscale oxidation mechanisms and kinetics in real time and at high spatial resolution and can be broadly applied to understand the basic high-temperature oxidation mechanisms for a wide range of alloy compositions.« less

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.

Detecting diffusion-diffraction patterns in size distribution phantoms using double-pulsed field gradient NMR: Theory and experiments.

PubMed

Shemesh, Noam; Ozarslan, Evren; Basser, Peter J; Cohen, Yoram

2010-01-21

NMR observable nuclei undergoing restricted diffusion within confining pores are important reporters for microstructural features of porous media including, inter-alia, biological tissues, emulsions and rocks. Diffusion NMR, and especially the single-pulsed field gradient (s-PFG) methodology, is one of the most important noninvasive tools for studying such opaque samples, enabling extraction of important microstructural information from diffusion-diffraction phenomena. However, when the pores are not monodisperse and are characterized by a size distribution, the diffusion-diffraction patterns disappear from the signal decay, and the relevant microstructural information is mostly lost. A recent theoretical study predicted that the diffusion-diffraction patterns in double-PFG (d-PFG) experiments have unique characteristics, such as zero-crossings, that make them more robust with respect to size distributions. In this study, we theoretically compared the signal decay arising from diffusion in isolated cylindrical pores characterized by lognormal size distributions in both s-PFG and d-PFG methodologies using a recently presented general framework for treating diffusion in NMR experiments. We showed the gradual loss of diffusion-diffraction patterns in broadening size distributions in s-PFG and the robustness of the zero-crossings in d-PFG even for very large standard deviations of the size distribution. We then performed s-PFG and d-PFG experiments on well-controlled size distribution phantoms in which the ground-truth is well-known a priori. We showed that the microstructural information, as manifested in the diffusion-diffraction patterns, is lost in the s-PFG experiments, whereas in d-PFG experiments the zero-crossings of the signal persist from which relevant microstructural information can be extracted. This study provides a proof of concept that d-PFG may be useful in obtaining important microstructural features in samples characterized by size distributions.

Experimental data from coastal diffusion tests. [Smoke diffusion over coastal waters

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

Raynor, G S; Brown, R M; SethuRaman, S

1976-10-01

Data are reported from a series of seven experiments on the diffusion of smoke plumes over northeast Atlantic Ocean coastal waters in response to wind fluctuations and other meteorological variables. A qualitative description of smoke behavior during each experiment is included and photographs of the smoke are included to illustrate the type of diffusion observed. (CH)

Improving the accuracy of the gradient method for determining soil carbon dioxide efflux

USDA-ARS?s Scientific Manuscript database

Continuous soil CO2 efflux (Fsoil) estimates can be obtained by the gradient method (GM), but the utility of the method is hindered by uncertainties in the application of published models for the diffusion coefficient (Ds). We compared two in-situ methods for determining Ds, one based calibrating th...

Multiphysics processes in partially saturated fractured rock: Experiments and models from Yucca Mountain

NASA Astrophysics Data System (ADS)

Rutqvist, Jonny; Tsang, Chin-Fu

2012-09-01

The site investigations at Yucca Mountain, Nevada, have provided us with an outstanding data set, one that has significantly advanced our knowledge of multiphysics processes in partially saturated fractured geological media. Such advancement was made possible, foremost, by substantial investments in multiyear field experiments that enabled the study of thermally driven multiphysics and testing of numerical models at a large spatial scale. The development of coupled-process models within the project have resulted in a number of new, advanced multiphysics numerical models that are today applied over a wide range of geoscientific research and geoengineering applications. Using such models, the potential impact of thermal-hydrological-mechanical (THM) multiphysics processes over the long-term (e.g., 10,000 years) could be predicted and bounded with some degree of confidence. The fact that the rock mass at Yucca Mountain is intensively fractured enabled continuum models to be used, although discontinuum models were also applied and are better suited for analyzing some issues, especially those related to predictions of rockfall within open excavations. The work showed that in situ tests (rather than small-scale laboratory experiments alone) are essential for determining appropriate input parameters for multiphysics models of fractured rocks, especially related to parameters defining how permeability might evolve under changing stress and temperature. A significant laboratory test program at Yucca Mountain also made important contributions to the field of rock mechanics, showing a unique relation between porosity and mechanical properties, a time dependency of strength that is significant for long-term excavation stability, a decreasing rock strength with sample size using very large core experiments, and a strong temperature dependency of the thermal expansion coefficient for temperatures up to 200°C. The analysis of in situ heater experiments showed that fracture closure/opening caused by changes in normal stress across fractures was the dominant mechanism for thermally induced changes in intrinsic fracture permeability during rock mass heating/cooling and that fracture shear dilation appears to be less significant. Significant effort was devoted to predicting the long-term stability of underground excavations under (mechanical) strength degradation and seismic loading, perhaps one of the most challenging tasks within the project. We note that such long-term strength degradation is actually an example of a chemically mediated process governed by underlying (microscopic) stress corrosion and chemical diffusion processes. In the Yucca Mountain Project, such chemically mediated mechanical changes were considered implicitly through model calibrations against laboratory and in situ heater experiments at temperatures anticipated to be experienced by the rock. A possible future research direction would be to simulate such processes mechanistically in a complete coupled THMC framework where C denotes chemical processes.

Non-invasive characterization of colorants by portable diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy and chemometrics

NASA Astrophysics Data System (ADS)

Manfredi, Marcello; Barberis, Elettra; Aceto, Maurizio; Marengo, Emilio

2017-06-01

During the last years the need for non-invasive and non-destructive analytical methods brought to the development and application of new instrumentation and analytical methods for the in-situ analysis of cultural heritage objects. In this work we present the application of a portable diffuse reflectance infrared Fourier transform (DRIFT) method for the non-invasive characterization of colorants prepared according to ancient recipes and using egg white and Gum Arabic as binders. Approximately 50 colorants were analyzed with the DRIFT spectroscopy: we were able to identify and discriminate the most used yellow (i.e. yellow ochres, Lead-tin Yellow, Orpiment, etc.), red (i.e. red ochres, Hematite) and blue (i.e. Lapis Lazuli, Azurite, indigo) colorants, creating a complete DRIFT spectral library. The Principal Component Analysis-Discriminant Analysis (PCA-DA) was then employed for the colorants classification according to the chemical/mineralogical composition. The DRIFT analysis was also performed on a gouache painting of the artist Sutherland; and the colorants used by the painter were identified directly in-situ and in a non-invasive manner.

Diffusion of Salt in Tap Water

ERIC Educational Resources Information Center

Booth, C.; And Others

1978-01-01

A simple experiment is described to measure the diffusion coefficient of a solute in a fluid. Laboratory-made floats are used to monitor the density changes associated with diffusion behavior. The experiment is ideally suited for undergraduate project work. (BB)

A large-scale field trial of thin-layer capping of PCDD/F-contaminated sediments: Sediment-to-water fluxes up to 5 years post-amendment.

PubMed

Cornelissen, Gerard; Schaanning, Morten; Gunnarsson, Jonas S; Eek, Espen

2016-04-01

The longer-term effect (3-5 y) of thin-layer capping on in situ sediment-to-surface water fluxes was monitored in a large-scale field experiment in the polychlorinated dibenzodioxin and dibenzofuran (PCDD/F) contaminated Grenlandfjords, Norway (4 trial plots of 10,000 to 40,000 m(2) at 30 to 100 m water depth). Active caps (designed thickness 2.5 cm) were established in 2 fjords, consisting of dredged clean clay amended with powdered activated carbon (PAC) from anthracite. These active caps were compared to 2 nonactive caps in one of the fjords (designed thickness 5 cm) consisting of either clay only (i.e., without PAC) or crushed limestone. Sediment-to-water PCDD/F fluxes were measured in situ using diffusion chambers. An earlier study showed that during the first 2 years after thin-layer capping, flux reductions relative to noncapped reference fields were more extensive at the fields capped with nonactive caps (70%-90%) than at the ones with PAC-containing caps (50%-60%). However, the present work shows that between 3 and 5 years after thin-layer capping, this trend was reversed and cap effectiveness in reducing fluxes was increasing to 80% to 90% for the PAC caps, whereas cap effectiveness of the nonactive caps decreased to 20% to 60%. The increasing effectiveness over time of PAC-containing "active" caps is explained by a combination of slow sediment-to-PAC mass transfer of PCDD/Fs and bioturbation by benthic organisms. The decreasing effectiveness of "nonactive" limestone and clay caps is explained by deposition of contaminated particles on top of the caps. The present field data indicate that the capping efficiency of thin active caps (i.e., enriched with PAC) can improve over time as a result of slow diffusive PCDD/F transfer from sediment to PAC particles and better mixing of the PAC by bioturbation. © 2015 SETAC.

NMR-based diffusion pore imaging.

PubMed

Laun, Frederik Bernd; Kuder, Tristan Anselm; Wetscherek, Andreas; Stieltjes, Bram; Semmler, Wolfhard

2012-08-01

Nuclear magnetic resonance (NMR) diffusion experiments offer a unique opportunity to study boundaries restricting the diffusion process. In a recent Letter [Phys. Rev. Lett. 107, 048102 (2011)], we introduced the idea and concept that such diffusion experiments can be interpreted as NMR imaging experiments. Consequently, images of closed pores, in which the spins diffuse, can be acquired. In the work presented here, an in-depth description of the diffusion pore imaging technique is provided. Image artifacts due to gradient profiles of finite duration, field inhomogeneities, and surface relaxation are considered. Gradients of finite duration lead to image blurring and edge enhancement artifacts. Field inhomogeneities have benign effects on diffusion pore images, and surface relaxation can lead to a shrinkage and shift of the pore image. The relation between boundary structure and the imaginary part of the diffusion weighted signal is analyzed, and it is shown that information on pore coherence can be obtained without the need to measure the phase of the diffusion weighted signal. Moreover, it is shown that quite arbitrary gradient profiles can be used for diffusion pore imaging. The matrices required for numerical calculations are stated and provided as supplemental material.

The rise and fall of stellar across the peak of cosmic star formation history: effects of mergers versus diffuse stellar mass acquisition

NASA Astrophysics Data System (ADS)

Welker, C.; Dubois, Y.; Devriendt, J.; Pichon, C.; Kaviraj, S.; Peirani, S.

2017-02-01

Building galaxy merger trees from a state-of-the-art cosmological hydrodynamical simulation, Horizon-AGN, we perform a statistical study of how mergers and diffuse stellar mass acquisition processes drive galaxy morphologic properties above z > 1. By diffuse mass acquisition here, we mean both accretion of stars by unresolved mergers (relative stellar mass growth smaller than 4.5 per cent) as well as in situ star formation when no resolved mergers are detected along the main progenitor branch of a galaxy. We investigate how stellar densities, galaxy sizes and galaxy morphologies (defined via shape parameters derived from the inertia tensor of the stellar density) depend on mergers of different mass ratios. We investigate how stellar densities, effective radii and shape parameters derived from the inertia tensor depend on mergers of different mass ratios. We find strong evidence that diffuse stellar accretion and in situ formation tend to flatten small galaxies over cosmic time, leading to the formation of discs. On the other hand, mergers, and not only the major ones, exhibit a propensity to puff up and destroy stellar discs, confirming the origin of elliptical galaxies. We confirm that mergers grow galaxy sizes more efficiently than diffuse processes (r_{0.5}∝ M_s^{0.85} and r_{0.5}∝ M_s^{0.1} on average, respectively) and we also find that elliptical galaxies are more susceptible to grow in size through mergers than disc galaxies with a size-mass evolution r_{0.5}∝ M_s^{1.2} instead of r_{0.5}∝ M_s^{-0.5}-M^{0.5} for discs depending on the merger mass ratio. The gas content drives the size-mass evolution due to merger with a faster size growth for gas-poor galaxies r_{0.5}∝ M_s2 than for gas-rich galaxies r0.5 ∝ Ms.

Flat-plate solar array project process development area, process research of non-CZ silicon material

NASA Technical Reports Server (NTRS)

Campbell, R. B.

1984-01-01

The program is designed to investigate the fabrication of solar cells on N-type base material by a simultaneous diffusion of N-type and P-type dopants to form an P(+)NN(+) structure. The results of simultaneous diffusion experiments are being compared to cells fabricated using sequential diffusion of dopants into N-base material in the same resistivity range. The process used for the fabrication of the simultaneously diffused P(+)NN(+) cells follows the standard Westinghouse baseline sequence for P-base material except that the two diffusion processes (boron and phosphorus) are replaced by a single diffusion step. All experiments are carried out on N-type dendritic web grown in the Westinghouse pre-pilot facility. The resistivities vary from 0.5 (UC OMEGA)cm to 5 (UC OMEGA)cm. The dopant sources used for both the simultaneous and sequential diffusion experiments are commercial metallorganic solutions with phosphorus or boron components. After these liquids are applied to the web surface, they are baked to form a hard glass which acts as a diffusion source at elevated temperatures. In experiments performed thus far, cells produced in sequential diffusion tests have properties essentially equal to the baseline N(+)PP(+) cells. However, the simultaneous diffusions have produced cells with much lower IV characteristics mainly due to cross-doping of the sources at the diffusion temperature. This cross-doping is due to the high vapor pressure phosphorus (applied as a metallorganic to the back surface) diffusion through the SiO2 mask and then acting as a diffusant source for the front surface.

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.

Homogenization kinetics of a nickel-based superalloy produced by powder bed fusion laser sintering

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

Zhang, Fan; Levine, Lyle E.; Allen, Andrew J.

2017-04-01

Additively manufactured (AM) metal components often exhibit fine dendritic microstructures and elemental segregation due to the initial rapid solidification and subsequent melting and cooling during the build process, which without homogenization would adversely affect materials performance. In this letter, we report in situ observation of the homogenization kinetics of an AM nickel-based superalloy using synchrotron small angle X-ray scattering. The identified kinetic time scale is in good agreement with thermodynamic diffusion simulation predictions using microstructural dimensions acquired by ex situ scanning electron microscopy. These findings could serve as a recipe for predicting, observing, and validating homogenization treatments in AM materials.

Homogenization Kinetics of a Nickel-based Superalloy Produced by Powder Bed Fusion Laser Sintering.

PubMed

Zhang, Fan; Levine, Lyle E; Allen, Andrew J; Campbell, Carelyn E; Lass, Eric A; Cheruvathur, Sudha; Stoudt, Mark R; Williams, Maureen E; Idell, Yaakov

2017-04-01

Additively manufactured (AM) metal components often exhibit fine dendritic microstructures and elemental segregation due to the initial rapid solidification and subsequent melting and cooling during the build process, which without homogenization would adversely affect materials performance. In this letter, we report in situ observation of the homogenization kinetics of an AM nickel-based superalloy using synchrotron small angle X-ray scattering. The identified kinetic time scale is in good agreement with thermodynamic diffusion simulation predictions using microstructural dimensions acquired by ex situ scanning electron microscopy. These findings could serve as a recipe for predicting, observing, and validating homogenization treatments in AM materials.

On the role of humic acids' carboxyl groups in the binding of charged organic compounds.

PubMed

Smilek, Jiří; Sedláček, Petr; Kalina, Michal; Klučáková, Martina

2015-11-01

Interactions of humic acids (HAs) with two cationic dyes (methylene blue and rhodamine 6G) were studied using a unique combination of diffusion and partitioning studies in HAs, containing hydrogels and batch sorption experiments. In order to investigate the involvement of carboxyl groups of HAs in these interactions, all experiments were performed for both, the original lignite HAs and HAs with selectively methylated carboxyls. The results of the diffusion experiments confirm that the interactions between the solute and humic substances have a strong impact on the rate of diffusion process. Surprisingly, the effect is almost equally approved for original and methylated HAs. On the other hand, the results of batch sorption experiments show strong improvement of the sorption capacity (methylated HAs), which is explained by changed morphology of alkylated HAs. The comparison of the results of diffusion and adsorption experiments shows that the diffusion experiments simulate the transport of solutes in natural humics containing environment more reasonably. Copyright © 2015 Elsevier Ltd. All rights reserved.

Kinetics of Hydrolysis of Acetic Anhydride by In-Situ FTIR Spectroscopy: An Experiment for the Undergraduate Laboratory

ERIC Educational Resources Information Center

Haji, Shaker; Erkey, Can

2005-01-01

A reaction kinetics experiment for the chemical engineering undergraduate laboratory course was developed in which in-situ Fourier Transfer Infrared spectroscopy was used to measure reactant and product concentrations. The kinetics of the hydrolysis of acetic anhydride was determined by experiments carried out in a batch reactor. The results…

High density diffusion-free nanowell arrays.

PubMed

Takulapalli, Bharath R; Qiu, Ji; Magee, D Mitchell; Kahn, Peter; Brunner, Al; Barker, Kristi; Means, Steven; Miersch, Shane; Bian, Xiaofang; Mendoza, Alex; Festa, Fernanda; Syal, Karan; Park, Jin G; LaBaer, Joshua; Wiktor, Peter

2012-08-03

Proteomics aspires to elucidate the functions of all proteins. Protein microarrays provide an important step by enabling high-throughput studies of displayed proteins. However, many functional assays of proteins include untethered intermediates or products, which could frustrate the use of planar arrays at very high densities because of diffusion to neighboring features. The nucleic acid programmable protein array (NAPPA) is a robust in situ synthesis method for producing functional proteins just-in-time, which includes steps with diffusible intermediates. We determined that diffusion of expressed proteins led to cross-binding at neighboring spots at very high densities with reduced interspot spacing. To address this limitation, we have developed an innovative platform using photolithographically etched discrete silicon nanowells and used NAPPA as a test case. This arrested protein diffusion and cross-binding. We present confined high density protein expression and display, as well as functional protein-protein interactions, in 8000 nanowell arrays. This is the highest density of individual proteins in nanovessels demonstrated on a single slide. We further present proof of principle results on ultrahigh density protein arrays capable of up to 24000 nanowells on a single slide.

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.

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.

Size dependent behavior of Fe 3O 4 crystals during electrochemical (de)lithiation: an in situ X-ray diffraction, ex situ X-ray absorption spectroscopy, transmission electron microscopy and theoretical investigation

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

Bock, David C.; Pelliccione, Christopher J.; Zhang, Wei

Here, the iron oxide magnetite, Fe 3O 4, is a promising conversion type lithium ion battery anode material due to its high natural abundance, low cost and high theoretical capacity. While the close packing of ions in the inverse spinel structure of Fe 3O 4 enables high energy density, it also limits the kinetics of lithium ion diffusion in the material. Nanosizing of Fe 3O 4 to reduce the diffusion path length is an effective strategy for overcoming this issue and results in improved rate capability. However, the impact of nanosizing on the multiple structural transformations that occur during themore » electrochemical (de)lithiation reaction in Fe 3O 4 is poorly understood. In this study, the influence of crystallite size on the lithiation-conversion mechanisms in Fe 3O 4 is investigated using complementary X-ray techniques along with transmission electron microscopy (TEM) and continuum level simulations on electrodes of two different Fe 3O 4 crystallite sizes. In situ X-ray diffraction (XRD) measurements were utilized to track the changes to the crystalline phases during (de)lithiation. X-ray absorption spectroscopy (XAS) measurements at multiple points during the (de)lithiation processes provided local electronic and atomic structural information. Tracking the crystalline and nanocrystalline phases during the first (de)lithiation provides experimental evidence that (1) the lithiation mechanism is non-uniform and dependent on crystallite size, where increased Li + diffusion length in larger crystals results in conversion to Fe 0 metal while insertion of Li + into spinel-Fe 3O 4 is still occurring, and (2) the disorder and size of the Fe metal domains formed when either material is fully lithiated impacts the homogeneity of the FeO phase formed during the subsequent delithiation.« less

Size dependent behavior of Fe 3O 4 crystals during electrochemical (de)lithiation: an in situ X-ray diffraction, ex situ X-ray absorption spectroscopy, transmission electron microscopy and theoretical investigation

DOE PAGES

Bock, David C.; Pelliccione, Christopher J.; Zhang, Wei; ...

2017-07-17

Here, the iron oxide magnetite, Fe 3O 4, is a promising conversion type lithium ion battery anode material due to its high natural abundance, low cost and high theoretical capacity. While the close packing of ions in the inverse spinel structure of Fe 3O 4 enables high energy density, it also limits the kinetics of lithium ion diffusion in the material. Nanosizing of Fe 3O 4 to reduce the diffusion path length is an effective strategy for overcoming this issue and results in improved rate capability. However, the impact of nanosizing on the multiple structural transformations that occur during themore » electrochemical (de)lithiation reaction in Fe 3O 4 is poorly understood. In this study, the influence of crystallite size on the lithiation-conversion mechanisms in Fe 3O 4 is investigated using complementary X-ray techniques along with transmission electron microscopy (TEM) and continuum level simulations on electrodes of two different Fe 3O 4 crystallite sizes. In situ X-ray diffraction (XRD) measurements were utilized to track the changes to the crystalline phases during (de)lithiation. X-ray absorption spectroscopy (XAS) measurements at multiple points during the (de)lithiation processes provided local electronic and atomic structural information. Tracking the crystalline and nanocrystalline phases during the first (de)lithiation provides experimental evidence that (1) the lithiation mechanism is non-uniform and dependent on crystallite size, where increased Li + diffusion length in larger crystals results in conversion to Fe 0 metal while insertion of Li + into spinel-Fe 3O 4 is still occurring, and (2) the disorder and size of the Fe metal domains formed when either material is fully lithiated impacts the homogeneity of the FeO phase formed during the subsequent delithiation.« less

Fluorescence correlation spectroscopy experiments to quantify free diffusion coefficients in reaction-diffusion systems: The case of Ca2 + and its dyes

NASA Astrophysics Data System (ADS)

Sigaut, Lorena; Villarruel, Cecilia; Ponce, María Laura; Ponce Dawson, Silvina

2017-06-01

Many cell signaling pathways involve the diffusion of messengers that bind and unbind to and from intracellular components. Quantifying their net transport rate under different conditions then requires having separate estimates of their free diffusion coefficient and binding or unbinding rates. In this paper, we show how performing sets of fluorescence correlation spectroscopy (FCS) experiments under different conditions, it is possible to quantify free diffusion coefficients and on and off rates of reaction-diffusion systems. We develop the theory and present a practical implementation for the case of the universal second messenger, calcium (Ca2 +) and single-wavelength dyes that increase their fluorescence upon Ca2 + binding. We validate the approach with experiments performed in aqueous solutions containing Ca2 + and Fluo4 dextran (both in its high and low affinity versions). Performing FCS experiments with tetramethylrhodamine-dextran in Xenopus laevis oocytes, we infer the corresponding free diffusion coefficients in the cytosol of these cells. Our approach can be extended to other physiologically relevant reaction-diffusion systems to quantify biophysical parameters that determine the dynamics of various variables of interest.

A compilation of global bio-optical in situ data for ocean-colour satellite applications

NASA Astrophysics Data System (ADS)

Valente, André; Sathyendranath, Shubha; Brotas, Vanda; Groom, Steve; Grant, Michael; Taberner, Malcolm; Antoine, David; Arnone, Robert; Balch, William M.; Barker, Kathryn; Barlow, Ray; Bélanger, Simon; Berthon, Jean-François; Beşiktepe, Şükrü; Brando, Vittorio; Canuti, Elisabetta; Chavez, Francisco; Claustre, Hervé; Crout, Richard; Frouin, Robert; García-Soto, Carlos; Gibb, Stuart W.; Gould, Richard; Hooker, Stanford; Kahru, Mati; Klein, Holger; Kratzer, Susanne; Loisel, Hubert; McKee, David; Mitchell, Brian G.; Moisan, Tiffany; Muller-Karger, Frank; O'Dowd, Leonie; Ondrusek, Michael; Poulton, Alex J.; Repecaud, Michel; Smyth, Timothy; Sosik, Heidi M.; Twardowski, Michael; Voss, Kenneth; Werdell, Jeremy; Wernand, Marcel; Zibordi, Giuseppe

2016-06-01

A compiled set of in situ data is important to evaluate the quality of ocean-colour satellite-data records. Here we describe the data compiled for the validation of the ocean-colour products from the ESA Ocean Colour Climate Change Initiative (OC-CCI). The data were acquired from several sources (MOBY, BOUSSOLE, AERONET-OC, SeaBASS, NOMAD, MERMAID, AMT, ICES, HOT, GeP&CO), span between 1997 and 2012, and have a global distribution. Observations of the following variables were compiled: spectral remote-sensing reflectances, concentrations of chlorophyll a, spectral inherent optical properties and spectral diffuse attenuation coefficients. The data were from multi-project archives acquired via the open internet services or from individual projects, acquired directly from data providers. Methodologies were implemented for homogenisation, quality control and merging of all data. No changes were made to the original data, other than averaging of observations that were close in time and space, elimination of some points after quality control and conversion to a standard format. The final result is a merged table designed for validation of satellite-derived ocean-colour products and available in text format. Metadata of each in situ measurement (original source, cruise or experiment, principal investigator) were preserved throughout the work and made available in the final table. Using all the data in a validation exercise increases the number of matchups and enhances the representativeness of different marine regimes. By making available the metadata, it is also possible to analyse each set of data separately. The compiled data are available at doi:10.1594/PANGAEA.854832 (Valente et al., 2015).

In situ electrochemical investigations of the kinetic and thermodynamic properties of nickel-metal hydride traction batteries

NASA Astrophysics Data System (ADS)

Yang, Xiao Guang; Liaw, Bor Yann

Although large ampere hour nickel-metal hydride (Ni-MH) traction batteries are in the stage of being commercialized for electric and hybrid vehicle applications, little is known about their performance characteristics. By using a standard Hg/HgO reference electrode in a commercial Ni-MH battery, we were able to conduct in situ measurements to determine both kinetic and thermodynamic properties of the system, including the characteristics of individual electrodes. Using the galvanostatic intermittent titration technique (GITT), we simultaneously and effectively determined the open-circuit voltage of the battery, the equilibrium electrode potentials, and the diffusion coefficient of proton and hydrogen in the nickel and metal hydride electrode, respectively, as a function of the states of charge (SOC). Using the current-step excitation technique, we found that the internal resistance of the battery primarily comes from the metal hydride electrode, which is greater by one order of magnitude than that of the Ni electrode. The cyclic linear micro-polarization experiments, on the other hand, showed that the charge-transfer resistance of the electrochemical reaction at the metal hydride electrode is about twice larger than that of the Ni counterpart above 20% SOC. In comparison, the internal resistance is an order of magnitude smaller than those of the electrochemical charge-transfer reactions. The micro-polarization technique also allowed us to calculate the exchange current densities of the respective electrode electrochemical reactions and the associated specific exchange current densities. These in situ, simple but detailed, characterizations of the thermodynamic and kinetic properties of the Ni-MH system provided valuable information for better understanding of the battery performance.

Evaluation of polymerization shrinkage of resin cements through in vitro and in situ experiments

NASA Astrophysics Data System (ADS)

Franco, A. P. G. O.; Karam, L. Z.; Pulido, C. A.; Gomes, O. M. M.; Kalinowski, H. J.

