Quantum Chemical Study of Water Adsorption on the Surfaces of SrTiO3 Nanotubes.

PubMed

Bandura, Andrei V; Kuruch, Dmitry D; Evarestov, Robert A

2015-07-20

We have studied the adsorption of water molecules on the inner and outer surfaces of nanotubes generated by rolling (001) layers of SrTiO3 cubic crystals. The stability and the atomic and electronic structures of the adsorbed layers are determined by using hybrid density functional theory. The absorption energy and the preferred adsorbate structure are essentially governed by the nature of the surface of the nanotube. Dissociative adsorption prevails on the outer nanotube surfaces. The stability of the adsorbed layers on the inner surfaces is related to the possibility of the formation of hydrogen bonds between water molecules and surface oxygen atoms, and depends on the surface curvature. The presence of water molecules on the inner surface of the nanotubes leads to an increase of the electronic band gap. Externally TiO2 -terminated nanotubes could be used for the photocatalytic decomposition of water by ultraviolet radiation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stability of organic solar cells: challenges and strategies.

PubMed

Cheng, Pei; Zhan, Xiaowei

2016-05-03

Organic solar cells (OSCs) present some advantages, such as simple preparation, light weight, low cost and large-area flexible fabrication, and have attracted much attention in recent years. Although the power conversion efficiencies have exceeded 10%, the inferior device stability still remains a great challenge. In this review, we summarize the factors limiting the stability of OSCs, such as metastable morphology, diffusion of electrodes and buffer layers, oxygen and water, irradiation, heating and mechanical stress, and survey recent progress in strategies to increase the stability of OSCs, such as material design, device engineering of active layers, employing inverted geometry, optimizing buffer layers, using stable electrodes and encapsulation. Some research areas of device stability that may deserve further attention are also discussed to help readers understand the challenges and opportunities in achieving high efficiency and high stability of OSCs towards future industrial manufacture.

Boundary layer transition observations on a body of revolution with surface heating and cooling in water

NASA Astrophysics Data System (ADS)

Arakeri, V. H.

1980-04-01

Boundary layer flow visualization in water with surface heat transfer was carried out on a body of revolution which had the predicted possibility of laminar separation under isothermal conditions. Flow visualization was by in-line holographic technique. Boundary layer stabilization, including elimination of laminar separation, was observed to take place on surface heating. Conversely, boundary layer destabilization was observed on surface cooling. These findings are consistent with the theoretical predictions of Wazzan et al. (1970).

Effect of thermal behavior of β-lactoglobulin on the oxidative stability of menhaden oil-in-water emulsions.

PubMed

Phoon, Pui Yeu; Narsimhan, Ganesan; San Martin-Gonzalez, Maria Fernanda

2013-02-27

This study reports how emulsion oxidative stability was affected by the interfacial structure of β-lactoglobulin due to different heat treatments. Four percent (v/v) menhaden oil-in-water emulsions, stabilized by 1% (w/v) β-lactoglobulin at pH 7, were prepared by homogenization under different thermal conditions. Oxidative stability was monitored by the ferric thiocyanate peroxide value assay. Higher oxidative stability was attained by β-lactoglobulin in the molten globule state than in the native or denatured state. From atomic force microscopy of β-lactoglobulin adsorbed onto highly ordered pyrolytic graphite in buffer, native β-lactoglobulin formed a relatively smooth interfacial layer of 1.2 GPa in Young's modulus, whereas additional aggregates of similar stiffness were found when β-lactoglobulin was preheated to the molten globule state. For denatured β-lactoglobulin, although aggregates were also observed, they were larger and softer (Young's modulus = 0.45 GPa), suggesting increased porosity and thus an offset in the advantage of increased layer coverage on oxidative stability.

Molecular dynamics simulation of the cooperative adsorption of barley lipid transfer protein and cis-isocohumulone at the vacuum-water interface.