2014-08-01

The aim of this study was to evaluate the behavior of two types of resin cements , conventional dual and dual self adhesive, through in vitro and in situ experiments. For the in vitro assay were selected two resin cements that were handled and dispensed over a mylar strip supported by a glass plate. The Bragg grating sensors were positioned and another portion of cement. was placed, covered by another mylar strip. For the in situ experiment 16 single-rooted teeth were selected who were divided into 2 groups: group 1 - conventional dual resin cement Relyx ARC and group 2 - dual self adhesive resin cement Relyx U200 ( 3M/ESPE ). The teeth were treated and prepared to receive the intracanal posts. Two Bragg grating sensors were recorded and introduced into the root canal at different apical and coronal positions. The results showed that the in vitro experiment presented similar values of polymerization shrinkage that the in situ experiment made in cervical position; whereas Relyx ARC resulted lower values compared to Relyx U200; and cervical position showed higher shrinkage than the apical.

Discerning crystal growth from diffusion profiles in zoned olivine by in situ Mg–Fe isotopic analyses

USGS Publications Warehouse

Sio, Corliss Kin I.; Dauphas, Nicolas; Teng, Fang-Zhen; Chaussidon, Marc; Helz, Rosalind T.; Roskosz, Mathieu

2013-01-01

Mineral zoning is used in diffusion-based geospeedometry to determine magmatic timescales. Progress in this field has been hampered by the challenge to discern mineral zoning produced by diffusion from concentration gradients inherited from crystal growth. A zoned olivine phenocryst from Kilauea Iki lava lake (Hawaii) was selected for this study to evaluate the potential of Mg and Fe isotopes for distinguishing these two processes. Microdrilling of the phenocryst (∼300 μm drill holes) followed by MC-ICPMS analysis of the powders revealed negatively coupled Mg and Fe isotopic fractionations (δ26Mg from +0.1‰ to −0.2‰ and δ56Fe from −1.2‰ to −0.2‰ from core to rim), which can only be explained by Mg–Fe exchange between melt and olivine. The data can be explained with ratios of diffusivities of Mg and Fe isotopes in olivine scaling as D2/D1 = (m1/m2)β with βMg ∼0.16 and βFe ∼0.27. LA-MC-ICPMS and MC-SIMS Fe isotopic measurements are developed and are demonstrated to yield accurate δ56Fe measurements within precisions of ∼0.2‰ (1 SD) at spatial resolutions of ∼50 μm. δ56Fe and δ26Mg stay constant with Fo# in the rim (late-stage overgrowth), whereas in the core (original phenocryst) δ56Fe steeply trends toward lighter compositions and δ26Mg trends toward heavier compositions with higher Fo#. A plot of δ56Fe vs. Fo# immediately distinguishes growth-controlled from diffusion-controlled zoning in these two regions. The results are consistent with the idea that large isotopic fractionation accompanies chemical diffusion in crystals, whereas fractional crystallization induces little or no isotopic fractionation. The cooling timescale inferred from the chemical-isotope zoning profiles is consistent with the documented cooling history of the lava lake. In the absence of geologic context, in situ stable isotopic measurements may now be used to interpret the nature of mineral zoning. Stable isotope measurements by LA-MC-ICPMS and MC-SIMS can be used as standard petrologic tools to identify samples for diffusion-based geospeedometry.

Estimation of Knudsen diffusion coefficients from tracer experiments conducted with a binary gas system and a porous medium.

PubMed

Hibi, Yoshihiko; Kashihara, Ayumi

2018-03-01

A previous study has reported that Knudsen diffusion coefficients obtained by tracer experiments conducted with a binary gas system and a porous medium are consistently smaller than those obtained by permeability experiments conducted with a single-gas system and a porous medium. To date, however, that study is the only one in which tracer experiments have been conducted with a binary gas system. Therefore, to confirm this difference in Knudsen diffusion coefficients, we used a method we had developed previously to conduct tracer experiments with a binary carbon dioxide-nitrogen gas system and five porous media with permeability coefficients ranging from 10 -13 to 10 -11  m 2 . The results showed that the Knudsen diffusion coefficient of N 2 (D N2 ) (cm 2 /s) was related to the effective permeability coefficient k e (m 2 ) as D N2  = 7.39 × 10 7 k e 0.767 . Thus, the Knudsen diffusion coefficients of N 2 obtained by our tracer experiments were consistently 1/27 of those obtained by permeability experiments conducted with many porous media and air by other researchers. By using an inversion simulation to fit the advection-diffusion equation to the distribution of concentrations at observation points calculated by mathematically solving the equation, we confirmed that the method used to obtain the Knudsen diffusion coefficient in this study yielded accurate values. Moreover, because the Knudsen diffusion coefficient did not differ when columns with two different lengths, 900 and 1500 mm, were used, this column property did not influence the flow of gas in the column. The equation of the dusty gas model already includes obstruction factors for Knudsen diffusion and molecular diffusion, which relate to medium heterogeneity and tortuosity and depend only on the structure of the porous medium. Furthermore, there is no need to take account of any additional correction factor for molecular diffusion except the obstruction factor because molecular diffusion is only treated in a multicomponent gas system. Thus, molecular diffusion considers only the obstruction factor related to tortuosity. Therefore, we introduced a correction factor for a multicomponent gas system into the DGM equation, multiplying the Knudsen diffusion coefficient, which includes the obstruction factor related to tortuosity, by this correction factor. From the present experimental results, the value of this correction factor was 1/27, and it depended only on the structure of the gas system in the porous medium. Copyright © 2018 Elsevier B.V. All rights reserved.

Estimation of Knudsen diffusion coefficients from tracer experiments conducted with a binary gas system and a porous medium

NASA Astrophysics Data System (ADS)

Hibi, Yoshihiko; Kashihara, Ayumi

2018-03-01

A previous study has reported that Knudsen diffusion coefficients obtained by tracer experiments conducted with a binary gas system and a porous medium are consistently smaller than those obtained by permeability experiments conducted with a single-gas system and a porous medium. To date, however, that study is the only one in which tracer experiments have been conducted with a binary gas system. Therefore, to confirm this difference in Knudsen diffusion coefficients, we used a method we had developed previously to conduct tracer experiments with a binary carbon dioxide-nitrogen gas system and five porous media with permeability coefficients ranging from 10-13 to 10-11 m2. The results showed that the Knudsen diffusion coefficient of N2 (DN2) (cm2/s) was related to the effective permeability coefficient ke (m2) as DN2 = 7.39 × 107ke0.767. Thus, the Knudsen diffusion coefficients of N2 obtained by our tracer experiments were consistently 1/27 of those obtained by permeability experiments conducted with many porous media and air by other researchers. By using an inversion simulation to fit the advection-diffusion equation to the distribution of concentrations at observation points calculated by mathematically solving the equation, we confirmed that the method used to obtain the Knudsen diffusion coefficient in this study yielded accurate values. Moreover, because the Knudsen diffusion coefficient did not differ when columns with two different lengths, 900 and 1500 mm, were used, this column property did not influence the flow of gas in the column. The equation of the dusty gas model already includes obstruction factors for Knudsen diffusion and molecular diffusion, which relate to medium heterogeneity and tortuosity and depend only on the structure of the porous medium. Furthermore, there is no need to take account of any additional correction factor for molecular diffusion except the obstruction factor because molecular diffusion is only treated in a multicomponent gas system. Thus, molecular diffusion considers only the obstruction factor related to tortuosity. Therefore, we introduced a correction factor for a multicomponent gas system into the DGM equation, multiplying the Knudsen diffusion coefficient, which includes the obstruction factor related to tortuosity, by this correction factor. From the present experimental results, the value of this correction factor was 1/27, and it depended only on the structure of the gas system in the porous medium.

Detection of Explosive Vapors: The Roles of Exciton and Molecular Diffusion in Real-Time Sensing.

PubMed

Ali, Mohammad A; Shoaee, Safa; Fan, Shengqiang; Burn, Paul L; Gentle, Ian R; Meredith, Paul; Shaw, Paul E

2016-11-04

Time-resolved quartz crystal microbalance with in situ fluorescence measurements are used to monitor the sorption of the nitroaromatic (explosive) vapor, 2,4-dinitrotoluene (DNT) into a porous pentiptycene-containing poly(phenyleneethynylene) sensing film. Correlation of the nitroaromatic mass uptake with fluorescence quenching shows that the analyte diffusion follows the Case-II transport model, a film-swelling-limited process, in which a sharp diffusional front propagates at a constant velocity through the film. At a low vapor pressure of DNT of ≈16 ppb, the analyte concentration in the front is sufficiently high to give an average fluorophore-analyte separation of ≈1.5 nm. Hence, a long exciton diffusion length is not required for real-time sensing in the solid state. Rather the diffusion behavior of the analyte and the strength of the binding interaction between the analyte and the polymer play first-order roles in the fluorescence quenching process. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Proposed uses of laser light scattering instruments for polymerization studies

NASA Technical Reports Server (NTRS)

Mathias, Lon J.; Hoyle, Charles E.; Mclaughlin, Kevin; Mcmanus, Samuel P.; Caruthers, James M.; Runge, Michael L.

1989-01-01

Microgravity offers a unique environment for studying polymer diffusion and polymer polymerization reactions. The absence of convection currents, which are the major mode of mixing at the molecular level on Earth, are eliminated or reduced in the microgravity environment. More importantly, the prediction of unique copolymer composition development in microgravity allows controlled formation of new compositions of matter. The absence of mixing at the molecular level should produce unique short block copolymers available for the first time for comonomer compositions which normally lead to random or long block copolymer under good mixing. The investigation of fundamental polymer diffusion and polymer polymerization processes in microgravity is proposed. This effort will involve fundamental studies of monomer and polymer diffusion; their effects on initiation, propagation, and especially termination kinetics rate constant; and the accurate evaluation of copolymerization reactivity ratios in microgravity. The experimental design is presented for these studies along with an evaluation technique for in situ monitoring of polymer diffusion and polymerization kinetics.

Vertical phase separation in bulk heterojunction solar cells formed by in situ polymerization of fulleride

PubMed Central

Zhang, Lipei; Xing, Xing; Zheng, Lingling; Chen, Zhijian; Xiao, Lixin; Qu, Bo; Gong, Qihuang

2014-01-01

Vertical phase separation of the donor and the acceptor in organic bulk heterojunction solar cells is crucial to improve the exciton dissociation and charge transport efficiencies. This is because whilst the exciton diffusion length is limited, the organic film must be thick enough to absorb sufficient light. However, it is still a challenge to control the phase separation of a binary blend in a bulk heterojunction device architecture. Here we report the realization of vertical phase separation induced by in situ photo-polymerization of the acrylate-based fulleride. The power conversion efficiency of the devices with vertical phase separation increased by 20%. By optimising the device architecture, the power conversion efficiency of the single junction device reached 8.47%. We believe that in situ photo-polymerization of acrylate-based fulleride is a universal and controllable way to realise vertical phase separation in organic blends. PMID:24861168

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.

Analytic expressions for ULF wave radiation belt radial diffusion coefficients

PubMed Central

Ozeke, Louis G; Mann, Ian R; Murphy, Kyle R; Jonathan Rae, I; Milling, David K

2014-01-01

We present analytic expressions for ULF wave-derived radiation belt radial diffusion coefficients, as a function of L and Kp, which can easily be incorporated into global radiation belt transport models. The diffusion coefficients are derived from statistical representations of ULF wave power, electric field power mapped from ground magnetometer data, and compressional magnetic field power from in situ measurements. We show that the overall electric and magnetic diffusion coefficients are to a good approximation both independent of energy. We present example 1-D radial diffusion results from simulations driven by CRRES-observed time-dependent energy spectra at the outer boundary, under the action of radial diffusion driven by the new ULF wave radial diffusion coefficients and with empirical chorus wave loss terms (as a function of energy, Kp and L). There is excellent agreement between the differential flux produced by the 1-D, Kp-driven, radial diffusion model and CRRES observations of differential electron flux at 0.976 MeV—even though the model does not include the effects of local internal acceleration sources. Our results highlight not only the importance of correct specification of radial diffusion coefficients for developing accurate models but also show significant promise for belt specification based on relatively simple models driven by solar wind parameters such as solar wind speed or geomagnetic indices such as Kp. Key Points Analytic expressions for the radial diffusion coefficients are presented The coefficients do not dependent on energy or wave m value The electric field diffusion coefficient dominates over the magnetic PMID:26167440

Siderophile trace element diffusion in Fe-Ni alloys

NASA Astrophysics Data System (ADS)

Watson, Heather C.; Watson, E. Bruce

2003-09-01

Experiments were performed in a piston cylinder apparatus to characterize the diffusion behavior of the siderophile elements, Mo, Cu, Pd, Au, and Re in solid Fe-Ni alloy (90 wt.% Fe, 10 wt.% Ni). All experiments were conducted at 1 GPa and temperatures ranging from 1175 to 1400 °C. Activation energies of all elements fall between 270 kJ/mol (Cu) and 360 kJ/mol (Mo). Mo, Cu, Pd, and Au all show similar diffusivities at the same conditions, but the diffusivity of Re was consistently close to an order of magnitude lower. Initial experiments on other refractory elements (Os, Pt, and Ir) indicate that their diffusivities are close to or slightly lower than that of Re.

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.

Diffusion of 99-technetium in compacted bentonite under aerobic and anaerobic conditions

NASA Astrophysics Data System (ADS)

Večerník, P.; Jedináková-Křížová, V.

2006-01-01

The main aim of this study was to investigate diffusion of technetium 99Tc under different conditions. Because technetium represents one of the most dangerous fission products due to its very long halftime and high mobility in aerobic conditions diffusion experiments of technetium (as 99TcO 4 - anion) in Czech bentonite from Rokle locality have been carried out. For performance and evaluation of experiments the through-diffusion method was chosen and apparent (Da) and effective (De) diffusion coefficients were evaluated. The effects of particle mesh-size, dry bulk density and aerobic or anaerobic conditions on diffusion were studied. In the presence of oxygen, technetium occurs in oxidation state VII, as an anion, soluble and mobile in the environment. However, under reducing conditions it occurs in a lower oxidation states, mainly as insoluble oxides or hydroxides. Aerobic experiments were carried out under laboratory conditions and anaerobic experiments were performed in a nitrogen atmosphere in a glove box, to simulate the real underground conditions.

From screen to structure with a harvestable microfluidic device.

PubMed

Stojanoff, Vivian; Jakoncic, Jean; Oren, Deena A; Nagarajan, V; Poulsen, Jens-Christian Navarro; Adams-Cioaba, Melanie A; Bergfors, Terese; Sommer, Morten O A

2011-08-01

Advances in automation have facilitated the widespread adoption of high-throughput vapour-diffusion methods for initial crystallization screening. However, for many proteins, screening thousands of crystallization conditions fails to yield crystals of sufficient quality for structural characterization. Here, the rates of crystal identification for thaumatin, catalase and myoglobin using microfluidic Crystal Former devices and sitting-drop vapour-diffusion plates are compared. It is shown that the Crystal Former results in a greater number of identified initial crystallization conditions compared with vapour diffusion. Furthermore, crystals of thaumatin and lysozyme obtained in the Crystal Former were used directly for structure determination both in situ and upon harvesting and cryocooling. On the basis of these results, a crystallization strategy is proposed that uses multiple methods with distinct kinetic trajectories through the protein phase diagram to increase the output of crystallization pipelines.

Prepreg cure monitoring using diffuse reflectance-FTIR. [Fourier Transform Infrared Technique

NASA Technical Reports Server (NTRS)

Young, P. R.; Chang, A. C.

1984-01-01

An in situ diffuse reflectance-Fourier transform infrared technique was developed to determine infrared spectra of graphite fiber prepregs as they were being cured. A bismaleimide, an epoxy, and addition polyimide matrix resin prepregs were studied. An experimental polyimide adhesive was also examined. Samples were positioned on a small heater at the focal point of diffuse reflectance optics and programmed at 15 F/min while FTIR spectra were being scanned, averaged, and stored. An analysis of the resulting spectra provided basic insights into changes in matrix resin molecular structure which accompanied reactions such as imidization and crosslinking. An endo-exothermal isomerization involving reactive end-caps was confirmed for the addition polyimide prepregs. The results of this study contribute to a fundamental understanding of the processing of composites and adhesives. Such understanding will promote the development of more efficient cure cycles.

Memristors with diffusive dynamics as synaptic emulators for neuromorphic computing

DOE PAGES

Wang, Zhongrui; Joshi, Saumil; Savel’ev, Sergey E.; ...

2016-09-26

The accumulation and extrusion of Ca 2+ in the pre- and postsynaptic compartments play a critical role in initiating plastic changes in biological synapses. In order to emulate this fundamental process in electronic devices, we developed diffusive Ag-in-oxide memristors with a temporal response during and after stimulation similar to that of the synaptic Ca 2+ dynamics. In situ high-resolution transmission electron microscopy and nanoparticle dynamics simulations both demonstrate that Ag atoms disperse under electrical bias and regroup spontaneously under zero bias because of interfacial energy minimization, closely resembling synaptic influx and extrusion of Ca 2+, respectively. Furthermore, the diffusive memristormore » and its dynamics enable a direct emulation of both short- and long-term plasticity of biological synapses, representing an advance in hardware implementation of neuromorphic functionalities.« less

Gettering in multicrystalline silicon: A design-of-experiments approach

NASA Astrophysics Data System (ADS)

Schubert, W. K.

1994-12-01

Design-of-experiment methods were used to study gettering due to phosphorus diffusion and aluminum alloying in four industrial multicrystalline silicon materials: Silicon-Film material from AstroPower, heat-exchanger method (HEM) material from Crystal Systems, edge-defined film-fed growth (EFG) material from Mobil Solar, and cast material from Solarex. Time and temperature for the diffusion and alloy processes were chosen for a four-factor quadratic interaction experiment. Simple diagnostic devices were used to evaluate the gettering. Only EFG and HEM materials exhibited statistically significant gettering effects within the ranges used for the various parameters. Diffusion and alloying temperature were significant for HEM material; also there was a second-order interaction between the diffusion time and temperature. There was no interaction between the diffusion and alloying processes in HEM material. EFG material showed a first-order dependence on diffusion temperature and a second-order interaction between the diffusion temperature and the alloying time. Gettering recommendations for the HEM material were used to produce the best-yet Sandia cells on this material, but correlation with the gettering experiment was not strong. Some of the discrepancy arises from necessary processing differences between the diagnostic devices and regular solar cells. This issue and other lessons learned concerning this type of experiment are discussed.

Neutron Production from In-situ Heavy Ice Coated Targets at Vulcan

NASA Astrophysics Data System (ADS)

Morrison, John; Krygier, A. G.; Kar, S.; Ahmed, H.; Alejo, A.; Clarke, R.; Fuchs, J.; Green, A.; Jung, D.; Kleinschmidt, A.; Najmudin, Z.; Nakamura, H.; Norreys, P.; Notley, M.; Oliver, M.; Roth, M.; Vassura, L.; Zepf, M.; Borghesi, M.; Freeman, R. R.

2015-05-01

Laser based neutron production experiments have been performed utilizing ultra-high intensity laser accelerated ions impinging upon a secondary target. The neutron yield from such experiments may be improved if the accelerated ions were primarily deuterons taking advantage of the d-d cross section. Recent experiments have demonstrated that selective deuteron acceleration from in-situ heavy ice coating of targets can produce ion spectra where deuterons comprise > 99 % of the measured ions. Results will be presented from integrated neutron production experiments from heavy ice targets coated in-situ recently performed on the Vulcan laser at Rutherford Appleton Laboratory. We are grateful for the Staff at RAL and acknowledge funding from the US DoE. AFOSR, European Social Fund, and the Czech Republic.

Moisture Content and Migration Dynamics in Unsaturated Porous Media

NASA Technical Reports Server (NTRS)

Homsy, G. M.

1993-01-01

Fundamental studies of fluid mechanics and transport in partially saturated soils are presented. Solution of transient diffusion problems in support of the development of probes for the in-situ measurement of moisture content is given. Numerical and analytical methods are used to study the fundamental problem of meniscus and saturation front propagation in geometric models of porous media.

Vadose Zone Flow and Transport of Dissolved Organic Carbon at Multiple Scales in Humid Regimes

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

Jardine, Philip M; Mayes, Melanie; Mulholland, Patrick J

2006-06-01

Scientists must embrace the necessity to offset global CO{sub 2} emissions regardless of politics. Efforts to enhance terrestrial organic carbon sequestration have traditionally focused on aboveground biomass and surface soils. An unexplored potential exists in thick lower horizons of widespread, mature soils such as Alfisols, Ultisols, and Oxisols. We present a case study of fate and transport of dissolved organic carbon (DOC) in a highly weathered Ultisol, involving spatial scales from the laboratory to the landscape. Our objectives were to interpret processes observed at various scales and provide an improved understanding of coupled hydrogeochemical mechanisms that control DOC mobility andmore » sequestration in deep subsoils within humid climatic regimes. Our approach is multiscale, using laboratory-scale batch and soil columns (0.2 by 1.0 m), an in situ pedon (2 by 2 by 3 m), a well-instrumented subsurface facility on a subwatershed (0.47 ha), and ephemeral and perennial stream discharge at the landscape scale (38.4 ha). Laboratory-scale experiments confirmed that lower horizons have the propensity to accumulate DOC, but that preferential fracture flow tends to limit sequestration. Intermediate-scale experiments demonstrated the beneficial effects of C diffusion into soil micropores. Field- and landscape-scale studies demonstrated coupled hydrological, geochemical, and microbiological mechanisms that limit DOC sequestration, and their sensitivity to local environmental conditions. Our results suggest a multi-scale approach is necessary to assess the propensity of deep subsoils to sequester organic C in situ. By unraveling fundamental organic C sequestration mechanisms, we improve the conceptual and quantitative understanding needed to predict and alter organic C budgets in soil systems.« less

In situ synthesis of g-C3N4/TiO2 heterojunction nanocomposites as a highly active photocatalyst for the degradation of Orange II under visible light irradiation.

PubMed

Ren, Bin; Wang, Tiecheng; Qu, Guangzhou; Deng, Fang; Liang, Dongli; Yang, Wenli; Liu, Meishan

2018-05-04

As a highly active photocatalyst, g-C 3 N 4 /TiO 2 heterojunction nanocomposites were in situ synthesized by simple ultrasonic mixing and calcination by using TiO 2 and melamine as precursors. The morphology and structure of the prepared photocatalysts were characterized by field emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, UV-Vis diffuse reflectance spectroscopy, and X-ray photoelectron spectroscopy. The photocatalytic activities of g-C 3 N 4 /TiO 2 nanocomposites to degrade Orange II (AO7) under visible light irradiation were evaluated. Results showed that the photocatalytic rate of the prepared g-C 3 N 4 /TiO 2 photocatalyst to degrade AO7 was about three times than that of pristine TiO 2 and g-C 3 N 4 . The g-C 3 N 4 /TiO 2 composite with a ratio of 1:4 had the highest degradation efficiency for AO7 solution. Its degradation efficiency under acidic conditions was significantly higher than that under alkaline conditions. The enhancement of photocatalytic activity can be attributed to the formation of heterojunctions between g-C 3 N 4 and TiO 2 , which leads to rapid charge transfer and the efficient separation of photogenerated electron-hole pairs. The recycling experiment indicated that the photocatalyst of g-C 3 N 4 /TiO 2 nanocomposites still maintained good photochemical stability and recyclability after five cycles; this finding was important for its practical applications. A series of free radical trapping experiments showed that •O 2 - played a crucial role in the degradation of AO7. Graphical Abstract ᅟ.

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

NASA Astrophysics Data System (ADS)

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

2014-01-01

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

Systematic variations of argon diffusion in feldspars and implications for thermochronometry

DOE PAGES

Cassata, William S.; Renne, Paul R.

2013-03-07

Coupled information about the time-dependent production and temperature-dependent diffusion of radiogenic argon in feldspars can be used to constrain the thermal evolution attending a host of Earth and planetary processes. To better assess the accuracy of thermal models, an understanding of the mechanisms and pathways by which argon diffuses in feldspars is desirable. Here we present step-heating Ar diffusion experiments conducted on feldspars with diverse compositions, structural states, and microstructural characteristics. The experiments reveal systematic variations in diffusive behavior that appear closely related to these variables, with apparent closure temperatures for 0.1–1 mm grains of ~200–400 °C (assuming a 10more » °C/Ma cooling rate). Given such variability, there is no broadly applicable set of diffusion parameters that can be utilized in feldspar thermal modeling; sample-specific data are required. Diffusion experiments conducted on oriented cleavage flakes do not reveal directionally-dependent diffusive anisotropy to within the resolution limits of our approach (approximately a factor of 2). Additional experiments aimed at constraining the physical significance of the diffusion domain are presented and indicate that unaltered feldspar crystals with or without coherent exsolution lamellae diffuse at the grain-scale, whereas feldspars containing hydrothermal alteration and/or incoherent sub-grain intergrowths do not. Arrhenius plots for argon diffusion in plagioclase and alkali feldspars appear to reflect a confluence of intrinsic diffusion kinetics and structural transitions that occur during incremental heating experiments. These structural transitions, along with sub-grain domain size variations, cause deviations from linearity (i.e., upward and downward curvature) on Arrhenius plots. An atomistic model for Arrhenius behavior is proposed that incorporates the variable lattice deformations of different feldspars in response to heating and compression. Furthermore, the resulting implications for accurately extrapolating laboratory-derived diffusion parameters to natural settings and over geologic time are discussed. We find that considerable inaccuracies may exist in published thermal histories obtained using multiple diffusion domain (MDD) models fit to Arrhenius plots for exsolved alkali feldspar, where the inferred Ar partial retention zones may be spuriously hot.« less

A Practical and Convenient Diffusion Apparatus: An Undergraduate Physical Chemistry Experiment.

ERIC Educational Resources Information Center

Clifford, Ben; Ochiai, E. I.

1980-01-01

Described is a diffusion apparatus to be used in an undergraduate physical chemistry laboratory experiment to determine the diffusion coefficients of aqueous solutions of sucrose and potassium dichromate. Included is the principle of the method, apparatus design and description, and experimental procedure. (Author/DS)

Scale-up considerations for surface collecting agent assisted in-situ burn crude oil spill response experiments in the Arctic: Laboratory to field-scale investigations.