PubMed

Euston, S R; Hughes, P; Naser, Md A; Westacott, R E

2008-11-01

Molecular dynamic simulations have been carried out on systems containing a mixture of barley lipid transfer protein (LTP) and cis-isocohumulone (a hop derived iso-alpha-acid) in one of its enol forms, in bulk water and at the vacuum-water interface. In solution, the cis-isocohumulone molecules bind to the surface of the LTP molecule. The mechanism of binding appears to be purely hydrophobic in nature via desolvation of the protein surface. Binding of hop acids to the LTP leads to a small change in the 3-D conformation of the protein, but no change in the proportion of secondary structure present in helices, even though there is a significant degree of hop acid binding to the helical regions. At the vacuum-water interface, cis-isocohumulone shows a high surface activity and adsorbs rapidly at the interface. LTP then shows a preference to bind to the preadsorbed hop acid layer at the interface rather than to the bare water-vacuum interface. The free energy of adsorption of LTP at the hop-vacuum-water interface is more favorable than for adsorption at the vacuum-water interface. Our results support the view that hop iso-alpha-acids promote beer foam stability by forming bridges between separate adsorbed protein molecules, thus strengthening the adsorbed protein layer and reducing foam breakdown by lamellar phase drainage. The results also suggest a second mechanism may also occur, whereby the concentration of protein at the interface is increased via enhanced protein adsorption to adsorbed hop acid layers. This too would increase foam stability through its effect on the stabilizing protein layer around the foam bubbles.

Separated rupture and retraction of a bi-layer free film

NASA Astrophysics Data System (ADS)

Stewart, Peter; Feng, Jie; Griffiths, Ian

2017-11-01

We investigate the dynamics of a rising air bubble in an aqueous phase coated with a layer of oil. Recent experiments have shown that bubble rupture at the compound air/oil/aqueous interface can effectively disperse submicrometre oil droplets into the aqueous phase, suggesting a possible mechanism for clean-up of oil spillages on the surface of the ocean. Using a theoretical model we consider the stability of the long liquid free film formed as the bubble reaches the free surface, composed of two immiscible layers of differing viscosities, where each layer experiences a van der Waals force between its interfaces. For an excess of surfactant on one gas-liquid interface we show that the instability manifests as distinct rupture events, with the oil layer rupturing first and retracting over the in-tact water layer beneath, consistent with the experimental observations. We use our model to examine the dynamics of oil retraction, showing that it follows a power-law for short times, and examine the influence of retraction on the stability of the water layer.

The structure of the yeast plasma membrane SNARE complex reveals destabilizing water-filled cavities.

PubMed

Strop, Pavel; Kaiser, Stephen E; Vrljic, Marija; Brunger, Axel T

2008-01-11

SNARE proteins form a complex that leads to membrane fusion between vesicles, organelles, and plasma membrane in all eukaryotic cells. We report the 1.7A resolution structure of the SNARE complex that mediates exocytosis at the plasma membrane in the yeast Saccharomyces cerevisiae. Similar to its neuronal and endosomal homologues, the S. cerevisiae SNARE complex forms a parallel four-helix bundle in the center of which is an ionic layer. The S. cerevisiae SNARE complex exhibits increased helix bending near the ionic layer, contains water-filled cavities in the complex core, and exhibits reduced thermal stability relative to mammalian SNARE complexes. Mutagenesis experiments suggest that the water-filled cavities contribute to the lower stability of the S. cerevisiae complex.

Groundwater monitoring of an open-pit limestone quarry: groundwater characteristics, evolution and their connections to rock slopes.