PubMed

Bullock, Robin J; Aggarwal, Srijan; Perkins, Robert A; Schnabel, William

2017-04-01

In the event of a marine oil spill in the Arctic, government agencies, industry, and the public have a stake in the successful implementation of oil spill response. Because large spills are rare events, oil spill response techniques are often evaluated with laboratory and meso-scale experiments. The experiments must yield scalable information sufficient to understand the operability and effectiveness of a response technique under actual field conditions. Since in-situ burning augmented with surface collecting agents ("herders") is one of the few viable response options in ice infested waters, a series of oil spill response experiments were conducted in Fairbanks, Alaska, in 2014 and 2015 to evaluate the use of herders to assist in-situ burning and the role of experimental scale. This study compares burn efficiency and herder application for three experimental designs for in-situ burning of Alaska North Slope crude oil in cold, fresh waters with ∼10% ice cover. The experiments were conducted in three project-specific constructed venues with varying scales (surface areas of approximately 0.09 square meters, 9 square meters and 8100 square meters). The results from the herder assisted in-situ burn experiments performed at these three different scales showed good experimental scale correlation and no negative impact due to the presence of ice cover on burn efficiency. Experimental conclusions are predominantly associated with application of the herder material and usability for a given experiment scale to make response decisions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Biofouling: A critical consideration for evaluating in situ biotreatment feasibility

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

Kaufman, K.A.

1995-09-01

It is recognized by the EPA and many state and local regulatory agencies that in situ bioremedial treatment can be a technically sound and highly cost-effective method for the mitigation of soil and groundwater contamination, and numerous case histories corroborate this belief. Though not widely publicized (for understandable reasons), notable failures of similar treatment attempts can be traced to the consequences of biofouling, resultant from the inappropriate use of in situ treatment technologies. Such consequences can be related to the development of anaerobiosis due to inadequate diffusion of bioavailable oxygen to allow for aerobic metabolism within the contaminated soil matrix.more » Appropriate engineering and hydrogeological considerations of a site`s compatibility with in situ treatment requirements prior to process initiation can preclude the potential for the generation of noxious and/or toxic/explosive gases, as well as toxic endproducts of anaerobic microbial metabolism. Appropriate utilization of hydrogen peroxide, taking into account for the requirement for the enzyme catalase, and the biotoxic nature of hydrogen peroxide to many microorganisms, can minimize the deleterious effects of anaerobiosis and enhance oxidative bioremedial activity.« less

Optical in situ monitoring of plasma-enhanced atomic layer deposition process

NASA Astrophysics Data System (ADS)

Zeeshan Arshad, Muhammad; Jo, Kyung Jae; Kim, Hyun Gi; Jeen Hong, Sang

2018-06-01

An optical in situ process monitoring method for the early detection of anomalies in plasma process equipment is presented. Cyclic process steps of precursor treatment and plasma reaction for the deposition of an angstrom-scale film increase their complexity to ensure the process quality. However, a small deviation in process parameters, for instance, gas flow rate, process temperature, or RF power, may jeopardize the deposited film quality. As a test vehicle for the process monitoring, we have investigated the aluminum-oxide (Al2O3) encapsulation process in plasma-enhanced atomic layer deposition (PEALD) to form a moisture and oxygen diffusion barrier in organic-light emitting diodes (OLEDs). By optical in situ monitoring, we successfully identified the reduction in oxygen flow rates in the reaction steps, which resulted in a 2.67 times increase in the water vapor transmission ratio (WVTR) of the deposited Al2O3 films. Therefore, we are convinced that the suggested in situ monitoring method is useful for the detection of process shifts or drifts that adversely affect PEALD film quality.

In situ SEM Study of Lithium Intercalation in individual V 2O 5 Nanowires

DOE PAGES

Strelcov, Evgheni; Cothren, Joshua E.; Leonard, Donovan N.; ...

2015-01-08

Progress in rational engineering of Li-ion batteries requires better understanding of the electrochemical processes and accompanying transformations in the electrode materials on multiple length scales. In spite of recent progress in utilizing transmission electron microscopy (TEM) to analyze these materials, in situ scanning electron microscopy (SEM) was mostly overlooked as a powerful tool that allows probing these phenomena on the nano and mesoscale. In this paper, we report on in situ SEM study of lithiation in a V 2O 5-based single-nanobelt battery with ionic liquid electrolyte. Coupled with cyclic voltammetry measurements, in situ SEM revealed the peculiarities of subsurface intercalation,more » formation of solid-electrolyte interface (SEI) and electromigration of liquid. We observed that single-crystalline vanadia nanobelts do not undergo large-scale amorphization or fracture during electrochemical cycling, but rather transform topochemically with only a slight shape distortion. Lastly, the SEI layer seems to have significant influence on the lithium ion diffusion and overall capacity of the single-nanobelt battery.« less

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.

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

Knox, Anna Sophia; Paller, Michael H.; Milliken, Charles E.

One challenge to all remedial approaches for contaminated sediments is the continued influx of contaminants from uncontrolled sources following remediation. We investigated the effects of ongoing contamination in mesocosms employing sediments remediated by different types of active and passive caps and in-situ treatment. Our hypothesis was that the sequestering agents used in active caps and in situ treatment will bind elements (arsenic, chromium, cadmium, cobalt, copper, nickel, lead, selenium, and zinc) from ongoing sources thereby reducing their bioavailability and protecting underlying remediated sediments from recontamination. Most element concentrations in surface water remained significantly lower in mesocosms with apatite and mixedmore » amendment caps than in mesocosms with passive caps (sand), uncapped sediment, and spike solution throughout the 2520 hour experiment. Element concentrations were significantly higher in Lumbriculus variegatus from untreated sediment than in Lumbriculus from most active caps. Moreover, Pearson correlations between element concentrations in Lumbriculus and metal concentrations in the top 2.5 cm of sediment or cap measured by diffusive gradient in thin films (DGT) sediment probes were generally strong (as high as 0.98) and significant (p<0.05) for almost all tested elements. Metal concentrations in both Lumbriculus and sediment/cap were lowest in apatite, mixed amendment, and activated carbon treatments. Finally, these findings show that some active caps can protect remediated sediments by reducing the bioavailable pool of metals/metalloids in ongoing sources of contamination.« less

Environmental impact of ongoing sources of metal contamination on remediated sediments

DOE PAGES

Knox, Anna Sophia; Paller, Michael H.; Milliken, Charles E.; ...

2016-04-29

One challenge to all remedial approaches for contaminated sediments is the continued influx of contaminants from uncontrolled sources following remediation. We investigated the effects of ongoing contamination in mesocosms employing sediments remediated by different types of active and passive caps and in-situ treatment. Our hypothesis was that the sequestering agents used in active caps and in situ treatment will bind elements (arsenic, chromium, cadmium, cobalt, copper, nickel, lead, selenium, and zinc) from ongoing sources thereby reducing their bioavailability and protecting underlying remediated sediments from recontamination. Most element concentrations in surface water remained significantly lower in mesocosms with apatite and mixedmore » amendment caps than in mesocosms with passive caps (sand), uncapped sediment, and spike solution throughout the 2520 hour experiment. Element concentrations were significantly higher in Lumbriculus variegatus from untreated sediment than in Lumbriculus from most active caps. Moreover, Pearson correlations between element concentrations in Lumbriculus and metal concentrations in the top 2.5 cm of sediment or cap measured by diffusive gradient in thin films (DGT) sediment probes were generally strong (as high as 0.98) and significant (p<0.05) for almost all tested elements. Metal concentrations in both Lumbriculus and sediment/cap were lowest in apatite, mixed amendment, and activated carbon treatments. Finally, these findings show that some active caps can protect remediated sediments by reducing the bioavailable pool of metals/metalloids in ongoing sources of contamination.« less

In situ polymerization synthesis of Z-scheme tungsten trioxide/polyimide photocatalyst with enhanced visible-light photocatalytic activity

NASA Astrophysics Data System (ADS)

Meng, Pengcheng; Heng, Huimin; Sun, Yanhong; Liu, Xia

2018-01-01

A novel direct Z-scheme P-containing tungsten trioxide/polyimide (PWO/PI) photocatalyst was synthesized by an in-situ solid-state polymerization strategy to enhance the visible-light photocatalytic oxidation capacity of PI. The effects of polymerization temperature and PWO content on the physicochemical properties of PWO/PI composites and photocatalytic degradation efficiency of imidacloprid were investigated. The photocatalysts were characterized by X-ray powder diffraction, Fourier transformed infrared spectra, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, UV-vis diffused reflection spectra and N2 adsorption-desorption isothermals. The results showed that the photocatalysts with visible-light photocatalytic activity can already be prepared at 300 °C. The PWO/PI composites exhibited a lamellar structure and PWO was wrapped by PI. After PWO was introduced, there was a significant interaction between PWO and PI, and the visible light response of photocatalysts was also improved. The visible-light photocatalytic degradation efficiency of imidacloprid on 3% PWO/PI-300 composite was about 3.2 times of commercial P25, and the corresponding pseudo-first-order rate constant was about 2.9 times of pristine PI. The Z-scheme photocatalytic system of PWO/PI composites was confirmed by the electron spin resonance technology, terephthalic acid photoluminescence probing technique, reactive species trapping experiments, X-ray photoelectron spectroscopy and photoluminescence of PWO/PI composites and pristine photocatalysts.

Active cleaning technique for removing contamination from optical surfaces in space

NASA Technical Reports Server (NTRS)

Shannon, R. L.; Gillette, R. B.; Cruz, G. A.

1973-01-01

An active cleaning technique for removing contaminants from optical surfaces in space was investigated with emphasis on the feasibility of using plasma exposure as a means of in-situ cleaning. The major work accomplished includes: (1) development of an in-situ reflectometer for use in conjunction with the contaminant film deposition/cleaning facility; (2) completion of Apollo Telescope Mount (ATM) filter treatment experiments to assess the effects of plasma exposure on the UV transmittance; (3) attempts to correlate the atomic oxygen flux with cleaning rate; (4) completion of in-situ butadien contamination/plasma cleaning/UV reflectance measurement experiments; (5) carbon cleaning experiments using various gases; (6) completion of silicone contamination/cleaning experiments; and (7) experiments conducted at low chamber pressures to determine cleaning rate distribution and contamination of surfaces adjacent to those being cleaned.

Visualizing and measuring flow in shale matrix using in situ synchrotron X-ray microtomography

NASA Astrophysics Data System (ADS)

Kohli, A. H.; Kiss, A. M.; Kovscek, A. R.; Bargar, J.

2017-12-01

Natural gas production via hydraulic fracturing of shale has proliferated on a global scale, yet recovery factors remain low because production strategies are not based on the physics of flow in shale reservoirs. In particular, the physical mechanisms and time scales of depletion from the matrix into the simulated fracture network are not well understood, limiting the potential to optimize operations and reduce environmental impacts. Studying matrix flow is challenging because shale is heterogeneous and has porosity from the μm- to nm-scale. Characterizing nm-scale flow paths requires electron microscopy but the limited field of view does not capture the connectivity and heterogeneity observed at the mm-scale. Therefore, pore-scale models must link to larger volumes to simulate flow on the reservoir-scale. Upscaled models must honor the physics of flow, but at present there is a gap between cm-scale experiments and μm-scale simulations based on ex situ image data. To address this gap, we developed a synchrotron X-ray microscope with an in situ cell to simultaneously visualize and measure flow. We perform coupled flow and microtomography experiments on mm-scale samples from the Barnett, Eagle Ford and Marcellus reservoirs. We measure permeability at various pressures via the pulse-decay method to quantify effective stress dependence and the relative contributions of advective and diffusive mechanisms. Images at each pressure step document how microfractures, interparticle pores, and organic matter change with effective stress. Linking changes in the pore network to flow measurements motivates a physical model for depletion. To directly visualize flow, we measure imbibition rates using inert, high atomic number gases and image periodically with monochromatic beam. By imaging above/below X-ray adsorption edges, we magnify the signal of gas saturation in μm-scale porosity and nm-scale, sub-voxel features. Comparing vacuumed and saturated states yields image-based measurements of the distribution and time scales of imbibition. We also characterize nm-scale structure via focused ion beam tomography to quantify sub-voxel porosity and connectivity. The multi-scale image and flow data is used to develop a framework to upscale and benchmark pore-scale models.

High angular resolution diffusion imaging with stimulated echoes: compensation and correction in experiment design and analysis.

PubMed

Lundell, Henrik; Alexander, Daniel C; Dyrby, Tim B

2014-08-01

Stimulated echo acquisition mode (STEAM) diffusion MRI can be advantageous over pulsed-gradient spin-echo (PGSE) for diffusion times that are long compared with T2 . It therefore has potential for biomedical diffusion imaging applications at 7T and above where T2 is short. However, gradient pulses other than the diffusion gradients in the STEAM sequence contribute much greater diffusion weighting than in PGSE and lead to a disrupted experimental design. Here, we introduce a simple compensation to the STEAM acquisition that avoids the orientational bias and disrupted experiment design that these gradient pulses can otherwise produce. The compensation is simple to implement by adjusting the gradient vectors in the diffusion pulses of the STEAM sequence, so that the net effective gradient vector including contributions from diffusion and other gradient pulses is as the experiment intends. High angular resolution diffusion imaging (HARDI) data were acquired with and without the proposed compensation. The data were processed to derive standard diffusion tensor imaging (DTI) maps, which highlight the need for the compensation. Ignoring the other gradient pulses, a bias in DTI parameters from STEAM acquisition is found, due both to confounds in the analysis and the experiment design. Retrospectively correcting the analysis with a calculation of the full B matrix can partly correct for these confounds, but an acquisition that is compensated as proposed is needed to remove the effect entirely. © 2014 The Authors. NMR in Biomedicine published by John Wiley & Sons, Ltd.

Probing the Interplay of Size, Shape, and Solution Environment in Macromolecular Diffusion Using a Simple Refraction Experiment

ERIC Educational Resources Information Center

Mankidy, Bijith D.; Coutinho, Cecil A.; Gupta, Vinay K.

2010-01-01

The diffusion coefficient of polymers is a critical parameter in biomedicine, catalysis, chemical separations, nanotechnology, and other industrial applications. Here, measurement of macromolecular diffusion in solutions is described using a visually instructive, undergraduate-level optical refraction experiment based on Weiner's method. To…

Resonant scattering of energetic electrons in the outer radiation belt by HAARP-induced ELF/VLF waves

NASA Astrophysics Data System (ADS)

Chang, Shanshan; Zhu, Zhengping; Ni, Binbin; Cao, Xing; Luo, Weihua

2016-10-01

Several extremely low-frequency (ELF)/very low-frequency (VLF) wave generation experiments have been performed successfully at High-Frequency Active Auroral Research Program (HAARP) heating facility and the artificial ELF/VLF signals can leak into the outer radiation belt and contribute to resonant interactions with energetic electrons. Based on the artificial wave properties revealed by many of in situ observations, we implement test particle simulations to evaluate the effects of energetic electron resonant scattering driven by the HAARP-induced ELF/VLF waves. The results indicate that for both single-frequency/monotonic wave and multi-frequency/broadband waves, the behavior of each electron is stochastic while the averaged diffusion effect exhibits temporal linearity in the wave-particle interaction process. The computed local diffusion coefficients show that, the local pitch-angle scattering due to HARRP-induced single-frequency ELF/VLF whistlers with an amplitude of ∼10 pT can be intense near the loss cone with a rate of ∼10-2 rad2 s-1, suggesting the feasibility of HAARP-induced ELF/VLF waves for removal of outer radiation belt energetic electrons. In contrast, the energy diffusion of energetic electrons is relatively weak, which confirms that pitch-angle scattering by artificial ELF/VLF waves can dominantly lead to the precipitation of energetic electrons. Moreover, diffusion rates of the discrete, broadband waves, with the same amplitude of each discrete frequency as the monotonic waves, can be much larger, which suggests that it is feasible to trigger a reasonable broadband wave instead of the monotonic wave to achieve better performance of controlled precipitation of energetic electrons. Moreover, our test particle scattering simulation show good agreement with the predictions of the quasi-linear theory, confirming that both methods are applied to evaluate the effects of resonant interactions between radiation belt electrons and artificially generated discrete ELF/VLF waves.

Technical Approach for In Situ Biological Treatment Research: Bench- Scale Experiments

DTIC Science & Technology

1993-08-01

1 CONVERSION FACTORS, NON-SI TO SI (METRIC) UNITS OF MEASUREMENT . . 5 PART I: INTRODUCTION...141 REFERENCES ....................... .............................. 142 TABLES 1 -4 APPENDIX A: IN SITU IMPLEMENTATION CASE STUDIES...TREATMENT RESEARCH: BENCH-SCALE EXPERIMENTS PART I: INTRODUCTION Background 1 . Many US Army installations have areas of contamination requiring

Novel micro-reactor flow cell for investigation of model catalysts using in situ grazing-incidence X-ray scattering

PubMed Central

Kehres, Jan; Pedersen, Thomas; Masini, Federico; Andreasen, Jens Wenzel; Nielsen, Martin Meedom; Diaz, Ana; Nielsen, Jane Hvolbæk; Hansen, Ole

2016-01-01

The design, fabrication and performance of a novel and highly sensitive micro-reactor device for performing in situ grazing-incidence X-ray scattering experiments of model catalyst systems is presented. The design of the reaction chamber, etched in silicon on insulator (SIO), permits grazing-incidence small-angle X-ray scattering (GISAXS) in transmission through 10 µm-thick entrance and exit windows by using micro-focused beams. An additional thinning of the Pyrex glass reactor lid allows simultaneous acquisition of the grazing-incidence wide-angle X-ray scattering (GIWAXS). In situ experiments at synchrotron facilities are performed utilizing the micro-reactor and a designed transportable gas feed and analysis system. The feasibility of simultaneous in situ GISAXS/GIWAXS experiments in the novel micro-reactor flow cell was confirmed with CO oxidation over mass-selected Ru nanoparticles. PMID:26917133

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.

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.

Small-scale structure and turbulence observed in MAP/WINE)

NASA Technical Reports Server (NTRS)

Blix, T. A.

1989-01-01

During MAP/WINE small scale structure and turbulence in the mesosphere and lower thermosphere was studied in situ by rocket-borne instruments as well as from the ground by remote sensing techniques. The eight salvoes launched during the campaign resulted in a wealth of information on the dynamical structure of these regions. The experimental results are reviewed and their interpretation is discussed in terms of gravity waves and turbulence. It is shown that eddy diffusion coefficients and turbulent energy dissipation rates may be derived from the in situ measurements in a consistent manner. The observations are also shown to be consistent with the hypothesis that turbulence can be created by a process of gravity wave saturation.

Crystallization dynamics in glass-forming systems

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

Cullinan, Timothy Edward

Crystallization under far-from-equilibrium conditions is investigated for two different scenarios: crystallization of the metallic glass alloy Cu 50Zr 50 and solidification of a transparent organic compound, o-terphenyl. For Cu 50Zr 50, crystallization kinetics are quanti ed through a new procedure that directly fits thermal analysis data to the commonly utilized JMAK model. The phase evolution during crystallization is quantified through in-situ measurements (HEXRD, DSC) and ex-situ microstructural analysis (TEM, HRTEM). The influence of chemical partitioning, diffusion, and crystallographic orientation on this sequence are examined. For o-terphenyl, the relationship between crystal growth velocity and interface undercooling is systematically studied via directionalmore » solidification.« less

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.

Model of turnover kinetics in the lamellipodium: implications of slow- and fast- diffusing capping protein and Arp2/3 complex

NASA Astrophysics Data System (ADS)

McMillen, Laura M.; Vavylonis, Dimitrios

2016-12-01

Cell protrusion through polymerization of actin filaments at the leading edge of motile cells may be influenced by spatial gradients of diffuse actin and regulators. Here we study the distribution of two of the most important regulators, capping protein and Arp2/3 complex, which regulate actin polymerization in the lamellipodium through capping and nucleation of free barbed ends. We modeled their kinetics using data from prior single molecule microscopy experiments on XTC cells. These experiments have provided evidence for a broad distribution of diffusion coefficients of both capping protein and Arp2/3 complex. The slowly diffusing proteins appear as extended ‘clouds’ while proteins bound to the actin filament network appear as speckles that undergo retrograde flow. Speckle appearance and disappearance events correspond to assembly and dissociation from the actin filament network and speckle lifetimes correspond to the dissociation rate. The slowly diffusing capping protein could represent severed capped actin filament fragments or membrane-bound capping protein. Prior evidence suggests that slowly diffusing Apr2/3 complex associates with the membrane. We use the measured rates and estimates of diffusion coefficients of capping protein and Arp2/3 complex in a Monte Carlo simulation that includes particles in association with a filament network and diffuse in the cytoplasm. We consider two separate pools of diffuse proteins, representing fast and slowly diffusing species. We find a steady state with concentration gradients involving a balance of diffusive flow of fast and slow species with retrograde flow. We show that simulations of FRAP are consistent with prior experiments performed on different cell types. We provide estimates for the ratio of bound to diffuse complexes and calculate conditions where Arp2/3 complex recycling by diffusion may become limiting. We discuss the implications of slowly diffusing populations and suggest experiments to distinguish among mechanisms that influence long range transport.

Diffusion of Siderophile Elements in Iron Meteorites

NASA Astrophysics Data System (ADS)

Watson, H. C.; Watson, E. B.

2001-12-01

Preliminary results for diffusion of siderophile elements (Cu, Os, Pd, Re, Os, and Mo) in an iron meteorite analog were obtained at 1400° C and 1GPa from diffusion couple experiments in a piston-cylinder apparatus. Alloys were prepared by synthesizing mixtures of pure metal powders. The alloys were made from a 90 wt% Fe and 10 wt% Ni base mixture, and approximately 1wt% of the various siderophile elements was added (individually) to the same base mixture to make the doped alloys. The powders were packed in pre-drilled holes (~1 mm dia. by 8 mm deep) in MgO cylinders, and run in a piston cylinder apparatus at 1400° C and 1GPa for 48 hours. The resulting homogeneous alloys were then sectioned into wafers approximately 1mm thick, and the faces were polished to prepare for the diffusion experiments. A diffusion couple experiment was conducted by mating a pure alloy wafer and a doped wafer, and placing the couple into an MgO capsule for pressurization and heating in the piston cylinder. The duration of the diffusion experiments ranged from 33 hours to 72 hours. Upon run completion, the diffusion couples were extracted, sectioned lengthwise, and polished for analysis. Diffusion profiles were measured using an electron microprobe. From these experiments it was found that at 1400° C and 1GPa the diffusion coefficient of Os is 1.6E-14 m2/s, the diffusion coefficient of Re is 2.8E-14 m2/s, for Pd it is 9.2E-14 m2/s, for Cu it is 1.2E-13 m2/s, and for Mo it is 2.3E-13 m2/s. These preliminary results raise the possibility that significant diffusive fraction of siderophile elements may occur in metal-silicate systems that fail to equilibrate fully, or under disequilibrium crystallization in pure metal systems.

Helium Diffusion in Olivine

NASA Astrophysics Data System (ADS)

Cherniak, D. J.; Watson, E. B.

2011-12-01

Diffusion of helium has been characterized in natural Fe-bearing olivine (~Fo90) and synthetic forsterite. Polished, oriented slabs of olivine were implanted with 3He, at 100 keV at a dose of 5x1015/cm2 or at 3.0 MeV at a dose of 1x1016/cm2. A set of experiments on the implanted olivine were run in 1-atm furnaces. In addition to the one-atm experiments, experiments on implanted samples were also run at higher pressures (2.6 and 2.7 GPa) to assess the potential effects of pressure on He diffusion and the applicability of the measured diffusivities in describing He transport in the mantle. The high-pressure experiments were conducted in a piston-cylinder apparatus using an "ultra-soft" pressure cell, with the diffusion sample directly surrounded by AgCl. 3He distributions following experiments were measured with Nuclear Reaction Analysis using the reaction 3He(d,p)4He. This direct profiling method permits us to evaluate anisotropy of diffusion, which cannot be easily assessed using bulk-release methods. For diffusion in forsterite parallel to c we obtain the following Arrhenius relation over the temperatures 250-950°C: D = 3.91x10-6exp(-159 ± 4 kJ mol-1/RT) m2/sec. The data define a single Arrhenius line spanning more than 7 orders of magnitude in D and 700°C in temperature. Diffusion parallel to a appears slightly slower, yielding an activation energy for diffusion of 135 kJ/mol and a pre-exponential factor of 3.73x10-8 m2/sec. Diffusion parallel to b is slower than diffusion parallel to a (by about two-thirds of a log unit); for this orientation an activation energy of 138 kJ/mol and a pre-exponential factor of 1.34x10-8 m2/sec are obtained. This anisotropy is broadly consistent with observations for diffusion of Ni and Fe-Mg in olivine. Diffusion in Fe-bearing olivine (transport parallel to b) agrees within uncertainty with findings for He diffusion in forsterite. The higher-pressure experiments yield diffusivities in agreement with those from the 1-atm experiments, indicating that the results reported here can be reasonably applied to modeling He transport in the upper mantle. The insensitivity of He diffusion to pressure over the investigated range of conditions suggests that compression of the mineral lattice is not sufficient to significantly influence migration of the relatively small helium atoms, which likely diffuse via crystal interstices. The He diffusivities in this work are generally consistent with results from the study of Futagami et al. (1993), who measured He diffusion in natural olivine by outgassing 4He implanted samples, and with the diffusivities measured by bulk-release of 4He and 3He by Shuster et al. (2003), but are about 2 orders of magnitude slower than the recent findings of Tolstikhin et al. (2010) and Blard et al. (2008) . An up-temperature extrapolation of our data also show reasonable agreement with the higher-temperature measurements of Hart (1984). Blard et al. (2008) GCA 72, 3788-3803; Futagami et al. (1993) GCA 57, 3177-3194; Hart (1984) EPSL 70, 297-302; Shuster et al.( 2003) EPSL 217, 19-32; Tolstikhin et al. (2010) GCA 74, 1436-1447

In Situ and ex Situ Catalytic Pyrolysis of Pine in a Bench-Scale Fluidized Bed Reactor System

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

Iisa, Kristiina; French, Richard J.; Orton, Kellene A.

In situ and ex situ catalytic pyrolysis were compared in a system with two 2-in. bubbling fluidized bed reactors. Pine was pyrolyzed in the system with a catalyst, HZSM-5 with a silica-to-alumina ratio of 30, placed either in the first (pyrolysis) reactor or the second (upgrading) reactor. Both the pyrolysis and upgrading temperatures were 500 degrees C, and the weight hourly space velocity was 1.1 h -1. Five catalytic cycles were completed in each experiment. The catalytic cycles were continued until oxygenates in the vapors became dominant. The catalyst was then oxidized, after which a new catalytic cycle was begun.more » The in situ configuration gave slightly higher oil yield but also higher oxygen content than the ex situ configuration, which indicates that the catalyst deactivated faster in the in situ configuration than the ex situ configuration. Analysis of the spent catalysts confirmed higher accumulation of metals in the in situ experiment. In all experiments, the organic oil mass yields varied between 14 and 17% and the carbon efficiencies between 20 and 25%. The organic oxygen concentrations in the oils were 16-18%, which represented a 45% reduction compared to corresponding noncatalytic pyrolysis oils prepared in the same fluidized bed reactor system. GC/MS analysis showed the oils to contain one- to four-ring aromatic hydrocarbons and a variety of oxygenates (phenols, furans, benzofurans, methoxyphenols, naphthalenols, indenols). Lastly, high fractions of oxygen were rejected as water, CO, and CO 2, which indicates the importance of dehydration, decarbonylation, and decarboxylation reactions. Light gases were the major sources of carbon losses, followed by char and coke.« less

In Situ and ex Situ Catalytic Pyrolysis of Pine in a Bench-Scale Fluidized Bed Reactor System

DOE PAGES

Iisa, Kristiina; French, Richard J.; Orton, Kellene A.; ...

2016-02-03

In situ and ex situ catalytic pyrolysis were compared in a system with two 2-in. bubbling fluidized bed reactors. Pine was pyrolyzed in the system with a catalyst, HZSM-5 with a silica-to-alumina ratio of 30, placed either in the first (pyrolysis) reactor or the second (upgrading) reactor. Both the pyrolysis and upgrading temperatures were 500 degrees C, and the weight hourly space velocity was 1.1 h -1. Five catalytic cycles were completed in each experiment. The catalytic cycles were continued until oxygenates in the vapors became dominant. The catalyst was then oxidized, after which a new catalytic cycle was begun.more » The in situ configuration gave slightly higher oil yield but also higher oxygen content than the ex situ configuration, which indicates that the catalyst deactivated faster in the in situ configuration than the ex situ configuration. Analysis of the spent catalysts confirmed higher accumulation of metals in the in situ experiment. In all experiments, the organic oil mass yields varied between 14 and 17% and the carbon efficiencies between 20 and 25%. The organic oxygen concentrations in the oils were 16-18%, which represented a 45% reduction compared to corresponding noncatalytic pyrolysis oils prepared in the same fluidized bed reactor system. GC/MS analysis showed the oils to contain one- to four-ring aromatic hydrocarbons and a variety of oxygenates (phenols, furans, benzofurans, methoxyphenols, naphthalenols, indenols). Lastly, high fractions of oxygen were rejected as water, CO, and CO 2, which indicates the importance of dehydration, decarbonylation, and decarboxylation reactions. Light gases were the major sources of carbon losses, followed by char and coke.« less

Candle Flames in Microgravity Experiment

NASA Image and Video Library

1992-07-09

Closeup view inside glovebox showing a candle flame. The Candle Flames in Microgravity experiment is carried onboard Columbia to examine whether candle flames can be sustained in space; to study the interaction and physical properties of diffusion flames. In space, where buoyancy-driven convection is reduced, the role diffusion plays in sustaining candle flames can be isolated. Results have implications for other diffusion flame studies. Diffusion flames are the most common type of flame on Earth.

Reflection Matrix Method for Controlling Light After Reflection From a Diffuse Scattering Surface

DTIC Science & Technology

2016-12-22

reflective inverse diffusion, which was a proof-of-concept experiment that used phase modulation to shape the wavefront of a laser causing it to refocus...after reflection from a rough surface. By refocusing the light, reflective inverse diffusion has the potential to eliminate the complex radiometric model...photography. However, the initial reflective inverse diffusion experiments provided no mathematical background and were conducted under the premise that the

In Situ Powder Diffraction Studies of Electrode Materials in Rechargeable Batteries.

PubMed

Sharma, Neeraj; Pang, Wei Kong; Guo, Zaiping; Peterson, Vanessa K

2015-09-07

The ability to directly track the charge carrier in a battery as it inserts/extracts from an electrode during charge/discharge provides unparalleled insight for researchers into the working mechanism of the device. This crystallographic-electrochemical information can be used to design new materials or modify electrochemical conditions to improve battery performance characteristics, such as lifetime. Critical to collecting operando data used to obtain such information in situ while a battery functions are X-ray and neutron diffractometers with sufficient spatial and temporal resolution to capture complex and subtle structural changes. The number of operando battery experiments has dramatically increased in recent years, particularly those involving neutron powder diffraction. Herein, the importance of structure-property relationships to understanding battery function, why in situ experimentation is critical to this, and the types of experiments and electrochemical cells required to obtain such information are described. For each battery type, selected research that showcases the power of in situ and operando diffraction experiments to understand battery function is highlighted and future opportunities for such experiments are discussed. The intention is to encourage researchers to use in situ and operando techniques and to provide a concise overview of this area of research. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Self-diffusion of charged colloidal tracer spheres in transparent porous glass media: Effect of ionic strength and pore size

NASA Astrophysics Data System (ADS)

Kluijtmans, Sebastiaan G. J. M.; de Hoog, Els H. A.; Philipse, Albert P.

1998-05-01

The influence of charge on diffusion in porous media was studied for fluorescent colloidal silica spheres diffusing in a porous glass medium. The bicontinuous porous silica glasses were optically matched with an organic solvent mixture in which both glass and tracers are negatively charged. Using fluorescence recovery after photobleaching, the long-time self-diffusion coefficient DSL of the confined silica particles was monitored in situ as a function of the ionic strength and particle to pore size ratio. At high salt concentration DSL reaches a relatively high plateau value, which depends on the particle to pore size ratio. This plateau value is unexpectedly higher than the value found for uncharged silica spheres in these porous glasses, but still significantly smaller than the free particle bulk diffusion coefficient of the silica spheres. At low salt concentration DSL reduces markedly, up to the point where colloids are nearly immobilized. This peculiar retardation probably originates from potential traps and barriers at pore intersections due to deviations from cylinder symmetry in the double layer interactions between tracers and pore walls. This indicates that diffusion of charged particles in tortuous porous media may be very different from transport in long capillaries without such intersections.

Interdiffusion and stress development in single-crystalline Pd/Ag bilayers

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

Noah, Martin A., E-mail: m.noah@is.mpg.de; Flötotto, David; Wang, Zumin

Interdiffusion and stress evolution in single-crystalline Pd/single-crystalline Ag thin films were investigated by Auger electron spectroscopy sputter-depth profiling and in-situ X-ray diffraction, respectively. The concentration-dependent chemical diffusion coefficient, as well as the impurity diffusion coefficient of Ag in Pd could be determined in the low temperature range of 356 °C–455 °C. As a consequence of the similarity of the strong concentration-dependences of the intrinsic diffusion coefficients, the chemical diffusion coefficient varies only over three orders of magnitude over the whole composition range, despite the large difference of six orders of magnitude of the self-diffusion coefficients of Ag in Ag and Pd inmore » Pd. It is shown that the Darken-Manning treatment should be adopted for interpretation of the experimental data; the Nernst-Planck treatment yielded physically unreasonable results. Apart from the development of compressive thermal stress, the development of stress in both sublayers separately could be ascribed to compositional stress (tensile in the Ag sublayer and compressive in the Pd sublayer) and dominant relaxation processes, especially in the Ag sublayer. The effect of these internal stresses on the values determined for the diffusion coefficients is shown to be negligible.« less

Radial Diffusion Coefficients Using E and B Field Data from the Van Allen Probes: Comparison with the CRRES Study

NASA Astrophysics Data System (ADS)

Ali, A.; Elkington, S. R.; Malaspina, D.

2014-12-01

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. We are investigating the contributions from perturbations in both the magnetic and the electric fields in driving radial diffusion of charged particles and wish to probe two unanswered questions about ULF wave driven radial transport. First, how important are the fluctuations in the magnetic field compared with the fluctuations in the electric field in driving radial diffusion? Second, how does ULF wave power distribution in azimuth affect radial diffusion? Analytic treatments of the diffusion coefficients generally assume uniform distribution of power in azimuth but in situ measurements suggest otherwise. We present results from a study using the electric and magnetic field measurements from the Van Allen Probes to estimate the radial diffusion coefficients as a function of L and Kp. During the lifetime of the RBSP mission to date, there has been a dearth of solar activity. This compels us to consider Kp as the only time and activity dependent parameter instead of solar wind velocity and pressure.

Insights into cadmium diffusion mechanisms in two-stage diffusion profiles in solar-grade Cu(In,Ga)Se{sub 2} thin films

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

Biderman, N. J.; Sundaramoorthy, R.; Haldar, Pradeep

Cadmium diffusion experiments were performed on polished copper indium gallium diselenide (Cu(In,Ga)Se{sub 2} or CIGS) samples with resulting cadmium diffusion profiles measured by time-of-flight secondary ion mass spectroscopy. Experiments done in the annealing temperature range between 275 °C and 425 °C reveal two-stage cadmium diffusion profiles which may be indicative of multiple diffusion mechanisms. Each stage can be described by the standard solutions of Fick's second law. The slower cadmium diffusion in the first stage can be described by the Arrhenius equation D{sub 1} = 3 × 10{sup −4} exp (− 1.53 eV/k{sub B}T) cm{sup 2} s{sup −1}, possibly representing vacancy-meditated diffusion. The faster second-stage diffusion coefficients determined in these experiments matchmore » the previously reported cadmium diffusion Arrhenius equation of D{sub 2} = 4.8 × 10{sup −4} exp (−1.04 eV/k{sub B}T) cm{sup 2} s{sup −1}, suggesting an interstitial-based mechanism.« less

Revisiting point FRAP to quantitatively characterize anomalous diffusion in live cells.

PubMed

Daddysman, Matthew K; Fecko, Christopher J

2013-02-07

Fluorescence recovery after photobleaching (FRAP) is widely used to interrogate diffusion and binding of proteins in live cells. Herein, we apply two-photon excited FRAP with a diffraction limited bleaching and observation volume to study anomalous diffusion of unconjugated green fluorescence protein (GFP) in vitro and in cells. Experiments performed on dilute solutions of GFP reveal that reversible fluorophore bleaching can be mistakenly interpreted as anomalous diffusion. We derive a reaction-diffusion FRAP model that includes reversible photobleaching, and demonstrate that it properly accounts for these photophysics. We then apply this model to investigate the diffusion of GFP in HeLa cells and polytene cells of Drosophila larval salivary glands. GFP exhibits anomalous diffusion in the cytoplasm of both cell types and in HeLa nuclei. Polytene nuclei contain optically resolvable chromosomes, permitting FRAP experiments that focus separately on chromosomal or interchrosomal regions. We find that GFP exhibits anomalous diffusion in chromosomal regions but diffuses normally in regions devoid of chromatin. This observation indicates that obstructed transport through chromatin and not crowding by macromolecules is a source of anomalous diffusion in polytene nuclei. This behavior is likely true in other cells, so it will be important to account for this type of transport physics and for reversible photobleaching to properly interpret future FRAP experiments on DNA-binding proteins.

Experiments on tandem diffusers with boundary-layer suction applied in between

NASA Technical Reports Server (NTRS)

Barna, P. S.

1979-01-01

Experiments were performed on conical diffusers of various configurations with the same, but rather unusually large, 16:1 area ratio. Because available performance data on diffusers fall short of very large area ratio configurations, an unconventional design, consisting of two diffusers following each other in tandem, was proposed. Both diffusers had the same area ratio of 4:1, but had different taper angles. While for the first diffuser (called leading) the angle remained constant, for the second (called follower), the taper angle was stepped up to higher values. Boundary layer control, by way of suction, was applied between the diffusers, and a single slot suction ring was inserted between them. The leading diffuser had an enclosed nominal divergence angle 2 theta = 5 degrees, while the follower diffusers had either 10, 20, 30, or 40 degrees, respectively, giving 4 combinations. The experiments were performed at four different Reynolds numbers with various suction rates. The rates indicate a general improvement in the performance of all diffusers with boundary layer suction. It appears that the improvement of the pressure recovery depends on both the Reynolds number and the suction rate, and the largest increase, 0.075, was found at the lowest R sub e when the follower divergence was 2 theta = 40 degrees.

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

Determination of diffusion coefficients of carbon dioxide in water between 268 and 473 K in a high-pressure capillary optical cell with in situ Raman spectroscopic measurements

USGS Publications Warehouse

Lu, Wanjun; Guo, Huirong; Chou, I.-Ming; Burruss, R.C.; Li, Lanlan

2013-01-01

Accurate values of diffusion coefficients for carbon dioxide in water and brine at reservoir conditions are essential to our understanding of transport behavior of carbon dioxide in subsurface pore space. However, the experimental data are limited to conditions at low temperatures and pressures. In this study, diffusive transfer of carbon dioxide in water at pressures up to 45 MPa and temperatures from 268 to 473 K was observed within an optical capillary cell via time-dependent Raman spectroscopy. Diffusion coefficients were estimated by the least-squares method for the measured variations in carbon dioxide concentration in the cell at various sample positions and time. At the constant pressure of 20 MPa, the measured diffusion coefficients of carbon dioxide in water increase with increasing temperature from 268 to 473 K. The relationship between diffusion coefficient of carbon dioxide in water [D(CO2) in m2/s] and temperature (T in K) was derived with Speedy–Angell power-law approach as: D(CO2)=D0[T/Ts-1]m where D0 = 13.942 × 10−9 m2/s, Ts = 227.0 K, and m = 1.7094. At constant temperature, diffusion coefficients of carbon dioxide in water decrease with pressure increase. However, this pressure effect is rather small (within a few percent).

Materials, structures, and devices for high-speed electronics

NASA Technical Reports Server (NTRS)

Woollam, John A.; Snyder, Paul G.

1992-01-01

Advances in materials, devices, and instrumentation made under this grant began with ex-situ null ellipsometric measurements of simple dielectric films on bulk substrates. Today highly automated and rapid spectroscopic ellipsometers are used for ex-situ characterization of very complex multilayer epitaxial structures. Even more impressive is the in-situ capability, not only for characterization but also for the actual control of the growth and etching of epitaxial layers. Spectroscopic ellipsometry has expanded from the research lab to become an integral part of the production of materials and structures for state of the art high speed devices. Along the way, it has contributed much to our understanding of the growth characteristics and material properties. The following areas of research are summarized: Si3N4 on GaAs, null ellipsometry; diamondlike carbon films; variable angle spectroscopic ellipsometry (VASE) development; GaAs-AlGaAs heterostructures; Ta-Cu diffusion barrier films on GaAs; GaAs-AlGaAs superlattices and multiple quantum wells; superconductivity; in situ elevated temperature measurements of III-V's; optical constants of thermodynamically stable InGaAs; doping dependence of optical constants of GaAs; in situ ellipsometric studies of III-V epitaxial growth; photothermal spectroscopy; microellipsometry; and Si passivation and Si/SiGe strained-layer superlattices.

A Simple Educational Method for the Measurement of Liquid Binary Diffusivities

ERIC Educational Resources Information Center

Rice, Nicholas P.; de Beer, Martin P.; Williamson, Mark E.

2014-01-01

A simple low-cost experiment has been developed for the measurement of the binary diffusion coefficients of liquid substances. The experiment is suitable for demonstrating molecular diffusion to small or large undergraduate classes in chemistry or chemical engineering. Students use a cell phone camera in conjunction with open-source image…

A Simple Refraction Experiment for Probing Diffusion in Ternary Mixtures

ERIC Educational Resources Information Center

Coutinho, Cecil A.; Mankidy, Bijith D.; Gupta, Vinay K.

2010-01-01

Diffusion is a fundamental phenomenon that is vital in many chemical processes such as mass transport in living cells, corrosion, and separations. We describe a simple undergraduate-level experiment based on Weiner's Method to probe diffusion in a ternary aqueous mixture of small molecular-weight molecules. As an illustration, the experiment…

Experimental system for in-situ measurement of temperature rise in animal tissue under exposure to acoustic radiation force impulse.

PubMed

Nitta, Naotaka; Ishiguro, Yasunao; Sasanuma, Hideki; Taniguchi, Nobuyuki; Akiyama, Iwaki

2015-01-01

Acoustic radiation force impulse (ARFI) has recently been used for tissue elasticity measurement and imaging. On the other hand, it is predicted that a rise in temperature occurs. In-situ measurement of temperature rise in animal experiments is important, yet measurement using thermocouples has some problems such as position mismatch of the temperature measuring junction of the thermocouple and the focal point of ultrasound. Therefore, an in-situ measurement system for solving the above problems was developed in this study. The developed system is composed mainly of an ultrasound irradiation unit including a custom-made focused transducer with a through hole for inserting a thin-wire thermocouple, and a temperature measurement unit including the thermocouple. The feasibility of the developed system was evaluated by means of experiments using a tissue-mimicking material (TMM), a TMM containing a bone model or a chicken bone, and an extracted porcine liver. The similarity between the experimental results and the results of simulation using a finite element method (FEM) implied the reasonableness of in-situ temperature rise measured by the developed system. The developed system will become a useful tool for measuring in-situ temperature rise in animal experiments and obtaining findings with respect to the relationship between ultrasound irradiation conditions and in-situ temperature rise.

Dynamics and mechanisms of asbestos-fiber aggregate growth in water

NASA Astrophysics Data System (ADS)

Wu, L.; Ortiz, C. P.; Jerolmack, D. J.

2015-12-01

Most colloidal particles including asbestos fibers form aggregates in water, when solution chemistry provides favorable conditions. To date, the growth of colloidal aggregates has been observed in many model systems under optical and scanning electron microscopy; however, all of these studies have used near-spherical particles. The highly elongated nature of asbestos fibers may cause anomalous aggregate growth and morphology, but this has never been examined. Although the exposure pathway of concern for asbestos is through the air, asbestos particles typically reside in soil that is at least partially saturated, and aggregates formed in the aqueous phase may influence the mobility of particles in the environment. Here we study solution-phase aggregation kinetics of asbestos fibers using a liquid-cell by in situ microscopy, over micron to centimeter length scales and from a tenth of a second to hours. We employ an elliptical particle tracking technique to determine particle trajectories and to quantify diffusivity. Experiments reveal that diffusing fibers join by cross linking, but that such linking is sometimes reversible. The resulting aggregates are very sparse and non-compact, with a fractal dimension that is lower than any previously reported value. Their morphology, growth rate and particle size distribution exhibit non-classical behavior that deviates significantly from observations of aggregates composed of near-spherical particles. We also perform experiments using synthetic colloidal particles, and compare these to asbestos in order to separate the controls of particle shape vs. material properties. This direct method for quantitatively observing aggregate growth is a first step toward predicting asbestos fiber aggregate size distributions in the environment. Moreover, many emerging environmental contaminants - such as carbon nanotubes - are elongated colloids, and our work suggests that theories for aggregate growth may need to be modified in order to model these particles.

Imaging and modelling root water uptake

NASA Astrophysics Data System (ADS)

Zarebanadkouki, M.; Meunier, F.; Javaux, M.; Kaestner, A.; Carminati, A.

2017-12-01

Spatially resolved measurement and modelling of root water uptake is urgently needed to identify root traits that can improve capture of water from the soil. However, measuring water fluxes into roots of transpiring plants growing in soil remains challenging. Here, we describe an in-situ technique to measure local fluxes of water into roots. The technique consists of tracing the transport of deuterated water (D2O) in soil and roots using time series neutron radiography and tomography. A diffusion-convection model was used to model the transport of D2O in roots. The model includes root features such as the endodermis, xylem and the composite flow of water in the apoplastic and symplastic pathways. Diffusion permeability of root cells and of the endodermis were estimated by fitting the experiment during the night, when transpiration was negligible. The water fluxes at different position of the root system were obtained by fitting the experiments at daytime. The results showed that root water uptake was not uniform along root system and varied among different root types. The measured profiles of root water uptake into roots were used to estimate the radial and axial hydraulic of the roots. A three-dimensional model of root water uptake was used to fit the measured water fluxes by adjusting the root radial and axial hydraulic conductivities. We found that the estimated radial conductivities decreased with root age, while the axial conducances increased, and they are different among root types. The significance of this study is the development of a method to estimate 1) water uptake and 2) the radial and axial hydraulic conductivities of roots of transpiring plants growing in the soil.

Stability and Noise in the Cyanobacterial Circadian Clock

NASA Astrophysics Data System (ADS)

Mihalcescu, Irina

2008-03-01

Accuracy in cellular function has to be achieved despite random fluctuations (noise) in the concentrations of different molecular constituents inside and outside the cell. Single cell in vivo monitoring reveals that individual cells generate autonomous circadian rhythms in protein abundance. In multi-cellular organisms, the individual cell rhythms appear to be noisy with drifting phases and frequencies. However, the whole organism is significantly more accurate, the temporal precision being achieved most probably via intercellular coupling of the individual noisy oscillators. In cyanobacteria, we have shown that single cell oscillators are impressively stable and a first estimation rules out strong intercellular coupling. Interestingly, these prokaryotes also have the simplest molecular mechanism at the heart of their circadian clock. In the absence of transcriptional activity in vivo, as well alone in vitro, the three clock proteins KaiA, KaiB and KaiC generate a self-sustained circadian oscillation of autophosphorylation and dephosphorylation. Recent chemical kinetics models provide a possible understanding of the three-protein oscillator, but the measured in vivo stability remains yet unexplained. Is the clock stability a built-in property for each bacterium or does a weak intercellular coupling, make them appear like that? To address this question we first theoretically designed our experiment to be able to distinguish coupling, even weak, from phase diffusion. As the precision of our evaluation increases with the length of the experiments, we continuously monitor, for a couple of weeks, mixtures of cell populations with different initial phases. The inherent experimental noise contribution, initially dominant, is reduced by enhanced statistics. In addition, in situ entrainment experiments confirm our ability to detect a coupling of the circadian oscillator to an external force and to describe explicitly the dynamic change of the mean phase. We report a value of the coupling constant that is small compared to the diffusion constant. These results therefore confirm that the cyanobacterial clock stability is a built-in property: the cyanobacterian clock mechanism is not only the simplest but also the most robust.

Crystal Growth Using MEPHISTO

NASA Technical Reports Server (NTRS)

deGroh, Henry C., III

1999-01-01

The shuttle flight experiment "In Situ Monitoring of Crystal Growth Using MEPHISTO" was accomplished during STS-87 as part of the fourth flight of the United States Microgravity Payload (USMP-4), which was flown from November 19 to December 5, 1997. The data returned from that flight are just now beginning to yield quantitative results. This project is an international collaboration: the furnace system known as MEPHISTO was built in France by CNES (French National Space Agency) and CEA (French Atomic Energy Commission); the principal investigator, Prof. Reza Abbaschian, is from the University of Florida at Gainesville; and numerical and analytical modeling support includes collaborators from the University of New South Wales, Australia, the University of Wisconsin at Milwaukee, the National Institute of Standards and Technology, and the NASA Lewis Research Center. MEPHISTO is a French acronym that translates into English as Materials for the Study of Interesting Phenomena of Solidification on Earth and in Orbit. Since this was the fourth flight of the MEPHISTO furnace, the experiment is referred to as MEPHISTO-4. MEPHISTO-4 was a directional solidification experiment that studied the liquid-to-solid transformation of bismuth alloyed with tin. Directional solidification is a freezing technique common to the processing of the electronic materials used in integrated circuits and detectors, such as silicon and germanium. When liquids are frozen on Earth, they must be cooled. The cooling causes stirring because of density variations in the liquid. This stirring, known as natural convection, influences the quality of the resulting solid. During freezing, regions of high and low concentrations of tin are created. This introduces another important phenomenon: diffusion, or the movement by molecular action of matter from regions of high concentration to regions of lower concentration. In MEPHISTO-4, it is tin that diffuses from the high-concentration region in front of the solid-liquid interface to more distant low-concentration regions.

Microfluidic Platform for High-throughput Screening of Leach Chemistry.

PubMed

Yang, Die; Priest, Craig

2018-06-20

We demonstrate an optofluidic screening platform for studying thiosulfate leaching of Au in a transparent microchannel. The approach permits in situ (optical) monitoring of Au thickness, reduced reagent use, rapid optimization of reagent chem-istry, screening of temperature, and determination of the activation energy. The results demonstrate the critical importance of the (1) preparation and storage of the leach solution, (2) deposition and annealing of the Au film, and (3) lixiviant chem-istry. The density of sputter deposited Au films decreased with depth resulting in accelerating leach rates during experiments. Atomic leach rates were determined and were constant throughout each experiment. Annealing above 270 °C was found to prevent leaching, which can be attributed to diffusion of the chromium adhesion layer into the Au film. The optofluidic analysis revealed leach rates that are sensitive to the stoichiometric ratio of thiosulphate, ammonia and copper in the leach solution, and optimized for 10 mM CuSO 4 , 1 M Na 2 S 2 O 3 and 1 M NH 4 OH. The temperature dependence of the leach rate gave an apparent activation energy of ~ 40 kJ.mol -1 , based on Arrhenius' relationship.

Comparison with CLPX II airborne data using DMRT model

USGS Publications Warehouse

Xu, X.; Liang, D.; Andreadis, K.M.; Tsang, L.; Josberger, E.G.

2009-01-01

In this paper, we considered a physical-based model which use numerical solution of Maxwell Equations in three-dimensional simulations and apply into Dense Media Radiative Theory (DMRT). The model is validated in two specific dataset from the second Cold Land Processes Experiment (CLPX II) at Alaska and Colorado. The data were all obtain by the Ku-band (13.95GHz) observations using airborne imaging polarimetric scatterometer (POLSCAT). Snow is a densely packed media. To take into account the collective scattering and incoherent scattering, analytical Quasi-Crystalline Approximation (QCA) and Numerical Maxwell Equation Method of 3-D simulation (NMM3D) are used to calculate the extinction coefficient and phase matrix. DMRT equations were solved by iterative solution up to 2nd order for the case of small optical thickness and full multiple scattering solution by decomposing the diffuse intensities into Fourier series was used when optical thickness exceed unity. It was shown that the model predictions agree with the field experiment not only co-polarization but also cross-polarization. For Alaska region, the input snow structure data was obtain by the in situ ground observations, while for Colorado region, we combined the VIC model to get the snow profile. ??2009 IEEE.

Apparent Km of mitochondria for oxygen computed from Vmax measured in permeabilized muscle fibers is lower in water enriched in oxygen by electrolysis than injection

PubMed Central

Zoll, Joffrey; Bouitbir, Jamal; Sirvent, Pascal; Klein, Alexis; Charton, Antoine; Jimenez, Liliana; Péronnet, François R; Geny, Bernard; Richard, Ruddy

2015-01-01

Background It has been suggested that oxygen (O2) diffusion could be favored in water enriched in O2 by a new electrolytic process because of O2 trapping in water superstructures (clathrates), which could reduce the local pressure/content relationships for O2 and facilitate O2 diffusion along PO2 gradients. Materials and methods Mitochondrial respiration was compared in situ in saponin-skinned fibers isolated from the soleus muscles of Wistar rats, in solution enriched in O2 by injection or the electrolytic process 1) at an O2 concentration decreasing from 240 µmol/L to 10 µmol/L (132 mmHg to 5 mmHg), with glutamate–malate or N, N, N′, N′-tetramethyl-p-phenylenediamine dihydrochloride (TMPD)–ascorbate (with antimycin A) as substrates; and 2) at increasing adenosine diphosphate (ADP) concentration with glutamate–malate as substrate. Results As expected, maximal respiration decreased with O2 concentration and, when compared to glutamate–malate, the apparent Km O2 of mitochondria for O2 was significantly lower with TMPD–ascorbate with both waters. However, when compared to the water enriched in O2 by injection, the Km O2 was significantly lower with both electron donors in water enriched in O2 by electrolysis. This was not associated with any increase in the sensitivity of mitochondria to ADP; no significant difference was observed for the Km ADP between the two waters. Conclusion In this experiment, a higher affinity of the mitochondria for O2 was observed in water enriched in O2 by electrolysis than by injection. This observation is consistent with the hypothesis that O2 diffusion can be facilitated in water enriched in O2 by the electrolytic process. PMID:26203225

Apparent Km of mitochondria for oxygen computed from Vmax measured in permeabilized muscle fibers is lower in water enriched in oxygen by electrolysis than injection.