PubMed

Eang, Khy Eam; Igarashi, Toshifumi; Fujinaga, Ryota; Kondo, Megumi; Tabelin, Carlito Baltazar

2018-03-06

Groundwater flow and its geochemical evolution in mines are important not only in the study of contaminant migration but also in the effective planning of excavation. The effects of groundwater on the stability of rock slopes and other mine constructions especially in limestone quarries are crucial because calcite, the major mineral component of limestone, is moderately soluble in water. In this study, evolution of groundwater in a limestone quarry located in Chichibu city was monitored to understand the geochemical processes occurring within the rock strata of the quarry and changes in the chemistry of groundwater, which suggests zones of deformations that may affect the stability of rock slopes. There are three distinct geological formations in the quarry: limestone layer, interbedded layer of limestone and slaty greenstone, and slaty greenstone layer as basement rock. Although the hydrochemical facies of all groundwater samples were Ca-HCO 3 type water, changes in the geochemical properties of groundwater from the three geological formations were observed. In particular, significant changes in the chemical properties of several groundwater samples along the interbedded layer were observed, which could be attributed to the mixing of groundwater from the limestone and slaty greenstone layers. On the rainy day, the concentrations of Ca 2+ and HCO 3 - in the groundwater fluctuated notably, and the groundwater flowing along the interbedded layer was dominated by groundwater from the limestone layer. These suggest that groundwater along the interbedded layer may affect the stability of rock slopes.

Investigation of the structure and stability of SnO2 nanocrystal and its surface-bound water

NASA Astrophysics Data System (ADS)

Wang, H.; Wesolowski, D. J.; Proffen, T. E.; Kolesnikov, A. I.; Vlcek, L.; Wang, W.; Feygenson, M.; Sofo, J. O.; Anovitz, L.

2012-12-01

Driven partly by a myriad use of engineered metal oxide nanoparticles, understanding their stabilities and interactions with environmental matrix during and after applications are desired. SnO2 (cassiterite) is one of the frequently used oxides in solid-state gas sensors and oxidation catalysts. A close relationship between the gas sensitivity and catalysis of oxides with their surface chemistry ensures continuous interests in the study of SnO2-water interfacial complexity (unavoidable "contamination" in which water can potentially participate in reactions and change SnO2 conductivity). Such information is important, as the existence of hydration layers on the surface of SnO2 nanoparticles not only play a critical role in stabilizing the nanoparticle but also affect its selectivity/sensitivity, as a nanosensor. SnO2 nanoparticles (2-5 nm) synthesized by a wet chemical route are dominated by {110} faces and are capped with H2O or D2O water molecules (after purification), depending on isotopic composition of water used for syntheses. When water is in direct contact with terminal Sn and O atoms, there is a controversial argument as to whether or not dissociative adsorption occurs (i.e., formation of hydroxyl groups). Although theoretical studies point toward a tendency for dissociative configuration in the direct contact layer, experimental studies have not unambiguously confirmed this conclusion. We present combined investigations using neutron total scattering (NPDF at the NOMAD beamline, SNS) and inelastic neutron scattering (INS at the SEQUOIA beamline, SNS) techniques as static and dynamic probes to reveal structure and dynamics of water and SnO2 nanocrystalline stability upon dehydration. The NPDF results (measured with deuterated samples) suggest layered water configurations with G(r) signals dominated by O-D bonds at 0.98 Å, and the second hydration layer that gives a broad peak at 2.5-4 Å. There is no evidence of a third hydration layer at 5-7 Å as shown by our previous molecular dynamic (MD) simulations, perhaps because this outermost hydration layer is not laterally-ordered parallel to the oxide surface and thus contributes a much weaker G(r) signal than the first two layers. Additionally, due to the relatively broad distribution of D-D distances and Fourier termination ripples, NPDF results cannot provide unambiguous evidence about the formation of hydroxylated surfaces, even though the dissociative MD model gives a better fitted result. Upon heating to 250 °C (at 10-7 bar), SnO2 nanoparticles start to show surface transformation and increased crystallinity before completion of dehydration. This likely corresponds to the minimum concentration of surface-bound groups required to stabilize the nanoparticles (i.e., < 0.7 monolayer coverage). Attempts to remove D2O/OD- groups below this threshold lead to rapidly increase of crystallinity. INS experiments on SnO2 nanoparticles with a minimum threshold coverage and with those from a fully hydrated sample clearly suggested dissociated water configurations with no observations of H2O bending modes in the sample with a minimum threshold coverage. Corresponding ab initio MD simulation on SnO2 (110) surface for a comparison with INS results is underway to provide a complete picture of SnO2-water surface dynamics.