PubMed

Zoll, Joffrey; Bouitbir, Jamal; Sirvent, Pascal; Klein, Alexis; Charton, Antoine; Jimenez, Liliana; Péronnet, François R; Geny, Bernard; Richard, Ruddy

2015-01-01

It has been suggested that oxygen (O2) diffusion could be favored in water enriched in O2 by a new electrolytic process because of O2 trapping in water superstructures (clathrates), which could reduce the local pressure/content relationships for O2 and facilitate O2 diffusion along PO2 gradients. Mitochondrial respiration was compared in situ in saponin-skinned fibers isolated from the soleus muscles of Wistar rats, in solution enriched in O2 by injection or the electrolytic process 1) at an O2 concentration decreasing from 240 µmol/L to 10 µmol/L (132 mmHg to 5 mmHg), with glutamate-malate or N, N, N', N'-tetramethyl-p-phenylenediamine dihydrochloride (TMPD)-ascorbate (with antimycin A) as substrates; and 2) at increasing adenosine diphosphate (ADP) concentration with glutamate-malate as substrate. As expected, maximal respiration decreased with O2 concentration and, when compared to glutamate-malate, the apparent Km O2 of mitochondria for O2 was significantly lower with TMPD-ascorbate with both waters. However, when compared to the water enriched in O2 by injection, the Km O2 was significantly lower with both electron donors in water enriched in O2 by electrolysis. This was not associated with any increase in the sensitivity of mitochondria to ADP; no significant difference was observed for the Km ADP between the two waters. In this experiment, a higher affinity of the mitochondria for O2 was observed in water enriched in O2 by electrolysis than by injection. This observation is consistent with the hypothesis that O2 diffusion can be facilitated in water enriched in O2 by the electrolytic process.

Signatures of a quantum diffusion limited hydrogen atom tunneling reaction.

PubMed

Balabanoff, Morgan E; Ruzi, Mahmut; Anderson, David T

2017-12-20

We are studying the details of hydrogen atom (H atom) quantum diffusion in highly enriched parahydrogen (pH 2 ) quantum solids doped with chemical species in an effort to better understand H atom transport and reactivity under these conditions. In this work we present kinetic studies of the 193 nm photo-induced chemistry of methanol (CH 3 OH) isolated in solid pH 2 . Short-term irradiation of CH 3 OH at 1.8 K readily produces CH 2 O and CO which we detect using FTIR spectroscopy. The in situ photochemistry also produces CH 3 O and H atoms which we can infer from the post-photolysis reaction kinetics that display significant CH 2 OH growth. The CH 2 OH growth kinetics indicate at least three separate tunneling reactions contribute; (i) reactions of photoproduced CH 3 O with the pH 2 host, (ii) H atom reactions with the CH 2 O photofragment, and (iii) long-range migration of H atoms and reaction with CH 3 OH. We assign the rapid CH 2 OH growth to the following CH 3 O + H 2 → CH 3 OH + H → CH 2 OH + H 2 two-step sequential tunneling mechanism by conducting analogous kinetic measurements using deuterated methanol (CD 3 OD). By performing photolysis experiments at 1.8 and 4.3 K, we show the post-photolysis reaction kinetics change qualitatively over this small temperature range. We use this qualitative change in the reaction kinetics with temperature to identify reactions that are quantum diffusion limited. While these results are specific to the conditions that exist in pH 2 quantum solids, they have direct implications on the analogous low temperature H atom tunneling reactions that occur on metal surfaces and on interstellar grains.

The role of diffusion-controlled oscillatory nucleation in the formation of line rock in pegmatite-aplite dikes

USGS Publications Warehouse

Webber, K.L.; Falster, A.U.; Simmons, W.B.; Foord, E.E.

1997-01-01

The George Ashley Block (GAB), located in the Pala Pegmatite District, San Diego County, California, is a composite pegmatite-aplite dike of 8 m thickness displaying striking mineralogical layering in the aphte portion of the dike, referred to as line rock. Rhythmic layering is characterized by garnet-rich bands alternating with albite-quartz-muscovite-rich bands. Cumulus textures are notably absent from the layered portion of the dike. Elongated quartz, megacrysts are oriented perpendicular to the garnet-rich layers and poikilitically include garnet, albite, and muscovite. Calculated crystal-free magma viscosity with 3% H2O is 106.2 Pa s and the calculated settling velocity for garnet is 0??51 cm/year. Conductive cooling calculations based on emplacement of a 650??C dike into 150?? C fractured gabbroic country rock at 1??5 kbar, and accounting for latent heat of crystallization, demonstrate that the line rock portion of the dike cools to 550?? C in about 1 year. Crystal size distribution studies also suggest very rapid nucleation and crystallization. Diffusion-controlled gel crystallization experiments yield textures virtually identical to those observed in the layered aplite, including rhythmic banding, colloform layering, and band discontinuities. Thus, observed textures and calculated magmatic parameters suggest that mineralogical layering in the GAB results from an in situ diffusion-controlled process of oscillatory nucleation and crystallization. We propose that any event that promotes strong undercooling has the potential to initiate rapid heterogeneous nucleation and oscillatory crystal growth, leading to the development of a layer of excluded components in front of the crystallization front, and the formation of line rock.

The Impact of Biofilms on the Process of Back Diffusion From a Contaminated Rock Matrix

NASA Astrophysics Data System (ADS)

Yungwirth, G. A.; Novakowski, K. S.; Ross, N.

2005-12-01

Groundwater remediation in fractured rock settings is complicated by the diffusion of contaminants into the rock matrix and the subsequent back diffusion into the fractures. The process of back diffusion, in particular, leads to extended periods of low-level contamination in the fracture network that persists long after the source area is hydraulically or otherwise removed. In such a case, we hypothesize that back diffusion could be limited by growing a biofilm which coats the rock fracture surface and potentially invades the rock micropores. This would effectively sequester the contamination potentially in perpetuity. To explore the viability of this concept, diffusion experiments were conducted in which the effect of biofilm growth on diffusion through thin (0.8 to 1.2 cm) slices of dolostone core obtained from the Lockport Formation, Southern Ontario, was investigated. The experiments were conducted using a double-cell method, in which the core slices were encapsulated inside Teflon coated hydraulic hose, fitted with ultra high molecular weight polyethylene endcaps having stainless steel sample ports. Diffusion was established across the core slice by spiking one reservoir with a conservative tracer and monitoring the tracer arrival in the reservoir located on the other side of the coupon. The experiments were conducted both in the presence and absence of a biofilm. Biofilm was grown on the rock coupons in a separate bath before the coupons were transferred to the apparatus for the diffusion experiments. Microbial populations indigenous to the groundwater used in the bath were stimulated to form the biofilm with the addition of a beef extract and peptone nutrient broth in 1g/L concentration. The extent of biofilm growth was monitored using a modified Dubois et al (1956) colorimetric method for sugar determination. Results were simulated using an analytical model that was developed for the geometry of the diffusion experiments. Governing equations for the model are based on a cylindrical coordinate system where one equation was developed for the rock and another for the biofilm. The solution was found using the Laplace Transform method. Preliminary results show substantial biofilm growth, confirming that the method of biofilm stimulation is viable. Preliminary analysis of data from the diffusion experiments shows the impact of biofilm presence on back diffusion to be profound.

Application of New Chorus Wave Model from Van Allen Probe Observations in Earth's Radiation Belt Modeling

NASA Astrophysics Data System (ADS)

Wang, D.; Shprits, Y.; Spasojevic, M.; Zhu, H.; Aseev, N.; Drozdov, A.; Kellerman, A. C.

2017-12-01

In situ satellite observations, theoretical studies and model simulations suggested that chorus waves play a significant role in the dynamic evolution of relativistic electrons in the Earth's radiation belts. In this study, we developed new wave frequency and amplitude models that depend on Magnetic Local Time (MLT)-, L-shell, latitude- and geomagnetic conditions indexed by Kp for upper-band and lower-band chorus waves using measurements from the Electric and Magnetic Field Instrument Suite and Integrated Science (EMFISIS) instrument onboard the Van Allen Probes. Utilizing the quasi-linear full diffusion code, we calculated corresponding diffusion coefficients in each MLT sector (1 hour resolution) for upper-band and lower-band chorus waves according to the new developed wave models. Compared with former parameterizations of chorus waves, the new parameterizations result in differences in diffusion coefficients that depend on energy and pitch angle. Utilizing obtained diffusion coefficients, lifetime of energetic electrons is parameterized accordingly. In addition, to investigate effects of obtained diffusion coefficients in different MLT sectors and under different geomagnetic conditions, we performed simulations using four-dimensional Versatile Electron Radiation Belt simulations and validated results against observations.

High Density Diffusion-Free Nanowell Arrays

PubMed Central

Takulapalli, Bharath R; Qiu, Ji; Magee, D. Mitchell; Kahn, Peter; Brunner, Al; Barker, Kristi; Means, Steven; Miersch, Shane; Bian, Xiaofang; Mendoza, Alex; Festa, Fernanda; Syal, Karan; Park, Jin; LaBaer, Joshua; Wiktor, Peter

2012-01-01

Proteomics aspires to elucidate the functions of all proteins. Protein microarrays provide an important step by enabling high-throughput studies of displayed proteins. However, many functional assays of proteins include untethered intermediates or products, which could frustrate the use of planar arrays at very high densities because of diffusion to neighboring features. The nucleic acid programmable protein array (NAPPA), is a robust, in situ synthesis method for producing functional proteins just-in-time, which includes steps with diffusible intermediates. We determined that diffusion of expressed proteins led to cross-binding at neighboring spots at very high densities with reduced inter-spot spacing. To address this limitation, we have developed an innovative platform using photolithographically-etched discrete silicon nanowells and used NAPPA as a test case. This arrested protein diffusion and cross-binding. We present confined high density protein expression and display, as well as functional protein-protein interactions, in 8,000 nanowell arrays. This is the highest density of individual proteins in nano-vessels demonstrated on a single slide. We further present proof of principle results on ultra-high density protein arrays capable of up to 24,000 nanowells on a single slide. PMID:22742968

Field evaluation of a horizontal well recirculation system for groundwater treatment: Field demonstration at X-701B Portsmouth Gaseous Diffusion Plant, Piketon, Ohio

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

Korte, N.; Muck, M.; Kearl, P.

1998-08-01

This report describes the field-scale demonstration performed as part of the project, In Situ Treatment of Mixed Contaminants in Groundwater. This project was a 3{1/2} year effort comprised of laboratory work performed at Oak Ridge National Laboratory and fieldwork performed at the US Department of Energy (DOE) Portsmouth Gaseous Diffusion Plant (PORTS). The overall goal of the project was to evaluate in situ treatment of groundwater using horizontal recirculation coupled with treatment modules. Specifically, horizontal recirculation was tested because of its application to thin, interbedded aquifer zones. Mixed contaminants were targeted because of their prominence at DOE sites and becausemore » they cannot be treated with conventional methods. The project involved several research elements, including treatment process evaluation, hydrodynamic flow and transport modeling, pilot testing at an uncontaminated site, and full-scale testing at a contaminated site. This report presents the results of the work at the contaminated site, X-701B at PORTS. Groundwater contamination at X-701B consists of trichloroethene (TCE) (concentrations up to 1800 mg/L) and technetium-998 (Tc{sup 99}) (activities up to 926 pCi/L).« less

Tailored nanostructured platforms for boosting transcorneal permeation: Box–Behnken statistical optimization, comprehensive in vitro, ex vivo and in vivo characterization

PubMed Central

Elsayed, Ibrahim; Sayed, Sinar

2017-01-01

Ocular drug delivery systems suffer from rapid drainage, intractable corneal permeation and short dosing intervals. Transcorneal drug permeation could increase the drug availability and efficiency in the aqueous humor. The aim of this study was to develop and optimize nanostructured formulations to provide accurate doses, long contact time and enhanced drug permeation. Nanovesicles were designed based on Box–Behnken model and prepared using the thin film hydration technique. The formed nanodispersions were evaluated by measuring the particle size, polydispersity index, zeta potential, entrapment efficiency and gelation temperature. The obtained desirability values were utilized to develop an optimized nanostructured in situ gel and insert. The optimized formulations were imaged by transmission and scanning electron microscopes. In addition, rheological characters, in vitro drug diffusion, ex vivo and in vivo permeation and safety of the optimized formulation were investigated. The optimized insert formulation was found to have a relatively lower viscosity, higher diffusion, ex vivo and in vivo permeation, when compared to the optimized in situ gel. So, the lyophilized nanostructured insert could be considered as a promising carrier and transporter for drugs across the cornea with high biocompatibility and effectiveness. PMID:29133980

Multiplex Staining by Sequential Immunostaining and Antibody Removal on Routine Tissue Sections.

PubMed

Bolognesi, Maddalena Maria; Manzoni, Marco; Scalia, Carla Rossana; Zannella, Stefano; Bosisio, Francesca Maria; Faretta, Mario; Cattoretti, Giorgio

2017-08-01

Multiplexing, labeling for multiple immunostains in the very same cell or tissue section in situ, has raised considerable interest. The methods proposed include the use of labeled primary antibodies, spectral separation of fluorochromes, bleaching of the fluorophores or chromogens, blocking of previous antibody layers, all in various combinations. The major obstacles to the diffusion of this technique are high costs in custom antibodies and instruments, low throughput, and scarcity of specialized skills or facilities. We have validated a method based on common primary and secondary antibodies and diffusely available fluorescent image scanners. It entails rounds of four-color indirect immunofluorescence, image acquisition, and removal (stripping) of the antibodies, before another stain is applied. The images are digitally registered and the autofluorescence is subtracted. Removal of antibodies is accomplished by disulfide cleavage and a detergent or by a chaotropic salt treatment, this latter followed by antigen refolding. More than 30 different antibody stains can be applied to one single section from routinely fixed and embedded tissue. This method requires a modest investment in hardware and materials and uses freeware image analysis software. Multiplexing on routine tissue sections is a high throughput tool for in situ characterization of neoplastic, reactive, inflammatory, and normal cells.

Optimization of hydrogen dispersion in thermophilic up-flow reactors for ex situ biogas upgrading.

PubMed

Bassani, Ilaria; Kougias, Panagiotis G; Treu, Laura; Porté, Hugo; Campanaro, Stefano; Angelidaki, Irini

2017-06-01

This study evaluates the efficiency of four novel up-flow reactors for ex situ biogas upgrading converting externally provided CO 2 and H 2 to CH 4 , via hydrogenotrophic methanogenesis. The gases were injected through stainless steel diffusers combined with alumina ceramic sponge or through alumina ceramic membranes. Pore size, input gas loading and gas recirculation flow rate were modulated to optimize gas-liquid mass transfer, and thus methanation efficiency. Results showed that larger pore size diffusion devices achieved the best kinetics and output-gas quality converting all the injected H 2 and CO 2 , up to 3.6L/L REACTOR ·d H 2 loading rate. Specifically, reactors' CH 4 content increased from 23 to 96% and the CH 4 yield reached 0.25L CH4/ L H2 . High throughput 16S rRNA gene sequencing revealed predominance of bacteria belonging to Anaerobaculum genus and to uncultured order MBA08. Additionally, the massive increase of hydrogenotrophic methanogens, such as Methanothermobacter thermautotrophicus, and syntrophic bacteria demonstrates the selection-effect of H 2 on community composition. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

Ionospheric dynamo theory for production of far ultraviolet emissions on Uranus

NASA Technical Reports Server (NTRS)

Hudson, M. K.; Warren, J. A.; Clarke, J. T.

1989-01-01

A model is presented to explain diffuse FUV emissions from the outer planets, specifically Uranus, in excess of those diffuse emissions that are currently explainable by scattering of sunlight and/or excitation by photoelectrons. These electroglow emissions in H Ly-alpha and H2 bands, which occur in the sunlit hemisphere slightly above the homopause, appear to require particle excitation in the 10- to 50-eV range. An in situ mechanism for accelerating photoelectrons (and ions is proposed, involving neutral wind dynamo generation of field-aligned currents analogous to what occurs in the earth's equatorial E and F regions. Sufficiently strong field-aligned currents are found in the model calculation for Uranus to produce a potential drop of about 100 eV or greater between the F peak and homopause, concentrated at lower altitudes, and capable in principle of accelerating photoelectrons (and ions) to the 10- to 50-eV energies required to explain the observed emissions. The fact that the excitation and ionization cross sections are larger than elastic scattering cross sections in an H2 atmosphere at these energies makes in situ acceleration feasible for the production of UV on the outer planets.

In vivo oxygen transport in the normal rabbit femoral arterial wall.

PubMed Central

Crawford, D W; Back, L H; Cole, M A

1980-01-01

In vivo measurements of tissue oxygen tension were made at 10-micrometer intervals through functioning in situ rabbit femoral arterial walls, using inhalation anesthesia and recessed microcathodes with approximately 4-micrometer external diameters. External environment was controlled with a superfusion well at 30 torr PO2, 35 torr PCO2. Blood pressure, gas tension levels, and blood pH were held within the normal range. Radial PO2 measurements closely fit a mathematical model for unidimensional diffusion into a thick-walled artery with uniform oxygen consumption, and the distances traversed fit measured dimensions of quick-frozen in vivo sections. Using standard values of diffusion and solubility coefficients, mean calculated medial oxygen consumption was 99 nl0/ml-s. Mural oxygen consumption appeared to be related linearly to mean tangential wall stress. Differences in experimental design and technique were compared with previous in vivo and in vitro measurements of wall oxygenation, and largely account for the varying results obtained. Control of environment external to the artery, and maintenance of normally flowing blood in the lumen in vivo appeared critical to an understanding of mural oxygenation in life. If the conditions of this experiment prevailed in arteries with thicker avascular layers, PO2 could have been 20 torr at approximately 156 micrometer and 10 torr at 168 micrometer from blood (average values). Images PMID:7410554

Diffusion-driven proton exchange membrane fuel cell for converting fermenting biomass to electricity.

PubMed

Malati, P; Mehrotra, P; Minoofar, P; Mackie, D M; Sumner, J J; Ganguli, R

2015-10-01

A membrane-integrated proton exchange membrane fuel cell that enables in situ fermentation of sugar to ethanol, diffusion-driven separation of ethanol, and its catalytic oxidation in a single continuous process is reported. The fuel cell consists of a fermentation chamber coupled to a direct ethanol fuel cell. The anode and fermentation chambers are separated by a reverse osmosis (RO) membrane. Ethanol generated from fermented biomass in the fermentation chamber diffuses through the RO membrane into a glucose solution contained in the DEFC anode chamber. The glucose solution is osmotically neutral to the biomass solution in the fermentation chamber preventing the anode chamber from drying out. The fuel cell sustains >1.3 mW cm(-2) at 47°C with high discharge capacity. No separate purification or dilution is necessary, resulting in an efficient and portable system for direct conversion of fermenting biomass to electricity. Copyright © 2015 Elsevier Ltd. All rights reserved.

Nitriding of AISI 4140 steel by a low energy broad ion source

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

Ochoa, E. A.; Figueroa, C. A.; Alvarez, F.

2006-11-15

A comprehensive study of the thermochemical nitriding process of steel AISI 4140 by low energy ion implantation (Kaufmann cell) is reported. Different times of implantation were employed and the studied samples were characterized by x-ray diffraction, in situ photoemission electron spectroscopy, scanning electron microscopy, and hardness (nanoindentation) measurements. The linear relationship between nitrogen content and hardness was verified. The structure of the nitrided layer was characterized yielding that the compound layer is formed by coarse precipitates, around small grains, constituted principally by {epsilon}-Fe{sub 2-3}N and {gamma}-Fe{sub 4}N phases and the diffusion zone is formed by fine precipitates, around big grainsmore » of the original martensitic phase, constituted principally by {gamma}-Fe{sub 4}N phase. Finally, a diffusion model for multiphase systems was applied to determine effective diffusion coefficients of nitrogen in the different phases.« less

Superconducting MgB2 wires with vanadium diffusion barrier

NASA Astrophysics Data System (ADS)

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

2017-10-01

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

In-Situ Visualization Experiments with ParaView Cinema in RAGE

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

Kares, Robert John

2015-10-15

A previous paper described some numerical experiments performed using the ParaView/Catalyst in-situ visualization infrastructure deployed in the Los Alamos RAGE radiation-hydrodynamics code to produce images from a running large scale 3D ICF simulation. One challenge of the in-situ approach apparent in these experiments was the difficulty of choosing parameters likes isosurface values for the visualizations to be produced from the running simulation without the benefit of prior knowledge of the simulation results and the resultant cost of recomputing in-situ generated images when parameters are chosen suboptimally. A proposed method of addressing this difficulty is to simply render multiple images atmore » runtime with a range of possible parameter values to produce a large database of images and to provide the user with a tool for managing the resulting database of imagery. Recently, ParaView/Catalyst has been extended to include such a capability via the so-called Cinema framework. Here I describe some initial experiments with the first delivery of Cinema and make some recommendations for future extensions of Cinema’s capabilities.« less

Electrochemical atomic force microscopy: In situ monitoring of electrochemical processes

NASA Astrophysics Data System (ADS)

Reggente, Melania; Passeri, Daniele; Rossi, Marco; Tamburri, Emanuela; Terranova, Maria Letizia

2017-08-01

The in-situ electrodeposition of polyaniline (PANI), one of the most attractive conducting polymers (CP), has been monitored performing electrochemical atomic force microscopy (EC-AFM) experiments. The electropolymerization of PANI on a Pt working electrode has been observed performing cyclic voltammetry experiments and controlling the evolution of current flowing through the electrode surface, together with a standard AFM image. The working principle and the potentialities of this emerging technique are briefly reviewed and factors limiting the studying of the in-situ electrosynthesis of organic compounds discussed.

The parallel-antiparallel signal difference in double-wave-vector diffusion-weighted MR at short mixing times: A phase evolution perspective

NASA Astrophysics Data System (ADS)

Finsterbusch, Jürgen

2011-01-01

Experiments with two diffusion weightings applied in direct succession in a single acquisition, so-called double- or two-wave-vector diffusion-weighting (DWV) experiments at short mixing times, have been shown to be a promising tool to estimate cell or compartment sizes, e.g. in living tissue. The basic theory for such experiments predicts that the signal decays for parallel and antiparallel wave vector orientations differ by a factor of three for small wave vectors. This seems to be surprising because in standard, single-wave-vector experiments the polarity of the diffusion weighting has no influence on the signal attenuation. Thus, the question how this difference can be understood more pictorially is often raised. In this rather educational manuscript, the phase evolution during a DWV experiment for simple geometries, e.g. diffusion between parallel, impermeable planes oriented perpendicular to the wave vectors, is considered step-by-step and demonstrates how the signal difference develops. Considering the populations of the phase distributions obtained, the factor of three between the signal decays which is predicted by the theory can be reproduced. Furthermore, the intermediate signal decay for orthogonal wave vector orientations can be derived when investigating diffusion in a box. Thus, the presented “phase gymnastics” approach may help to understand the signal modulation observed in DWV experiments at short mixing times.

Ultrafast NMR diffusion measurements exploiting chirp spin echoes.

PubMed

Ahola, Susanna; Mankinen, Otto; Telkki, Ville-Veikko

2017-04-01

Standard diffusion NMR measurements require the repetition of the experiment multiple times with varying gradient strength or diffusion delay. This makes the experiment time-consuming and restricts the use of hyperpolarized substances to boost sensitivity. We propose a novel single-scan diffusion experiment, which is based on spatial encoding of two-dimensional data, employing the spin-echoes created by two successive adiabatic frequency-swept chirp π pulses. The experiment is called ultrafast pulsed-field-gradient spin-echo (UF-PGSE). We present a rigorous derivation of the echo amplitude in the UF-PGSE experiment, justifying the theoretical basis of the method. The theory reveals also that the standard analysis of experimental data leads to a diffusion coefficient value overestimated by a few per cent. Although the overestimation is of the order of experimental error and thus insignificant in many practical applications, we propose that it can be compensated by a bipolar gradient version of the experiment, UF-BP-PGSE, or by corresponding stimulated-echo experiment, UF-BP-pulsed-field-gradient stimulated-echo. The latter also removes the effect of uniform background gradients. The experiments offer significant prospects for monitoring fast processes in real time as well as for increasing the sensitivity of experiments by several orders of magnitude by nuclear spin hyperpolarization. Furthermore, they can be applied as basic blocks in various ultrafast multidimensional Laplace NMR experiments. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

In situ speciation of uranium in treated acid mine drainage using the diffusion gradients in thin films technique (DGT).

PubMed

Pedrobom, Jorge Henrique; Eismann, Carlos Eduardo; Menegário, Amauri A; Galhardi, Juliana Aparecida; Luko, Karen Silva; Dourado, Thiago de Araujo; Kiang, Chang Hung

2017-02-01

The exchange membranes P81 and DE81 and Chelex-100 resin were used to perform in situ speciation of uranium in treated acid mine drainage at the Osamu Utsumi mining site, Poços de Caldas city, Southeast Brazil. To investigate possible chemical modifications in the samples during analysis, the three ligands were deployed in situ and in a laboratory (in lab). The results obtained in situ were also compared to a speciation performed using Visual MINTEQ software. Chelex-100 retained total labile U for a period of up to 48 h. The labile U fraction determined by Chelex 100 ranged from 107 ± 6% to 147 ± 44% in situ and from 115 ± 22% to 191 ± 5% in lab. DE81 retained anionic U species up to 8 h, with labile fractions ranging from 37 ± 2% to 76 ± 3% in situ and 34 ± 12% to 180 ± 17% in lab. P81 exhibited a lower efficiency in retaining U species, with concentrations ranging from 6± 2% to 19± 2% in situ and 3± 2% to 18± 2% in lab. The speciation obtained from MINTEQ suggests that the major U species were UO 2 OH + , UO 2 (OH) 3- , UO 2 (OH) 2(aq) , Ca 2 UO 2 (CO 3 ) 3(aq) , CaUO 2 (CO 3 ) 3 2- , UO 2 (CO 3 ) 2 2- , and UO 2 (CO 3 ) 3 4- . This result is in accordance with the results obtained in situ. Differences concerning speciation and the total and soluble U concentrations were observed between the deployments performed in situ and in the laboratory, indicating that U speciation must be performed in situ. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effects of pore forming agents of potassium bicarbonate and drug loading method against dissolution mechanisms of amoxicillin drugs encapsulated in hydrogel full-Ipn chitosan-poly(N-vinylcaprolactam) as a floating drug delivery system

NASA Astrophysics Data System (ADS)

Aini, Nurul; Rahayu, Dyah Utami Cahyaning; Budianto, Emil

2018-04-01

The limitation of amoxicillin trihydrate in the treatment of H. pylori bacteria is relatively short retention time in the stomach. The FDDS (Floating Drug Delivery System) amoxicillin trihydrate into a chitosan-poly(N-vinylcaprolactam) full-Ipn hydrogel matrix using a pore-forming agent KHCO3 is expected to overcome these limitations. The pore-forming agent to be used is 15% KHCO3 compound. Chemical kinetics approach is performed to determine the dissolution mechanism of amoxicillin trihydrate from K-PNVCL hydrogel in vitro on gastric pH and characterization using SEM performed to confirm the dissolution mechanism. Hydrogels with the addition of pore-forming agents will be loading in situ loading and post loading. Fourier Transform Infra Red (FTIR) spectroscopy was used to characterize K-PNVCL and UV-Vis hydrogels used to calculate the efficiency of encapsulation and drug dissolution rate in K-PNVCL hydrogel. Hydrogel K-PNVCL / KHCO3 that encapsulated by in situ loading method resulted in an encapsulation efficiency of 93.5% and dissolution of 93.4%. While the Hydrogel K-PNVCL / KHCO3 which is drug encapsulation resulted in an encapsulation efficiency of 87.2% with dissolution of 81.5%. Chemical kinetics approach to in situ encapsulation of loading and post loading shows the dissolution mechanism occurring in the K-PNVCL / KHCO3 hydrogel matrix occurs by diffusion. Observation using optical microscope and SEM showed the mechanism of drug dissolution in Hydrogel K-PNVCL occurred by diffusion.

Comparative study to investigate the effect of meloxicam or minocycline HCl in situ gel system on local treatment of periodontal pockets.

PubMed

Kassem, Abeer Ahmed; Ismail, Fatma Ahmed; Naggar, Vivian Fahim; Aboulmagd, Elsayed

2014-08-01

In situ gelling formulations allow easy application to the target area. Gelation is induced by physiological stimuli at the site of application where the formula attains semisolid properties and exerts sustained drug release. In situ gelling formulations containing either 3% meloxicam (Mx) or 2% minocycline HCl (MH) were prepared for local application into the periodontal pockets. Gel formulations were based on the thermosensitive Pluronic(®) (Pl) and the pH-sensitive Carbopol(®) (C) polymers. C gels were prepared in combination with HPMC (H) to decrease its acidity. The total percent drug released from Pl formulae was 21.72% after 1 week for Mx and 85% after 3 days for MH. Their release kinetics data indicated anomalous non-Fickian behavior that could be controlled by both diffusion and chain relaxation. Addition of MH to C/H gels (1:2.5) resulted in liquefaction, followed by drug precipitation. Regarding C/H gel containing Mx, it showed a prolonged release rate up to 7 days with an initial burst effect; the kinetics data revealed Fickian-diffusion mechanism. The in vitro antibacterial activity studies for MH gel in Pl revealed that the drug released exceeded the minimum inhibitory concentration (MIC) of MH against Staphylococcus aureus ATCC 6538; placebo gel showed no effect on the microorganism. Clinical evaluation of Pl gels containing either Mx or MH showed significant improvement in chronic periodontitis patients, manifested by decrease in pocket depth and gingival index and increase in bone density.

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.

75 FR 51239 - Application(s) for Duty-Free Entry of Scientific Instruments

Federal Register 2010, 2011, 2012, 2013, 2014

2010-08-19

... electrically conduction as well as insulation nanostructures prepared by in situ deposition onto clean surfaces. In-situ capacities allow the preparation of clean and well-defined nanostructures on pristine... these experiments. The instrument also has in-situ preparation capability and the ability to operate in...

A novel approach to in-situ rutile petrochronology

NASA Astrophysics Data System (ADS)

Kooijman, Ellen; Smit, Matthijs; Kylander-Clark, Andrew

2017-04-01

Rutile petrochronology has become an increasingly important tool for deciphering the timing and conditions of petrological processes. Rutile provides a reliable single-mineral thermometer, capable of retaining temperature information during high and ultra-high temperature metamorphism. Its HFSE contents can be used to investigate the geochemical environment in which rutile crystallized. Most importantly, rutile strongly fractionates U/Pb and enables U-Pb thermochronology in the intermediate temperature range. Here we present a novel approach to using U-Pb thermochronology of rutile by exploring the use of Pb as a diffusive species in kinetics-based thermometry. We performed high spatial and analytical resolution micro-analysis of rutile by laser ablation multi-collector ICPMS to constrain Pb diffusion profiles in rutile from high-grade metamorphic rocks of the Western Gneiss Complex (WGC), Norway. The age and thermometric results from this analysis are used to constrain a full thermal history from single grains. Millimeter-sized single crystals of rutile from a rutile-rich phlogopitite vein in eclogite were mounted and polished to expose their geometric cores. The grains were analyzed in transects using rectangular spots (c. 15x45 μm). This ensures ablation of a significant volume while maintaining the required radial spatial resolution. The transects yielded well-defined Pb diffusion profiles, with U-Pb ages ranging from c. 415 Ma in the cores to c. 380 Ma in the outermost rims (±2%, 2σ on individual spots). Diffusion zoning length was used with well-established Pb diffusion parameters [1] to determine peak temperature conditions following the approach of [2]. The result, c. 810 ± 25 ˚ C, is consistent with 800 ± 25 ˚ C and c. 780 ˚ C estimated for the same sample using conventional and Zr-in-rutile thermometry, respectively. The cooling history that is reconstructed through age zoning analysis and diffusion modeling shows remarkable consistency with that established for the WGC through decades of 40Ar/39Ar dating. The data presented here demonstrate that in-situ rutile U-Pb analysis yields reliable and precise temperature and age information that can be combined to resolve full thermal histories from single crystals. This novel approach to the toolbox of rutile petrochronology has great potential for research into the tectonics and dynamics of the lithosphere. References [1] Cherniak (2000) Contrib. Mineral. Petrol. 139. 198-207. [2] Smit et al. (2013) J. Metamorph. Geol. 31. 339-358.

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).

Diffuse large B-cell lymphoma, not otherwise specified of the palate: A case report

PubMed Central

Pereira, Thaís SF.; Castro, Alexandre F.; Mesquita, Ricardo A.

2013-01-01

Diffuse large B-cell lymphoma (DLBCL) is the most frequent type of non-Hodgkin´s lymphoma found in oral and maxillofacial regions. A large number of cases may be biologically heterogeneous, which are commonly defined as DLBCL, not otherwise specified (NOS) by the World Health Organization (WHO-2008). The present case reports on an ulcer of raised and irregular edges, found on the border between the hard and soft palate, as the first and only manifestation of an extranodal non-Hodgkin lymphoma in an 85-year-old patient. Incisional biopsy was carried out, and the specimen revealed a proliferation of large lymphoid cells suggestive of diffuse large cell lymphoma. An immunohistochemical analysis was performed. EBV-RNA was assessed by in situ hybridization that also proved to be negative. Immunohistochemical and EBV analyses are important to avoid delays and inappropriate treatment strategies. Although advanced age is considered an adverse prognostic factor, early diagnosis did prove to be a key contributory factor in the cure of non-Hodgkin lymphoma. Key words:Diffuse large B-cell lymphoma, elderly, EBV. PMID:24455096

Lamination and mixing in laminar flows driven by Lorentz body forces

NASA Astrophysics Data System (ADS)

Rossi, L.; Doorly, D.; Kustrin, D.

2012-01-01

We present a new approach to the design of mixers. This approach relies on a sequence of tailored flows coupled with a new procedure to quantify the local degree of striation, called lamination. Lamination translates to the distance over which the molecular diffusion needs to act to finalise mixing. A novel in situ mixing is achieved by the tailored sequence of flows. This sequence is shown with the property that material lines and lamination grow exponentially, according to processes akin to the well-known baker's map. The degree of mixing (stirring coefficient) likewise shows exponential growth before the saturation of the stirring rate. Such saturation happens when the typical striations' thickness is smaller than the diffusion's length scale. Moreover, without molecular diffusion, the predicted striations' thickness would be smaller than the size of an atom of hydrogen within 40 flow turnover times. In fact, we conclude that about 3 minutes, i.e. 15 turnover times, are sufficient to mix species with very low diffusivities, e.g. suspensions of virus, bacteria, human cells, and DNA.

Consumption and diffusion of dissolved oxygen in sedimentary rocks.

PubMed

Manaka, M; Takeda, M

2016-10-01

Fe(II)-bearing minerals (e.g., biotite, chlorite, and pyrite) are a promising reducing agent for the consumption of atmospheric oxygen in repositories for the geological disposal of high-level radioactive waste. To estimate effective diffusion coefficients (D e , in m 2 s -1 ) for dissolved oxygen (DO) and the reaction rates for the oxidation of Fe(II)-bearing minerals in a repository environment, we conducted diffusion-chemical reaction experiments using intact rock samples of Mizunami sedimentary rock. In addition, we conducted batch experiments on the oxidation of crushed sedimentary rock by DO in a closed system. From the results of the diffusion-chemical reaction experiments, we estimated the values of D e for DO to lie within the range 2.69×10 -11

Prompt Ion Outflows and Artificial Ducts during High-Power HF Heating at HAARP: Effect of Suprathermal Electrons?

NASA Astrophysics Data System (ADS)

Mishin, E. V.; Milikh, G. M.

2014-12-01

In situ observations from the DMSP and Demeter satellites established that high-power HF heating of the ionosphere F-region results in significant ion outflows associated with 10-30% density enhancements in the topside ionosphere magnetically-conjugate to the heated region. As follows from the SAMI2 two-fluid model calculations, their formation time should exceed 5-7 minutes. However, specially designed DMSP-HAARP experiments have shown that artificial ducts and ion outflows appear on the topside within 2 minutes. We describe the results of these observations and present a semi-quantitative explanation of the fast timescale due to suprathermal electrons accelerated by HF-induced plasma turbulence. There are two possible effects of suprathermal electrons: (1) the increase of the ambipolar electric field over the usual thermal ambipolar diffusion and (2) excitation of heat flux-driven plasma instability resulting in an anomalous electron-ion momentum exchange. Both effects result in faster upward ion flows.

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.

Droplet Evolution and Refinement During Liquid-Liquid Decomposition of Zn-6 Wt Pct Bi Immiscible Alloy Under High Static Magnetic Fields

NASA Astrophysics Data System (ADS)

Zheng, Tianxiang; Zhong, Yunbo; Wang, Jiang; Ren, Zhongming; Ren, Weili; Lei, Zuosheng; Debray, Francois; Beaugnon, Eric; Wei, Xicheng

2018-05-01

In situ solidification experiments on Zn-6 wt pct Bi immiscible alloys were conducted to investigate the droplet evolution under high static magnetic fields (HSMFs). The results showed that a microstructure with extremely fine Bi-rich particles distributed in the matrix can be obtained under an HSMF of 29 T. The average diameter of the Bi-rich phase decreased with the increasing magnetic flux density. Stokes sedimentation disappeared when the HSMF was larger than 18 T. Starting at an HSMF of 18 T, Bi-rich droplets grew via pure diffusion in the liquid matrix. The HSMF decreased the spacing of the droplet arrays when the cooling rate (R) was approximately 1600 °C/min. The formation of a Zn-rich phase surrounded by a Bi-rich shell at HSMFs below 18 T, when R was approximately 60 °C/min, was attributed to the thermoelectric magnetic force.

Developments in the Implementation of Acoustic Droplet Ejection for Protein Crystallography.

PubMed

Wu, Ping; Noland, Cameron; Ultsch, Mark; Edwards, Bonnie; Harris, David; Mayer, Robert; Harris, Seth F

2016-02-01

Acoustic droplet ejection (ADE) enables crystallization experiments at the low-nanoliter scale, resulting in rapid vapor diffusion equilibration dynamics and efficient reagent usage in the empirical discovery of structure-enabling protein crystallization conditions. We extend our validation of this technology applied to the diverse physicochemical property space of aqueous crystallization reagents where dynamic fluid analysis coupled to ADE aids in accurate and precise dispensations. Addition of crystallization seed stocks, chemical additives, or small-molecule ligands effectively modulates crystallization, and we here provide examples in optimization of crystal morphology and diffraction quality by the acoustic delivery of ultra-small volumes of these cofactors. Additional applications are discussed, including set up of in situ proteolysis and alternate geometries of crystallization that leverage the small scale afforded by acoustic delivery. Finally, we describe parameters of a system of automation in which the acoustic liquid handler is integrated with a robotic arm, plate centrifuge, peeler, sealer, and stacks, which allows unattended high-throughput crystallization experimentation. © 2015 Society for Laboratory Automation and Screening.

Micro-stress dominant displacive reconstructive transition in lithium aluminate

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

Hu, Qiwei; Yan, Xiaozhi; Zhang, Leilei

It is supposed that diffusive reconstructive transitions usually take place under hydrostatic pressure or low stresses, and displacive reconstructive phase transitions easily occur at nonhydrostatic pressure. Here, by in-situ high pressure synchrotron X-ray diffraction and single-crystal Raman scattering studies on lithium aluminate at room temperature, we show that the reconstructive transition mechanism is dependent on the internal microscopic stresses rather than the macroscopic stresses. In this case, even hydrostatic pressure can favor the displacive transition if the compressibility of crystal is anisotropic. During hydrostatic compression, γ-LiAlO{sub 2} transforms to δ-LiAlO{sub 2} at about 4 GPa, which is much lower than thatmore » in previous nonhydrostatic experiments (above 9 GPa). In the region where both phases coexist, there are enormous microscopic stresses stemming from the lattice mismatch, suggesting that this transition is displacive. Furthermore, the atomic picture is drawn with the help of the shear Raman modes.« less

In vitro quantitative analysis of Salmonella typhimurium preference for amino acids secreted by human breast tumor

NASA Astrophysics Data System (ADS)

Choi, Eunpyo; Maeng, Bohee; Lee, Jae-hun; Chang, Hyung-kwan; Park, Jungyul

2016-12-01

Bacterial therapies have been paid significant attentions by their ability to penetrate deep into the solid tumor tissue and its propensity to naturally accumulate in tumors of living animals. Understanding the actual mechanism for bacteria to target the tumor is therapeutically crucial but is poorly understood. We hypothesized that amino acids released from the specific tumors induced bacteria to those tumors and the experiments for chemotactic response of bacteria toward the cancer secreting amino acids was then performed by using the diffusion based multiple chemical gradient generator constructed by in situ self-assembly of microspheres. The quantitative analysis was carried out by comparison of intensity using green fluorescent protein (GFP) tagged Salmonella typhimurium ( S. typhimurium) in the gradient generator, which showed the clear preference to the released amino acids, especially from breast cancer patients. The understanding chemotaxis toward the cancer secreting amino acids is essential for controlling S. typhimurium targeting in tumors and will allow for the development of bacterial therapies.

Bayesian framework for modeling diffusion processes with nonlinear drift based on nonlinear and incomplete observations.

PubMed

Wu, Hao; Noé, Frank

2011-03-01

Diffusion processes are relevant for a variety of phenomena in the natural sciences, including diffusion of cells or biomolecules within cells, diffusion of molecules on a membrane or surface, and diffusion of a molecular conformation within a complex energy landscape. Many experimental tools exist now to track such diffusive motions in single cells or molecules, including high-resolution light microscopy, optical tweezers, fluorescence quenching, and Förster resonance energy transfer (FRET). Experimental observations are most often indirect and incomplete: (1) They do not directly reveal the potential or diffusion constants that govern the diffusion process, (2) they have limited time and space resolution, and (3) the highest-resolution experiments do not track the motion directly but rather probe it stochastically by recording single events, such as photons, whose properties depend on the state of the system under investigation. Here, we propose a general Bayesian framework to model diffusion processes with nonlinear drift based on incomplete observations as generated by various types of experiments. A maximum penalized likelihood estimator is given as well as a Gibbs sampling method that allows to estimate the trajectories that have caused the measurement, the nonlinear drift or potential function and the noise or diffusion matrices, as well as uncertainty estimates of these properties. The approach is illustrated on numerical simulations of FRET experiments where it is shown that trajectories, potentials, and diffusion constants can be efficiently and reliably estimated even in cases with little statistics or nonequilibrium measurement conditions.

Quantifying the transport properties of lipid mesophases by theoretical modelling of diffusion experiments

NASA Astrophysics Data System (ADS)

Antognini, Luca M.; Assenza, Salvatore; Speziale, Chiara; Mezzenga, Raffaele

2016-08-01

Lyotropic Liquid Crystals (LLCs) are a class of lipid-based membranes with a strong potential for drug-delivery employment. The characterization and control of their transport properties is a central issue in this regard, and has recently prompted a notable volume of research on the topic. A promising experimental approach is provided by the so-called diffusion setup, where the drug molecules diffuse from a feeding chamber filled with water to a receiving one passing through a LLC. In the present work we provide a theoretical framework for the proper description of this setup, and validate it by means of targeted experiments. Due to the inhomogeneity of the system, a rich palette of different diffusion dynamics emerges from the interplay of the different time- and lengthscales thereby present. Our work paves the way to the employment of diffusion experiments to quantitatively characterize the transport properties of LLCs, and provides the basic tools for device diffusion setups with controlled kinetic properties.

Pore and Continuum Scale Study of the Effect of Subgrid Transport Heterogeneity on Redox Reaction Rates

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

Liu, Yuanyuan; Liu, Chongxuan; Zhang, Changyong

2015-08-01

A micromodel system with a pore structure for heterogeneous flow and transport was used to investigate the effect of subgrid transport heterogeneity on redox reaction rates. Hematite reductive dissolution by injecting a reduced form of flavin mononucleotide (FMNH2) at variable flow rates was used as an example to probe the variations of redox reaction rates in different subgrid transport domains. Experiments, pore-scale simulations, and macroscopic modeling were performed to measure and simulate in-situ hematite reduction and to evaluate the scaling behavior of the redox reaction rates from the pore to macroscopic scales. The results indicated that the measured pore-scale ratesmore » of hematite reduction were consistent with the predictions from a pore scale reactive transport model. A general trend is that hematite reduction followed reductant transport pathways, starting from the advection-dominated pores toward the interior of diffusion-dominated domains. Two types of diffusion domains were considered in the micromodel: a micropore diffusion domain, which locates inside solid grains or aggregates where reactant transport is limited by diffusion; and a macropore diffusion domain, which locates at wedged, dead-end pore spaces created by the grain-grain contacts. The rate of hematite reduction in the advection-dominated domain was faster than those in the diffusion-controlled domains, and the rate in the macropore diffusion domain was faster than that in the micropore domain. The reduction rates in the advection and macropore diffusion domains increased with increasing flow rate, but were affected by different mechanisms. The rate increase in the advection domain was controlled by the mass action effect as a faster flow supplied more reactants, and the rate increase in the macropore domain was more affected by the rate of mass exchange with the advection domain, which increased with increasing flow rate. The hematite reduction rate in the micropore domain was, however, not affected by the flow rate because molecular diffusion limits reductant supply to the micropore domain interior. Domain-based macroscopic models were evaluated to scale redox reaction rates from the pore to macroscopic scales. A single domain model, which ignores subgrid transport heterogeneity deviated significantly from the pore-scale results. Further analysis revealed that the rate expression for hematite reduction was not scalable from the pore to porous media using the single domain model. A three-domain model, which effectively considers subgrid reactive diffusion in the micropore and macropore domains, significantly improved model description. Overall this study revealed the importance of subgrid transport heterogeneity in the manifestation of redox reaction rates in porous media and in scaling reactions from the pore to porous media. The research also supported that the domain-based scaling approach can be used to directly scale redox reactions in porous media with subgrid transport heterogeneity.« 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.

A combined model of heat and mass transfer for the in situ extraction of volatile water from lunar regolith

NASA Astrophysics Data System (ADS)

Reiss, P.

2018-05-01

Chemical analysis of lunar soil samples often involves thermal processing to extract their volatile constituents, such as loosely adsorbed water. For the characterization of volatiles and their bonding mechanisms it is important to determine their desorption temperature. However, due to the low thermal diffusivity of lunar regolith, it might be difficult to reach a uniform heat distribution in a sample that is larger than only a few particles. Furthermore, the mass transport through such a sample is restricted, which might lead to a significant delay between actual desorption and measurable outgassing of volatiles from the sample. The entire volatiles extraction process depends on the dynamically changing heat and mass transfer within the sample, and is influenced by physical parameters such as porosity, tortuosity, gas density, temperature and pressure. To correctly interpret measurements of the extracted volatiles, it is important to understand the interaction between heat transfer, sorption, and gas transfer through the sample. The present paper discusses the molecular kinetics and mechanisms that are involved in the thermal extraction process and presents a combined parametrical computation model to simulate this process. The influence of water content on the gas diffusivity and thermal diffusivity is discussed and the issue of possible resorption of desorbed molecules within the sample is addressed. Based on the multi-physical computation model, a case study for the ProSPA instrument for in situ analysis of lunar volatiles is presented, which predicts relevant dynamic process parameters, such as gas pressure and process duration.

The Harrison Diffusion Kinetics Regimes in Solute Grain Boundary Diffusion

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

Belova, Irina; Fiedler, T; Kulkarni, Nagraj S

2012-01-01

Knowledge of the limits of the principal Harrison kinetics regimes (Type-A, B and C) for grain boundary diffusion is very important for the correct analysis of the depth profiles in a tracer diffusion experiment. These regimes for self-diffusion have been extensively studied in the past by making use of the phenomenological Lattice Monte Carlo (LMC) method with the result that the limits are now well established. The relationship of those self-diffusion limits to the corresponding ones for solute diffusion in the presence of solute segregation to the grain boundaries remains unclear. In the present study, the influence of solute segregationmore » on the limits is investigated with the LMC method for the well-known parallel grain boundary slab model by showing the equivalence of two diffusion models. It is shown which diffusion parameters are useful for identifying the limits of the Harrison kinetics regimes for solute grain boundary diffusion. It is also shown how the measured segregation factor from the diffusion experiment in the Harrison Type-B kinetics regime may differ from the global segregation factor.« less

Estimating the Diffusion Coefficients of Sugars Using Diffusion Experiments in Agar-Gel and Computer Simulations.

PubMed

Miyamoto, Shuichi; Atsuyama, Kenji; Ekino, Keisuke; Shin, Takashi

2018-01-01

The isolation of useful microbes is one of the traditional approaches for the lead generation in drug discovery. As an effective technique for microbe isolation, we recently developed a multidimensional diffusion-based gradient culture system of microbes. In order to enhance the utility of the system, it is favorable to have diffusion coefficients of nutrients such as sugars in the culture medium beforehand. We have, therefore, built a simple and convenient experimental system that uses agar-gel to observe diffusion. Next, we performed computer simulations-based on random-walk concepts-of the experimental diffusion system and derived correlation formulas that relate observable diffusion data to diffusion coefficients. Finally, we applied these correlation formulas to our experimentally-determined diffusion data to estimate the diffusion coefficients of sugars. Our values for these coefficients agree reasonably well with values published in the literature. The effectiveness of our simple technique, which has elucidated the diffusion coefficients of some molecules which are rarely reported (e.g., galactose, trehalose, and glycerol) is demonstrated by the strong correspondence between the literature values and those obtained in our experiments.

Assessing off-site impacts of wildfires on aquatic organisms using in-situ assays

NASA Astrophysics Data System (ADS)

Ré, Ana; Saraiva, MariaJoão; Puga, João; Campos, Isabel; Pereira, Joana; Keizer, Jacob; Goncalves, Fernando; Abrantes, Nelson

2017-04-01

Wildfires have been recognized as an important source of diffuse pollution to aquatic systems, particularly through the production and transport of pyrolytic substances such as polycyclic aromatic hydrocarbons (PAHs) and metals associated to ash/soil loads. However, the effects of these compounds from recently burnt areas on the aquatic biota have been largely ignored. Hence, the main goal of this study was to assess the ecotoxicological effects of wildfires in aquatic systems through the use of in situ experiments. In this sense, five sites were selected in a catchment partially burnt: two in the main water course - Ceira river (Miranda do Corvo, Portugal), being one located upstream (RUS) and the other downstream (RDS) the burnt area; two in tributary streams within the burnt area (SUS and SDS); and finally one in a stream located in the unburnt part of the catchment (CS). During the first post-fire rainfall events, distinct organisms, including the water flea Daphnia magna, the freshwater shrimp Atyaephyra desmaresti, the freshwater clam Corbicula fluminea and the mosquitofish Gambusia holbrooki were exposed in situ, in all five sites, using dedicated test chambers. After four days of field exposition, the mortality and post-exposure feeding inhibition were evaluated. Feeding depression after exposure time was selected as a sub-lethal endpoint because it is a quick, sensitive and ecologically relevant indicator of toxic stress. The results showed negligible mortality for all the species and sites, thus lethality was not sensitive to discern impacts among the assessed sites. Conversely, the sub-lethal post-exposure feeding inhibition endpoint, revealed a decrease of feeding rate, in streams within the burnt area (SUS and SDS), that seemed to be the most affected places in the study area. Conversely, the sites outside the burnt area, both on river (RUS) and on the stream (CS), showed no adverse effects in this endpoint. Hence, the current results pointed-out that in situ bioassays were a suitable tool to assess the risks of wildfire to aquatic species and that the post-fire runoff rich in concerning substances as PAHs and metals can sub-lethally impair the aquatic organisms in water bodies located within or downstream the burnt area.

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

Strelcov, Evgheni; Cothren, Joshua E.; Leonard, Donovan N.

Progress in rational engineering of Li-ion batteries requires better understanding of the electrochemical processes and accompanying transformations in the electrode materials on multiple length scales. In spite of recent progress in utilizing transmission electron microscopy (TEM) to analyze these materials, in situ scanning electron microscopy (SEM) was mostly overlooked as a powerful tool that allows probing these phenomena on the nano and mesoscale. In this paper, we report on in situ SEM study of lithiation in a V 2O 5-based single-nanobelt battery with ionic liquid electrolyte. Coupled with cyclic voltammetry measurements, in situ SEM revealed the peculiarities of subsurface intercalation,more » formation of solid-electrolyte interface (SEI) and electromigration of liquid. We observed that single-crystalline vanadia nanobelts do not undergo large-scale amorphization or fracture during electrochemical cycling, but rather transform topochemically with only a slight shape distortion. Lastly, the SEI layer seems to have significant influence on the lithium ion diffusion and overall capacity of the single-nanobelt battery.« less

X-ray reciprocal space mapping of dislocation-mediated strain relaxation during InGaAs/GaAs(001) epitaxial growth

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

Sasaki, Takuo; Ohshita, Yoshio; Kamiya, Itaru

2011-12-01

Dislocation-mediated strain relaxation during lattice-mismatched InGaAs/GaAs(001) heteroepitaxy was studied through in situ x-ray reciprocal space mapping (in situ RSM). At the synchrotron radiation facility SPring-8, a hybrid system of molecular beam epitaxy and x-ray diffractometry with a two-dimensional detector enabled us to perform in situ RSM at high-speed and high-resolution. Using this experimental setup, four results in terms of film properties were simultaneously extracted as functions of film thickness. These were the lattice constants, the diffraction broadenings along in-plane and out-of-plane directions, and the diffuse scattering. Based on correlations among these results, the strain relaxation processes were classified into fourmore » thickness ranges with different dislocation behavior. In addition, the existence of transition regimes between the thickness ranges was identified. Finally, the dominant dislocation behavior corresponding to each of the four thickness ranges and transition regimes was noted.« less

In situ application of a cellulose bag and an ion exchanger for differentiation of labile and inert metal species in aquatic systems.

PubMed

Goveia, Danielle; Rosa, André Henrique; Bellin, Iramaia Corrêa; Lobo, Fabiana Aparecida; Fraceto, Leonardo Fernandes; Roveda, José Arnaldo Frutuoso; Romão, Luciane Pimenta Cruz; Dias Filho, Newton Luiz

2008-02-01

This work involved the development and application of a new analytical procedure for in-situ characterization of the lability of metal species in aquatic systems by using a system equipped with a diffusion membrane and cellulose organomodified with p-aminobenzoic acid groups (DM-Cell-PAB). To this end, the DM-Cell-PAB system was prepared by adding cellulose organomodified with p-aminobenzoic acid groups (Cell-PAB) to pre-purified cellulose bags. After the DM-Cell-PAB system was sealed, it was examined in the laboratory. The in-situ application involved immersing the DM-Cell-PAB system in two different rivers, enabling us to study the relative lability of metal species (Cu, Cd, Fe, Mn, and Ni) as a function of time and quantity of exchanger. The procedure is simple and opens up a new perspective for understanding environmental phenomena relating to the complexation, transport, stability, and lability of metal species in aquatic systems rich in organic matter.

In situ synthesis and characterization of uranium carbide using high temperature neutron diffraction

NASA Astrophysics Data System (ADS)

Reiche, H. Matthias; Vogel, Sven C.; Tang, Ming

2016-04-01

We investigated the formation of UCx from UO2+x and graphite in situ using neutron diffraction at high temperatures with particular focus on resolving the conflicting reports on the crystal structure of non-quenchable cubic UC2. The agents were UO2 nanopowder, which closely imitates nano grains observed in spent reactor fuels, and graphite powder. In situ neutron diffraction revealed the onset of the UO2 + 2C → UC + CO2 reaction at 1440 °C, with its completion at 1500 °C. Upon further heating, carbon diffuses into the uranium carbide forming C2 groups at the octahedral sites. This resulting high temperature cubic UC2 phase is similar to the NaCl-type structure as proposed by Bowman et al. Our novel experimental data provide insights into the mechanism and kinetics of formation of UC as well as characteristics of the high temperature cubic UC2 phase which agree with proposed rotational rehybridization found from simulations by Wen et al.

Comparison of in situ DGT measurement with ex situ methods for predicting cadmium bioavailability in soils with combined pollution to biotas.

PubMed

Wang, Peifang; Liu, Cui; Yao, Yu; Wang, Chao; Wang, Teng; Yuan, Ye; Hou, Jun

2017-05-01

To assess the capabilities of the different techniques in predicting Cadmium (Cd) bioavailability in Cd-contaminated soils with the addition of Zn, one in situ technique (diffusive gradients in thin films; DGT) was compared with soil solution concentration and four widely used single-step extraction methods (acetic acid, EDTA, sodium acetate and CaCl 2 ). Wheat and maize were selected as tested species. The results demonstrated that single Cd-polluted soils inhibited the growth of wheat and maize significantly compared with control plants; the shoot and root biomasses of the plants both dropped significantly (P < 0.05). The addition of Zn exhibited a strong antagonism to the physiological toxicity induced by Cd. The Pearson correlation coefficient presented positive correlations (P < 0.01, R > 0.9) between Cd concentrations in two plants and Cd bioavailability indicated by each method in soils. Consequently, the results indicated that the DGT technique could be regarded as a good predictor of Cd bioavailability to plants, comparable to soil solution concentration and the four single-step extraction methods. Because the DGT technique can offer in situ data, it is expected to be widely used in more areas.

Nucleation Control for Large, Single Crystalline Domains of Monolayer Hexagonal Boron Nitride via Si-Doped Fe Catalysts

PubMed Central

2015-01-01

The scalable chemical vapor deposition of monolayer hexagonal boron nitride (h-BN) single crystals, with lateral dimensions of ∼0.3 mm, and of continuous h-BN monolayer films with large domain sizes (>25 μm) is demonstrated via an admixture of Si to Fe catalyst films. A simple thin-film Fe/SiO2/Si catalyst system is used to show that controlled Si diffusion into the Fe catalyst allows exclusive nucleation of monolayer h-BN with very low nucleation densities upon exposure to undiluted borazine. Our systematic in situ and ex situ characterization of this catalyst system establishes a basis for further rational catalyst design for compound 2D materials. PMID:25664483

Chemical vapour deposition growth of carbon nanotube forests: kinetics, morphology, composition, and their mechanisms

NASA Astrophysics Data System (ADS)

Vinten, Phillip

This thesis analyzes the chemical vapour deposition (CVD) growth of vertically aligned carbon nanotube (CNT) forests in order to understand how CNT forests grow, why they stop growing, and how to control the properties of the synthesized CNTs. in situ kinetics data of the growth of CNT forests are gathered by in situ optical microscopy. The overall morphology of the forests and the characteristics of the individual CNTs in the forests are investigated using scanning electron microscopy and Raman spectroscopy. The in situ data show that forest growth and termination are activated processes (with activation energies on the order of 1 eV), suggesting a possible chemical origin. The activation energy changes at a critical temperature for ethanol CVD (approximately 870°C). These activation energies and critical temperature are also seen in the temperature dependence of several important characteristics of the CNTs, including the defect density as determined by Raman spectroscopy. This observation is seen across several CVD processes and suggests a mechanism of defect healing. The CNT diameter also depends on the growth temperature. In this thesis, a thermodynamic model is proposed. This model predicts a temperature and pressure dependence of the CNT diameter from the thermodynamics of the synthesis reaction and the effect of strain on the enthalpy of formation of CNTs. The forest morphology suggests significant interaction between the constituent CNTs. These interactions may play a role in termination. The morphology, in particular a microscale rippling feature that is capable of diffracting light, suggest a non-uniform growth rate across the forest. A gas phase diffusion model predicts a non-uniform distribution of the source gas. This gas phase diffusion is suggested as a possible explanation for the non-uniform growth rate. The gas phase diffusion is important because growth by acetylene CVD is found to be very efficient (approximately 30% of the acetylene is converted to CNTs). It is seen that multiple mechanisms are active during CNT growth. The results of this thesis provide insight into both the basic understanding of the microscopic processes involved in CVD growth and how to control the properties of the synthesized CNTs.

Passive sampling of DDT, DDE and DDD in sediments: accounting for degradation processes with reaction-diffusion modeling.

PubMed

Tcaciuc, A Patricia; Borrelli, Raffaella; Zaninetta, Luciano M; Gschwend, Philip M

2018-01-24

Passive sampling is becoming a widely used tool for assessing freely dissolved concentrations of hydrophobic organic contaminants in environmental media. For certain media and target analytes, the time to reach equilibrium exceeds the deployment time, and in such cases, the loss of performance reference compounds (PRCs), loaded in the sampler before deployment, is one of the common ways used to assess the fractional equilibration of target analytes. The key assumption behind the use of PRCs is that their release is solely diffusion driven. But in this work, we show that PRC transformations in the sediment can have a measurable impact on the PRC releases and even allow estimation of that compound's transformation rate in the environment of interest. We found that in both field and lab incubations, the loss of the 13 C 2,4'-DDT PRC from a polyethylene (PE) passive sampler deployed at the sediment-water interface was accelerated compared to the loss of other PRCs ( 13 C-labeled PCBs, 13 C-labeled DDE and DDD). The DDT PRC loss was also accompanied by accumulation in the PE of its degradation product, 13 C 2,4'-DDD. Using a 1D reaction-diffusion model, we deduced the in situ degradation rates of DDT from the measured PRC loss. The in situ degradation rates increased with depth into the sediment bed (0.14 d -1 at 0-10 cm and 1.4 d -1 at 30-40 cm) and although they could not be independently validated, these rates compared favorably with literature values. This work shows that passive sampling users should be cautious when choosing PRCs, as degradation processes can affect some PRC's releases from the passive sampler. More importantly, this work opens up the opportunity for novel applications of passive samplers, particularly with regard to investigating in situ degradation rates, pathways, and products for both legacy and emerging contaminants. However, further work is needed to confirm that the rates deduced from model fitting of PRC loss are a true reflection of DDT transformation rates in sediments.

In vitro and in situ characterization of arthroscopic loop security and knot security of braided polyblend sutures: a biomechanical study.

PubMed

Armstrong, Lucas C; Chong, Alexander; Livermore, Ryan W; Prohaska, Daniel J; Doyon, Amanda N; Wooley, Paul H

2015-04-01

We conducted a study to evaluate biomechanical performance during destructive testing of several different suture materials in various arthroscopic knot configurations under both in vitro and in situ conditions. Surgeons of different levels of experience tied the knots. Three different arthroscopic knots (static surgeon's, Weston, Tennessee slider) with 3 reverse half-hitches on alternating posts were tested using Fiberwire, ForceFiber, Orthocord, and Ultrabraid suture materials under both in vitro and in situ (blood plasma at 37°C) conditions. Three surgeons of different experience levels tied the knots on a post 30 mm in circumference. A single load-to-failure test was performed. There were no significant in vitro-in situ differences for Ultrabraid in the different knot configurations or with the different experience levels. Surgeon B (intermediate experience) showed no significant differences between test conditions for any knot configuration or suture material. With Tennessee slider knots, surgeon C (least experience) showed significantly lower clinical failure load under both test conditions and had a higher percentage of complete knot slippage. Surgeon B had no knot slippage with use of Fiberwire. Both the aqueous environment and the surgeon's familiarity with certain knots have an effect on knot security.

Lithium isotope fractionation by diffusion in minerals Part 2: Olivine

NASA Astrophysics Data System (ADS)

Richter, Frank; Chaussidon, Marc; Bruce Watson, E.; Mendybaev, Ruslan; Homolova, Veronika

2017-12-01

Recent experiments have shown that lithium isotopes can be significantly fractionated by diffusion in silicate liquids and in augite. Here we report new laboratory experiments that document similarly large lithium isotopic fractionation by diffusion in olivine. Two types of experiments were used. A powder-source method where lithium from finely ground spodumene (LiAlSi2O6) diffused into oriented San Carlos olivine, and piston cylinder annealing experiments where Kunlun clinopyroxene (∼30 ppm lithium) and oriented San Carlos olivine (∼2 ppm lithium) were juxtaposed. The lithium concentration along traverses across the run products was measured using both laser ablation as a source for a Varian 820-MS quadrupole mass spectrometer and a CAMECA 1270 secondary ion mass spectrometer. The CAMECA 1270 was also used to measure the lithium isotopic fractionation across olivine grains recovered from the experiments. The lithium isotopes were found to be fractionationed by many tens of permil in the diffusion boundary layer at the grain edges as a result of 6Li diffusing significantly faster than 7Li. The lithium concentration and isotopic fractionation data across the olivine recovered from the different experiments were modeled using calculations in which lithium was assumed to be of two distinct types - one being fast diffusing interstitial lithium, the other much less mobile lithium on a metal site. The two-site diffusion model involves a large number of independent parameters and we found that different choices of the parameters can produce very comparable fits to the lithium concentration profiles and associated isotopic fractionation. Because of this nonuniqueness we are able to determine only a range for the relative diffusivity of 6Li compared to 7Li. When the mass dependence of lithium diffusion is parameterized as D6Li /D7Li =(7 / 6) β , the isotope fractionation for diffusion along the a and c crystallographic direction of olivine can be fit by β = 0.4 ± 0.1 while the fractionation in the b direction appears to be somewhat lower. Model calculations were also used to fit the lithium concentration and isotopic fractionation across a natural olivine grain from a peridotite xenolith from the Eastern North China Craton. The isotopic data were fit using β values (0.3-0.36) similar to that of the laboratory experiments. This, along with the fact that the isotopic fractionation is restricted to that part of the mineral with a gradient in lithium concentration, is strong evidence that the lithium zoning of this mineral grain is the result of lithium loss by diffusion and thus that it can be used, as illustrated, to constrain the cooling history.

The Use of Whole-Mount "in Situ" Hybridization to Illustrate Gene Expression Regulation

ERIC Educational Resources Information Center

Llamusí, Beatriz; Muñoz-Soriano, Verónica; Paricio, Nuria; Artero, Rubén

2014-01-01

"In situ" hybridization is a widely used technique for studying gene expression. Here, we describe two experiments addressed to postgraduate genetics students in which the effect of transcription factors on gene expression is analyzed in "Drosophila embryos of different genotypes by whole-mount in situ hybridization. In one of the…

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.

Diffusion of Carbon Dioxide in Cordierite-like Structures: a FTIR Imaging Approach

NASA Astrophysics Data System (ADS)

Radica, F.; Bellatreccia, F.; Della Ventura, G.; Freda, C.; Cinque, G.; Cestelli Guidi, M.

2013-12-01

In the last decades microporous and mesoporous minerals have been recognized to be very important materials from both a geological and a technological viewpoint. In this context, cordierite plays a key role since it represents the only case of a widespread microporous mineral able to trap significant amounts of molecular H2O and CO2 [1] under extreme geological conditions, spanning from the amphibolite facies to ultra-high temperature metamorphism to crustal anatexis [2]. The analysis of volatiles in cordierite can be a very useful tool to define the composition of coexisting fluids during its formation, thus a deeper knowledge of their diffusion mechanism through the structure is crucial in petrologic studies. However, it may have significant implications on technological issues such as the design of new strategies for the permanent sequestration of atmospheric CO2. The incorporation of CO2 into cordierite has been studied by several authors [1, 3], who pointed out the extreme difficulty to reach the sample saturation and homogenization, implying that in experimental studies knowledge of the actual distribution of the volatile molecules in the run samples is crucial to derive any scientific conclusion. In this work, we addressed this problem using FTIR imaging. Our experiments were carried out in tandem on natural cordierite and synthetic CO2-free beryl, a mineral which is isostructural with cordierite. All samples were treated in CO2-saturated atmosphere at different pressure, temperature and time conditions using a non end-load piston-cylinder apparatus at INGV. The run products were oriented using a spindle stage, cut and doubly polished, and analyzed using polarized micro-FTIR spectroscopy at INFN-LNF in order to study the distribution across the sample and quantify the CO2 content. Preliminary data show that both pressure and time play a major role on the diffusion of gaseous CO2 in both cordierite and beryl, whereas the effect of temperature is less noticeable. High-resolution FPA (focal-plane-array of detectors) SR (synchrotron radiation)-FTIR imaging was done at beamline B22, Diamond laboratory (Oxford, UK). The data show that the diffusion of CO2 occurs exclusively along the structural channels running along the c-axis direction. Notably, the diffusion path of CO2 does not exceed 200 μm even after 10 days treatment. Sample cracks formed during the experimental runs speed up the gas diffusion; measured CO2 contents along these cracks are up to 4 times higher. Several CO2-rich samples were heat-treated up to 1200 °C using a Linkam heating stage to investigate the rate of CO2 evacuation as a function of temperature. In situ FTIR spectra have shown that the decarbonation process starts around 800 °C. Continuous heating experiments on 60 μm thick slabs pointed out that the diffusion rates are very low; complete CO2 extraction could not be achieved even after 2 hour heating at 1000 °C. [1] Armbruster and Bloss (1982) Am. Mineral. 67, 284-291. [2] Vry et al. (1990) Am. Mineral. 75, 71-88 [3] Le Breton (1989) Contrib. Mineral. Petrol. 103, 387-396.

In situ and laboratory studies on the fate of specific organic compounds in an anaerobic landfill leachate plume, 1. Experimental conditions and fate of phenolic compounds

NASA Astrophysics Data System (ADS)

Nielsen, Per H.; Albrechtsen, Hans-Jørgen; Heron, Gorm; Christensen, Thomas H.

1995-11-01

The transformation of specific organic compounds was investigated by in situ and laboratory experiments in an anaerobic landfill leachate pollution plume at four different distances from the landfill. This paper presents the experimental conditions in the in situ microcosm and laboratory batch microcosm experiments performed and the results on the fate of 7 phenolic compounds. Part 2 of this series of papers, also published in this issue, presents the results on the fate of 8 aromatic compounds and 4 chlorinated aliphatic compounds. The redox conditions in the plume were characterized as methanogenic, Fe(III)-reducing and NO 3--reducing by the redox sensitive species present in groundwater and sediment and by bioassays. With a few exceptions the aquifer redox conditions were maintained throughout the experiments as monitored by redox sensitive species present in groundwater during the experiments, by redox sensitive species present in the sediment after the experiments and by bioassays performed after the experiments. Transformation of nitrophenol was very fast close to the landfill in strongly reducing conditions, while transformation was slower in the more oxidized part of the plume. Lag phases for the nitrophenols were short (maximum 10 days). Phenol was only transformed in the more distant part of the plume in experiments where NO 3-, Fe(III) and Mn(IV) reduction was dominant. Lag phases for phenol were either absent or lasted up to 2 months. Dichlorophenols were only transformed in experiments representing strongly reducing, presumably methanogenic, redox conditions close to the landfill after lag phases of up to 3 months. Transformation of o-cresol was not observed in any of the experiments throughout the plume. Generally, there was good accordance between the results obtained by in situ and laboratory experiments, both concerning redox conditions and the fate of the phenolic compounds. However, for phenol and 2,4-dichlorophenol, transformation was observed in some in situ experiments but not in the corresponding laboratory experiments. In some experiments, this coul be explained by differences in the redox conditions developing during the experiments. Nitrophenols were apparently transformed abiotically in the most reduced part of the plume, at 2 m from the landfill.

The diffusion dynamics of PEGylated liposomes in the intact vitreous of the ex vivo porcine eye: A fluorescence correlation spectroscopy and biodistribution study.

PubMed

Eriksen, Anne Z; Brewer, Jonathan; Andresen, Thomas L; Urquhart, Andrew J

2017-04-30

The diffusion dynamics of nanocarriers in the vitreous and the influence of nanocarrier physicochemical properties on these dynamics is an important aspect of the efficacy of intravitreal administered nanomedicines for the treatment of posterior segment eye diseases. Here we use fluorescence correlation spectroscopy (FCS) to determine liposome diffusion coefficients in the intact vitreous (D Vit ) of ex vivo porcine eyes using a modified Miyake-Apple technique to minimize the disruption of the vitreous fine structure. We chose to investigate whether the zeta potential of polyethylene glycol functionalized (i.e. PEGylated) liposomes altered liposome in situ diffusion dynamics in the vitreous. Non-PEGylated cationic nanocarriers have previously shown little to no diffusion in the vitreous, whilst neutral and anionic have shown diffusion. The liposomes investigated had diameters below 150nm and zeta potentials ranging from -20 to +12mV. We observed that PEGylated cationic liposomes had significantly lower D Vit values (1.14μm 2 s -1 ) than PEGylated neutral and anionic liposomes (2.78 and 2.87μm 2 s -1 ). However, PEGylated cationic liposomes had a similar biodistribution profile across the vitreous to the other systems. These results show that PEGylated cationic liposomes with limited cationic charge can diffuse across the vitreous and indicate that the vitreous as a barrier to nanocarriers (Ø<500nm) is more complicated than simply an electrostatic barrier as previously suggested. Copyright © 2017 Elsevier B.V. All rights reserved.

Engineering experimental program on the effects of near-space radiation on lithium doped solar cells

NASA Technical Reports Server (NTRS)

1971-01-01

The results of an experimental evaluation of the real-time degradation characteristics of lithium-diffused silicon solar cells are reported. A strontium-90 radioisotope was used for simulation of a typical earth-orbital electron environment. The experiment was performed in an ion pump vacuum chamber with samples maintained at -50, +20, +50, and +80 C. Samples were illuminated during the 6-month exposure run with solar cell 1-5 characteristics measured periodically in situ. This 6-month exposure corresponded to a 1 MeV equivalent fluence of approximately 10 to the 14th power electrons/sq cm. Several types of lithium cells were irradiatied and compared directly with conventional N/P cells. The best lithium cells compared favorably with N/P cells, particularly at the higher test temperatures. With a slight improvement of initial performance characteristics, lithium cells appear feasible for 5 to 10 year missions at synchronous altitude. Based on the reported results and those of other irradiation experiments, lithium cells would appear to be superior to N/P cells in proton-dominated earth-orbital environments. Another important conclusion of the effort was that illuminated/loaded cells degrade more rapidly than do dark/unloaded cells. The irradiation experiment provided data of high quality with a high degree of confidence because of the experimental and statistical analysis techniques utilized.

A Sounding Rocket Investigation of the Fine Structure in the Mesopause Region in Conjunction with High Spatial Resolution Lidar Measurements

NASA Technical Reports Server (NTRS)

Larsen, M. F.

2003-01-01

The grant funds were provided to carry out chemical tracer wind and turbulence measurements in the mesosphere and lower thermosphere as part of the Turbulent Oxygen Mixing Experiment (TOMEX) for which Dr. James Hecht of the Aerospace Corp. was the Principal Investigator. Clemson University designed, built, and tested two chemical tracer release payload sections for the 21.126 and 21.127 payloads which, in addition, had photometer and ionization gauge instrumentation. The tracer chemical was trimethyl aluminum (TMA). The experiment was carried out at White Sands Missile Range in New Mexico on October 26,2000. The location was chosen because of the proximity to the Starfire Optical Range (SOR) which hosted the powerful University of Illinois sodium lidar for an extended period prior to and also during the launch window. Since the SOR telescope is fully steerable, lidar measurements in the same volume sampled by the rocket were possible. The primary objective of the experiment was to measure the turbulent diffusion and mixing in the mesosphere and lower thermosphere, especially in layers characterized by convective and/or dynamical instabilities. The lidar, which is capable of measuring the sodium density, temperatures, and winds with good range and time resolution, provided the launch criteria, as well as context measurements for the in situ rocket observations.

Design and characterization of the Large-aperture Experiment to Detect the Dark Age (LEDA) radiometer systems

NASA Astrophysics Data System (ADS)

Price, D. C.; Greenhill, L. J.; Fialkov, A.; Bernardi, G.; Garsden, H.; Barsdell, B. R.; Kocz, J.; Anderson, M. M.; Bourke, S. A.; Craig, J.; Dexter, M. R.; Dowell, J.; Eastwood, M. W.; Eftekhari, T.; Ellingson, S. W.; Hallinan, G.; Hartman, J. M.; Kimberk, R.; Lazio, T. Joseph W.; Leiker, S.; MacMahon, D.; Monroe, R.; Schinzel, F.; Taylor, G. B.; Tong, E.; Werthimer, D.; Woody, D. P.

2018-05-01

The Large-Aperture Experiment to Detect the Dark Age (LEDA) was designed to detect the predicted O(100) mK sky-averaged absorption of the Cosmic Microwave Background by Hydrogen in the neutral pre- and intergalactic medium just after the cosmological Dark Age. The spectral signature would be associated with emergence of a diffuse Lyα background from starlight during `Cosmic Dawn'. Recently, Bowman et al. (2018) have reported detection of this predicted absorption feature, with an unexpectedly large amplitude of 530 mK, centered at 78 MHz. Verification of this result by an independent experiment, such as LEDA, is pressing. In this paper, we detail design and characterization of the LEDA radiometer systems, and a first-generation pipeline that instantiates a signal path model. Sited at the Owens Valley Radio Observatory Long Wavelength Array, LEDA systems include the station correlator, five well-separated redundant dual polarization radiometers and backend electronics. The radiometers deliver a 30-85 MHz band (16 < z < 34) and operate as part of the larger interferometric array, for purposes ultimately of in situ calibration. Here, we report on the LEDA system design, calibration approach, and progress in characterization as of January 2016. The LEDA systems are currently being modified to improve performance near 78 MHz in order to verify the purported absorption feature.

A Transition in the Cumulative Reaction Rate of Two Species Diffusion with Bimolecular Reaction

NASA Astrophysics Data System (ADS)

Rajaram, Harihar; Arshadi, Masoud

2015-04-01

Diffusion and bimolecular reaction between two initially separated reacting species is a prototypical small-scale description of reaction induced by transverse mixing. It is also relevant to diffusion controlled transport regimes as encountered in low-permeability matrix blocks in fractured media. In previous work, the reaction-diffusion problem has been analyzed as a Stefan problem involving a distinct moving boundary (reaction front), which predicts that front motion scales as √t, and the cumulative reaction rate scales as 1/√t-. We present a general non-dimensionalization of the problem and a perturbation analysis to show that there is an early time regime where the cumulative reaction rate scales as √t- rather than 1/√t. The duration of this early time regime (where the cumulative rate is kinetically rather than diffusion controlled) depends on the rate parameter, in a manner that is consistently predicted by our non-dimensionalization. We also present results on the scaling of the reaction front width. We present numerical simulations in homogeneous and heterogeneous porous media to demonstrate the limited influence of heterogeneity on the behavior of the reaction-diffusion system. We illustrate applications to the practical problem of in-situ chemical oxidation of TCE and PCE by permanganate, which is employed to remediate contaminated sites where the DNAPLs are largely dissolved in the rock matrix.

beta Phase Growth and Precipitation in the 5xxx Series Aluminum Alloy System

NASA Astrophysics Data System (ADS)

Scotto D'Antuono, Daniel

The 5xxx series aluminum alloys are commonly used for structural applications due to their high strength to weight ratio, corrosion resistance, and weldability. This material system is a non-heat treatable aluminum and derives its strength from a super saturation of magnesium (3%>), and from cold rolling. While these materials have many admiral properties, they can undergo a process known as sensitization when exposed to elevated temperatures (50-280°C) for extended periods of time. During this process, magnesium segregates toward the grain boundaries and forms the secondary precipitate β phase (Al3Mg2). When exposed to harsh environments such as sea water, a galvanic couple is formed between the Al matrix and the β phase precipitates. The precipitates become anodic to the matrix and preferentially dissolve leaving gaps along the boundary network, ultimately leading to stress corrosion cracking. While this problem has been known to occur for some time now, questions relating to nucleation sites, misorientation dependence, effect of prior strain, and preferred temperature regimes remain unanswered. The work contained in this thesis attempted to better understand the kinetics, growth, and misorientation dependence, of β phase precipitation using in situ transmission electron microscopy experiments which allowed for direct visualization of the precipitation process. Orientation imaging using a Nanomegas/ASTAR system (OIM in TEM) coupled with the in situ experiments, along with elemental STEM EELs mapping were used to better understand the diffusion of Mg and found low angle boundaries as potential sites for nucleation. The resulting STEM EELs experiments also showed that Mg is much more stable at the grain boundaries than previously thought. Concurrent bulk ex-situ studies were used to compare various heat treatments, as well as to failed in service material showing that the low temperature treatments yield the metastable β’ phase more readily than the β equilibrium phase. The work here has identified the size, location, and kinetics of β phase formation as well as the effects of pre-strain (cold rolling) and boundary misorientation on precipitation showing that increases in dislocations speeds up sensitization and increases nucleation sites but does not increase overall precipitate size. This work also compared precipitate type (β vs. β’) showing that the metastable β’ phase is more common in low temperature treated material and the main precipitate found in failed in service material. A comparison between the corrosion effects of the two precipitation showed that lower temperature treatments have a higher degree of sensitization further delineating between the two forms.

In-situ hydrogen in metal determination using a minimum neutron source strength and exposure time.

PubMed

Hatem, M; Agamy, S; Khalil, M Y

2013-08-01

Water is frequently present in the environment and is a source of hydrogen that can interact with many materials. Because of its small atomic size, a hydrogen atom can easily diffuse into a host metal, and though the metal may appear unchanged for a time, the metal will eventually abruptly lose its strength and ductility. Thus, measuring the hydrogen content in metals is important in many fields, such as in the nuclear industry, in automotive and aircraft fabrication, and particularly, in offshore oil and gas fields. It has been demonstrated that the use of nuclear methods to measure the hydrogen content in metals can achieve sensitivity levels on the order of parts per million. However, the use of nuclear methods in the field has not been conducted for two reasons. The first reason is due to exposure limitations. The second reason is due to the hi-tech instruments required for better accuracy. In this work, a new method using a low-strength portable neutron source is explored in conjunction with detectors based on plastic nuclear detection films. The following are the in-situ requirements: simplicity in setup, high reliability, minimal exposure dose, and acceptable accuracy at an acceptable cost. A computer model of the experimental setup is used to reproduce the results of a proof-of-concept experiment and to predict the sensitivity levels under optimised experimental conditions. Copyright © 2013 Elsevier Ltd. All rights reserved.

Gold catalyzed nickel disilicide formation: a new solid-liquid-solid phase growth mechanism.

PubMed

Tang, Wei; Picraux, S Tom; Huang, Jian Yu; Liu, Xiaohua; Tu, K N; Dayeh, Shadi A

2013-01-01

The vapor-liquid-solid (VLS) mechanism is the predominate growth mechanism for semiconductor nanowires (NWs). We report here a new solid-liquid-solid (SLS) growth mechanism of a silicide phase in Si NWs using in situ transmission electron microcopy (TEM). The new SLS mechanism is analogous to the VLS one in relying on a liquid-mediating growth seed, but it is fundamentally different in terms of nucleation and mass transport. In SLS growth of Ni disilicide, the Ni atoms are supplied from remote Ni particles by interstitial diffusion through a Si NW to the pre-existing Au-Si liquid alloy drop at the tip of the NW. Upon supersaturation of both Ni and Si in Au, an octahedral nucleus of Ni disilicide (NiSi2) forms at the center of the Au liquid alloy, which thereafter sweeps through the Si NW and transforms Si into NiSi2. The dissolution of Si by the Au alloy liquid mediating layer proceeds with contact angle oscillation at the triple point where Si, oxide of Si, and the Au alloy meet, whereas NiSi2 is grown from the liquid mediating layer in an atomic stepwise manner. By using in situ quenching experiments, we are able to measure the solubility of Ni and Si in the Au-Ni-Si ternary alloy. The Au-catalyzed mechanism can lower the formation temperature of NiSi2 by 100 °C compared with an all solid state reaction.

Novel in situ forming hydrogel microneedles for transdermal drug delivery.

PubMed

Sivaraman, Arunprasad; Banga, Ajay K

2017-02-01

Novel in situ forming hydrogel microneedles were evaluated for transdermal drug delivery using a biocompatible non-ionic triblock amphiphilic thermosensitive copolymer. The transition property of poloxamer from solution at room temperature to gel at skin temperature (32 °C) was utilized in preparation of in situ forming hydrogel microneedles. Methotrexate has been used to treat solid tumors, but because of its narrow safety margin, it requires sustained delivery within the therapeutic window. Formulations with and without poloxamer at different methotrexate concentrations were prepared and evaluated for drug permeation across skin using vertical Franz diffusion cell for 72 h. Sol-gel transition, skin resistance and thickness, microneedles geometry, microchannel depth, shape, formation and uniformity, viscoelasticity of skin, and in vitro drug permeation were characterized and tested. An average cumulative drug amount of 32.2 ± 15.76 and 114.54 ± 40.89 μg/cm 2 for porcine ear skin and 3.89 ± 0.60 and 10.27 ± 6.98 μg/cm 2 for dermatomed human skin from 0.2 % w/w and 0.4 % w/w methotrexate formulations was delivered by the in situ forming hydrogel microneedles. These in situ hydrogel microneedles embedded within the porated site of the skin provided a steady and sustained drug delivery.

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.

Solvent exchange-induced in situ forming gel comprising ethyl cellulose-antimicrobial drugs.

PubMed

Phaechamud, Thawatchai; Mahadlek, Jongjan

2015-10-15

Solvent-exchanged in situ forming gel is a drug delivery system which is in sol form before administration. When it contacts with the body fluid, then the water miscible organic solvent dissipates and water penetrates into the system, leading the polymer precipitation as in situ gel at the site of injection. The aim of this research was to study the parameters affecting the gel properties, drug release and antimicrobial activities of the in situ forming gels prepared from ethyl cellulose (EC) dissolved in N-methyl pyrrolidone (NMP) to deliver the antimicrobial agents (doxycycline hyclate, metronidazole and benzyl peroxide) for periodontitis treatment. The gel appearance, pH, viscosity, rheology, syringeability, gel formation, rate of water diffusion into the gels, in vitro degradation, drug release behavior and antimicrobial activities against Staphylococcus aureus, Escherichia coli, Candida albicans, Streptococcus mutans and Porphyrommonas gingivalis were determined. Increasing the amount of EC increased the viscosity of system while still exhibiting Newtonian flow and increased the work of syringeability whereas decreased the releasing of drug. The system transformed into the rigid gel formation after being injected into the simulated gingival crevicular fluid. The developed systems containing 5% w/w antimicrobial agent showed the antimicrobial activities against all test bacteria. Thus the developed solvent exchange-induced in situ forming gels comprising EC-antimicrobial drugs exhibited potential use for periodontitis treatment. Copyright © 2015 Elsevier B.V. All rights reserved.

Fractal Theory and Field Cover Experiments: Implications for the Fractal Characteristics and Radon Diffusion Behavior of Soils and Rocks.

PubMed

Tan, Wanyu; Li, Yongmei; Tan, Kaixuan; Duan, Xianzhe; Liu, Dong; Liu, Zehua

2016-12-01

Radon diffusion and transport through different media is a complex process affected by many factors. In this study, the fractal theories and field covering experiments were used to study the fractal characteristics of particle size distribution (PSD) of six kinds of geotechnical materials (e.g., waste rock, sand, laterite, kaolin, mixture of sand and laterite, and mixture of waste rock and laterite) and their effects on radon diffusion. In addition, the radon diffusion coefficient and diffusion length were calculated. Moreover, new formulas for estimating diffusion coefficient and diffusion length functional of fractal dimension d of PSD were proposed. These results demonstrate the following points: (1) the fractal dimension d of the PSD can be used to characterize the property of soils and rocks in the studies of radon diffusion behavior; (2) the diffusion coefficient and diffusion length decrease with increasing fractal dimension of PSD; and (3) the effectiveness of final covers in reducing radon exhalation of uranium tailings impoundments can be evaluated on the basis of the fractal dimension of PSD of materials.

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

PubMed

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

2015-06-19

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

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

NASA Astrophysics Data System (ADS)

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

2015-06-01

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

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

Constraints on oxygen fugacity within metal capsules

NASA Astrophysics Data System (ADS)

Faul, Ulrich H.; Cline, Christopher J., II; Berry, Andrew; Jackson, Ian; Garapić, Gordana

2018-06-01

Experiments were conducted with olivine encapsulated or wrapped in five different metals (Pt, Ni, Ni_{70}Fe_{30}, Fe, and Re) to determine the oxygen fugacity in the interior of large capsules used for deformation and seismic property experiments. Temperature (1200°C), pressure (300 MPa), and duration (24 h) were chosen to represent the most common conditions in these experiments. The oxygen fugacity was determined by analysing the Fe content of initially pure Pt particles that were mixed with the olivine powder prior to the experiments. Oxygen fugacities in the more oxidizing metal containers are substantially below their respective metal-oxide buffers, with the fO_2 of sol-gel olivine in Ni about 2.5 orders of magnitude below Ni-NiO. Analysis of olivine and metal blebs reveals three different length-, and hence diffusive time scales: (1) Fe loss to the capsule over ˜ 100 μ m, (2) fO_2 gradients at the sample-capsule interface up to 2 mm into the sample, and (3) constant interior fO_2 values with an ordering corresponding to the capsule material. The inferred diffusive processes are: Fe diffusion in olivine with a diffusivity ˜ 10^{-14} m^2/s, diffusion possibly of oxygen along grain boundaries with a diffusivity ˜ 10^{-12} m^2/s, and diffusion possibly involving pre-existing defects with a diffusivity ˜ 10^{-10} m^2/s. The latter, fast adjustment to changing fO_2 may consist of a rearrangement of pre-existing defects, representing a metastable equilibrium, analogous to decoration of pre-existing defects by hydrogen. Full adjustment to the external fO_2 requires atomic diffusion.

Integration of stable carbon isotope, microbial community, dissolved hydrogen gas, and 2HH2O tracer data to assess bioaugmentation for chlorinated ethene degradation in fractured rocks

USGS Publications Warehouse

Révész, Kinga M.; Lollar, Barbara Sherwood; Kirshtein, Julie D.; Tiedeman, Claire; Imbrigiotta, Thomas E.; Goode, Daniel J.; Shapiro, Allen M.; Voytek, Mary A.; Lancombe, Pierre J.; Busenberg, Eurybiades

2014-01-01

An in situ bioaugmentation (BA) experiment was conducted to understand processes controlling microbial dechlorination of trichloroethene (TCE) in groundwater at the Naval Air Warfare Center (NAWC), West Trenton, NJ. In the BA experiment, an electron donor (emulsified vegetable oil and sodium lactate) and a chloro-respiring microbial consortium were injected into a well in fractured mudstone of Triassic age. Water enriched in 2H was also injected as a tracer of the BA solution, to monitor advective transport processes. The changes in concentration and the δ13C of TCE, cis-dichloroethene (cis-DCE), and vinyl chloride (VC); the δ2H of water; changes in the abundance of the microbial communities; and the concentration of dissolved H2 gas compared to pre- test conditions, provided multiple lines of evidence that enhanced biodegradation occurred in the injection well and in two downgradient wells. For those wells where the biodegradation was stimulated intensively, the sum of the molar chlorinated ethene (CE) concentrations in post-BA water was higher than that of the sum of the pre-BA background molar CE concentrations. The concentration ratios of TCE/(cis-DCE + VC) indicated that the increase in molar CE concentration may result from additional TCE mobilized from the rock matrix in response to the oil injection or due to desorption/diffusion. The stable carbon isotope mass-balance calculations show that the weighted average 13C isotope of the CEs was enriched for around a year compared to the background value in a two year monitoring period, an effective indication that dechlorination of VC was occurring. Insights gained from this study can be applied to efforts to use BA in other fractured rock systems. The study demonstrates that a BA approach can substantially enhance in situ bioremediation not only in fractures connected to the injection well, but also in the rock matrix around the well due to processes such as diffusion and desorption. Because the effect of the BA was intensive only in wells where an amendment was distributed during injection, it is necessary to adequately distribute the amendments throughout the fractured rock to achieve substantial bioremediation. The slowdown in BA effect after a year is due to some extend to the decrease abundant of appropriate microbes, but more likely the decreased concentration of electron donor.

Integration of stable carbon isotope, microbial community, dissolved hydrogen gas, and ²HH₂O tracer data to assess bioaugmentation for chlorinated ethene degradation in fractured rocks.

PubMed

Révész, Kinga M; Lollar, Barbara Sherwood; Kirshtein, Julie D; Tiedeman, Claire R; Imbrigiotta, Thomas E; Goode, Daniel J; Shapiro, Allen M; Voytek, Mary A; Lacombe, Pierre J; Busenberg, Eurybiades

2014-01-01

An in situ bioaugmentation (BA) experiment was conducted to understand processes controlling microbial dechlorination of trichloroethene (TCE) in groundwater at the Naval Air Warfare Center (NAWC), West Trenton, NJ. In the BA experiment, an electron donor (emulsified vegetable oil and sodium lactate) and a chloro-respiring microbial consortium were injected into a well in fractured mudstone of Triassic age. Water enriched in ²H was also injected as a tracer of the BA solution, to monitor advective transport processes. The changes in concentration and the δ¹³C of TCE, cis-dichloroethene (cis-DCE), and vinyl chloride (VC); the δ²H of water; changes in the abundance of the microbial communities; and the concentration of dissolved H₂ gas compared to pre- test conditions, provided multiple lines of evidence that enhanced biodegradation occurred in the injection well and in two downgradient wells. For those wells where the biodegradation was stimulated intensively, the sum of the molar chlorinated ethene (CE) concentrations in post-BA water was higher than that of the sum of the pre-BA background molar CE concentrations. The concentration ratios of TCE/(cis-DCE+VC) indicated that the increase in molar CE concentration may result from additional TCE mobilized from the rock matrix in response to the oil injection or due to desorption/diffusion. The stable carbon isotope mass-balance calculations show that the weighted average ¹³C isotope of the CEs was enriched for around a year compared to the background value in a two year monitoring period, an effective indication that dechlorination of VC was occurring. Insights gained from this study can be applied to efforts to use BA in other fractured rock systems. The study demonstrates that a BA approach can substantially enhance in situ bioremediation not only in fractures connected to the injection well, but also in the rock matrix around the well due to processes such as diffusion and desorption. Because the effect of the BA was intensive only in wells where an amendment was distributed during injection, it is necessary to adequately distribute the amendments throughout the fractured rock to achieve substantial bioremediation. The slowdown in BA effect after a year is due to some extend to the decrease abundant of appropriate microbes, but more likely the decreased concentration of electron donor. © 2013. Published by Elsevier B.V. All rights reserved.

A Uniform Fault Zone Diffusivity Structure in the Simi Valley Based on Water Level Tidal and Barometric Response

NASA Astrophysics Data System (ADS)

Xue, L.; Brodsky, E. E.; Allègre, V.; Parker, B. L.; Cherry, J. A.

2016-12-01

Water levels inside conventional water wells can tap an artesian aquifer response to pressure head disturbances caused by the Earth tides and surface atmospheric loading. The fluctuation of water levels can measure the hydrogeologic properties of the formation surrounding these wells. Specifically, the amplitude of water level oscillation is determined by formation specific storage, and the phase shift between the water level oscillation and the pressure head disturbance is determined by formation permeability. We utilized 36 wells completed in fractured, interbedded sandstone of turbidite origin in an upland area of southern California to measure the in-situ hydrogeologic properties by combining the water level tidal and barometric responses. This site experiences north-south shortening and it has groups of NE-SW and east-west conjugate faults. The site has been intensively characterized and monitored hydrologically since the 1980's because of the groundwater contamination. Hence, this study provides a good opportunity to measure the in-situ hydrogeologic properties for comparison to other test types and scales. Most of the observed water level tidal responses have a lead phase response, which cannot be interpreted either by the water level response in a confined aquifer or the water level response in an unconfined aquifer. To interpret these observations, we utilized the water level response in a partially confined aquifer, resulting in both positive and negative phase information when fully considering all the observations. Due to the different mechanisms for tidal versus barometric water level responses, the combination can give better constraints on the inverted hydrologic properties. The range of the measured permeability is 10-15-10-13 m2 and the range of the specific storage is 10-7-10-5 1/m. The resulting diffusivity is within 10-2-10-1 m2/s which is relatively uniform. This indicates the fault damages in the site are relatively homogeneous at the scale of measurement and there is no major fault-guided hydrogeological channel at the site. Such homogenous by fault zone damage is possible in a region of multiple strands and copious secondary faulting.

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.

Microstructural changes in a cementitious membrane due to the application of a DC electric field.

PubMed

Covelo, Alba; Diaz, Belen; Freire, Lorena; Novoa, X Ramon; Perez, M Consuelo

2008-07-01

The use of electromigration techniques to accelerate chloride ions motion is commonly employed to characterise the permeability of cementitious samples to chlorides, a relevant parameter in reinforced concrete corrosion. This paper is devoted to the study of microstructure's changes occurring in mortar samples when submitted to natural diffusion and migration experiments. The application of an electric field reduces testing time in about one order of magnitude with respect to natural diffusion experiments. Nevertheless, the final sample's microstructure differs in both tests. Impedance Spectroscopy is employed for real time monitoring of microstructural changes. During migration experiments the global impedance undergoes important increase in shorter period of time compared to natural diffusion tests. So, the forced motion of ions through the concrete membrane induces significant variations in the porous structure, as confirmed by Mercury Intrusion Porosimetry. After migration experiments, an important increase in the capillary pore size (10-100 nm) was detected. Conversely, no relevant variations are found after natural diffusion tests. Results presented in this work cast doubt on the significance of diffusion coefficient values obtained under accelerated conditions.

Quantum diffusion of H/D on Ni(111)—A partially adiabatic centroid MD study

NASA Astrophysics Data System (ADS)

Hopkinson, A. R.; Probert, M. I. J.

2018-03-01

We present the results of a theoretical study of H/D diffusion on a Ni(111) surface at a range of temperatures, from 250 K to 75 K. The diffusion is studied using both classical molecular dynamics and the partially adiabatic centroid molecular dynamics method. The calculations are performed with the hydrogen (or deuterium) moving in 3D across a static nickel surface using a novel Fourier interpolated potential energy surface which has been parameterized to density functional theory calculations. The results of the classical simulations are that the calculated diffusion coefficients are far too small and with too large a variation with temperature compared with experiment. By contrast, the quantum simulations are in much better agreement with experiment and show that quantum effects in the diffusion of hydrogen are significant at all temperatures studied. There is also a crossover to a quantum-dominated diffusive regime for temperatures below ˜150 K for hydrogen and ˜85 K for deuterium. The quantum diffusion coefficients are found to accurately reproduce the spread in values with temperature, but with an absolute value that is a little high compared with experiment.

Mechanisms of Stochastic Diffusion of Energetic Ions in Spherical Tori

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

Ya.I. Kolesnichenko; R.B. White; Yu.V. Yakovenko

Stochastic diffusion of the energetic ions in spherical tori is considered. The following issues are addressed: (I) Goldston-White-Boozer diffusion in a rippled field; (ii) cyclotron-resonance-induced diffusion caused by the ripple; (iii) effects of non-conservation of the magnetic moment in an axisymmetric field. It is found that the stochastic diffusion in spherical tori with a weak magnetic field has a number of peculiarities in comparison with conventional tokamaks; in particular, it is characterized by an increased role of mechanisms associated with non-conservation of the particle magnetic moment. It is concluded that in current experiments on National Spherical Torus eXperiment (NSTX) themore » stochastic diffusion does not have a considerable influence on the confinement of energetic ions.« less

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.

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.

Evidence of rock matrix back-diffusion and abiotic dechlorination using a field testing approach

NASA Astrophysics Data System (ADS)

Schaefer, Charles E.; Lippincott, David R.; Klammler, Harald; Hatfield, Kirk

2018-02-01

An in situ field demonstration was performed in fractured rock impacted with trichloroethene (TCE) and cis-1,2-dichloroethene (DCE) to assess the impacts of contaminant rebound after removing dissolved contaminants within hydraulically conductive fractures. Using a bedrock well pair spaced 2.4 m apart, TCE and DCE were first flushed with water to create a decrease in dissolved contaminant concentrations. While hydraulically isolating the well pair from upgradient contaminant impacts, contaminant rebound then was observed between the well pair over 151 days. The magnitude, but not trend, of TCE rebound was reasonably described by a matrix back-diffusion screening model that employed an effective diffusion coefficient and first-order abiotic TCE dechlorination rate constant that was based on bench-scale testing. Furthermore, a shift in the TCE:DCE ratio and carbon isotopic enrichment was observed during the rebound, suggesting that both biotic and abiotic dechlorination were occurring within the rock matrix. The isotopic data and back-diffusion model together served as a convincing argument that matrix back-diffusion was the mechanism responsible for the observed contaminant rebound. Results of this field demonstration highlight the importance and applicability of rock matrix parameters determined at the bench-scale, and suggest that carbon isotopic enrichment can be used as a line of evidence for abiotic dechlorination within rock matrices.

Single shot damage mechanism of Mo/Si multilayer optics under intense pulsed XUV-exposure.

PubMed

Khorsand, A R; Sobierajski, R; Louis, E; Bruijn, S; van Hattum, E D; van de Kruijs, R W E; Jurek, M; Klinger, D; Pelka, J B; Juha, L; Burian, T; Chalupsky, J; Cihelka, J; Hajkova, V; Vysin, L; Jastrow, U; Stojanovic, N; Toleikis, S; Wabnitz, H; Tiedtke, K; Sokolowski-Tinten, K; Shymanovich, U; Krzywinski, J; Hau-Riege, S; London, R; Gleeson, A; Gullikson, E M; Bijkerk, F

2010-01-18

We investigated single shot damage of Mo/Si multilayer coatings exposed to the intense fs XUV radiation at the Free-electron LASer facility in Hamburg - FLASH. The interaction process was studied in situ by XUV reflectometry, time resolved optical microscopy, and "post-mortem" by interference-polarizing optical microscopy (with Nomarski contrast), atomic force microscopy, and scanning transmission electron microcopy. An ultrafast molybdenum silicide formation due to enhanced atomic diffusion in melted silicon has been determined to be the key process in the damage mechanism. The influence of the energy diffusion on the damage process was estimated. The results are of significance for the design of multilayer optics for a new generation of pulsed (from atto- to nanosecond) XUV sources.

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.

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

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

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

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

Experiments with a Supersonic Multi-Channel Radial Diffuser.

DTIC Science & Technology

1980-09-01

unlimited. 17 . DISTRIBUTION STATEMENT (o the *bsta~c entered nRItok 20, it dffttt Iton, Report) IS. SUPPLEMENTARY NOTES 19. KEY WORDS (Continue o...Improvements 17 VI SIGNIFICANT TEST RESULTS 20 1. General Considerations 20 2. Typical Radial Diffuser Performance 20 3. Flow Stability Experiments 22 VIII...Adjustments Indicated 39 16 Comparison of the Single Channel Performances for Two Extreme Channel Geometries 40 17 Typical Radial Diffuser Performance

Numerical simulations of short-mixing-time double-wave-vector diffusion-weighting experiments with multiple concatenations on whole-body MR systems

NASA Astrophysics Data System (ADS)

Finsterbusch, Jürgen

2010-12-01

Double- or two-wave-vector diffusion-weighting experiments with short mixing times in which two diffusion-weighting periods are applied in direct succession, are a promising tool to estimate cell sizes in the living tissue. However, the underlying effect, a signal difference between parallel and antiparallel wave vector orientations, is considerably reduced for the long gradient pulses required on whole-body MR systems. Recently, it has been shown that multiple concatenations of the two wave vectors in a single acquisition can double the modulation amplitude if short gradient pulses are used. In this study, numerical simulations of such experiments were performed with parameters achievable with whole-body MR systems. It is shown that the theoretical model yields a good approximation of the signal behavior if an additional term describing free diffusion is included. More importantly, it is demonstrated that the shorter gradient pulses sufficient to achieve the desired diffusion weighting for multiple concatenations, increase the signal modulation considerably, e.g. by a factor of about five for five concatenations. Even at identical echo times, achieved by a shortened diffusion time, a moderate number of concatenations significantly improves the signal modulation. Thus, experiments on whole-body MR systems may benefit from multiple concatenations.

Thermal diffusivity measurement of GaAs/AlGaAs thin-film structures

NASA Astrophysics Data System (ADS)

Chen, G.; Tien, C. L.; Wu, X.; Smith, J. S.

1994-05-01

This work develops a new measurement technique that determines the thermal diffusivity of thin films in both parallel and perpendicular directions, and presents experimental results on the thermal diffusivity of GaAs/AlGaAs-based thin-film structures. In the experiment, a modulated laser source heats up the sample and a fast-response temperature sensor patterned directly on the sample picks up the thermal response. From the phase delay between the heating source and the temperature sensor, the thermal diffusivity in either the parallel or perpendicular direction is obtained depending on the experimental configuration. The experiment is performed on a molecular-beam-epitaxy grown vertical-cavity surface-emitting laser (VCSEL) structure. The substrates of the samples are etched away to eliminate the effects of the interface between the film and the substrate. The results show that the thermal diffusivity of the VCSEL structure is 5-7 times smaller than that of its corresponding bulk media. The experiments also provide evidence on the anisotropy of thermal diffusivity caused solely by the effects of interfaces and boundaries of thin films.

Retrieval of the spectral diffuse attenuation coefficient Kd(λ) in open and coastal ocean waters using a neural network inversion

NASA Astrophysics Data System (ADS)

Jamet, C.; Loisel, H.; Dessailly, D.

2012-10-01

The diffuse attenuation coefficient, Kd(λ) is a fundamental radiometric parameter that is used to assess the light availability in the water column. A neural network approach is developed to assess Kd(λ) at any visible wavelengths from the remote sensing reflectances as measured by the SeaWiFS satellite sensor. The neural network (NN) inversion is trained using a combination of simulated and in-situ data sets covering a broad range ofKd(λ), between 0.0073 m-1 at 412 nm and 12.41 m-1at 510 nm. The performance of the retrieval is evaluated against two data sets, one consisting of mainly synthetic data while the other one contains in-situ data only and is compared to those obtained with previous published empirical (NASA, Morel and Maritorena (2001) and Zhang and Fell (2007)) and semi-analytical (Lee et al., 2005b) algorithms. On the in-situ data set from the COASTLOOC campaign, the retrieval accuracy of the present algorithm is quite similar to published algorithms for oligotrophic and mesotrophic ocean waters. But for Kd(490) > 0.25 m-1, the NN approach allows to retrieve Kd(490) with a much better accuracy than the four other methods. The results are consistent when compared with other SeaWiFS wavelengths. This new inversion is as suitable in the open ocean waters as in the turbid waters. The work here is straightforwardly applicable to the MERIS sensor and with few changes to the MODIS-AQUA sensor. The algorithm in matlab and C code is provided as auxiliary material.