Effects of chloride additives on the mechanical stability and environmental durability of porous MgF2 thin films

NASA Astrophysics Data System (ADS)

Schütz, F.; Scheurell, K.; Scholz, G.; Kemnitz, E.

2016-09-01

Porous antireflective thin films, prepared of nanoscopic MgF2 sols, exhibit a low refraction index and are useful for various optical applications. Due to their porosity, film stability and durability suffer from mechanical abrasion and water solubility, respectively. Hence, we present approaches of improved mechanical stability of MgF2 layers induced by chloride addition. Antireflective (AR) films were produced by dip-coating followed by thermal treatment. Afterwards, film stability and environmental durability was strained by crockmeter and water stability tests, respectively. In comparison to films prepared from chloride-free MgF2 sols, chloride mingled sols form coatings with increased mechanical stability and a lower solubility.

Harvesting Water from Air: Using Anhydrous Salt with Sunlight.

PubMed

Li, Renyuan; Shi, Yusuf; Shi, Le; Alsaedi, Mossab; Wang, Peng

2018-05-01

Atmospheric water is an abundant alternative water resource, equivalent to 6 times the water in all rivers on Earth. This work screens 14 common anhydrous and hydrated salt couples in terms of their physical and chemical stability, water vapor harvesting, and release capacity under relevant application scenarios. Among the salts screened, copper chloride (CuCl 2 ), copper sulfate (CuSO 4 ), and magnesium sulfate (MgSO 4 ) distinguish themselves and are further made into bilayer water collection devices, with the top layer being the photothermal layer, while the bottom layer acts as a salt-loaded fibrous membrane. The water collection devices are capable of capturing water vapor out of the air with low relative humidity (down to 15%) and releasing water under regular and even weakened sunlight (i.e., 0.7 kW/m 2 ). The work shines light on the potential use of anhydrous salt toward producing drinking water in water scarce regions.

The stability of two-phase flow over a swept-wing

NASA Technical Reports Server (NTRS)

Coward, Adrian; Hall, Philip

1994-01-01

We use numerical and asymptotic techniques to study the stability of a two-phase air/water flow above a flat porous plate. This flow is a model of the boundary layer which forms on a yawed cylinder and can be used as a useful approximation to the air flow over swept wings during heavy rainfall. We show that the interface between the water and air layers can significantly destabilize the flow, leading to traveling wave disturbances which move along the attachment line. This instability occurs for lower Reynolds numbers than in the case of the absence of a water layer. We also investigate the instability of inviscid stationary modes. We calculate the effective wavenumber and orientation of the stationary disturbance when the fluids have identical physical properties. Using perturbation methods we obtain corrections due to a small stratification in viscosity, thus quantifying the interfacial effects. Our analytical results are in agreement with the numerical solution which we obtain for arbitrary fluid properties.

Static and Dynamic Water Motion-Induced Instability in Oxide Thin-Film Transistors and Its Suppression by Using Low-k Fluoropolymer Passivation.

PubMed

Choi, Seungbeom; Jo, Jeong-Wan; Kim, Jaeyoung; Song, Seungho; Kim, Jaekyun; Park, Sung Kyu; Kim, Yong-Hoon

2017-08-09

Here, we report static and dynamic water motion-induced instability in indium-gallium-zinc-oxide (IGZO) thin-film transistors (TFTs) and its effective suppression with the use of a simple, solution-processed low-k (ε ∼ 1.9) fluoroplastic resin (FPR) passivation layer. The liquid-contact electrification effect, in which an undesirable drain current modulation is induced by a dynamic motion of a charged liquid such as water, can cause a significant instability in IGZO TFTs. It was found that by adopting a thin (∼44 nm) FPR passivation layer for IGZO TFTs, the current modulation induced by the water-contact electrification was greatly reduced in both off- and on-states of the device. In addition, the FPR-passivated IGZO TFTs exhibited an excellent stability to static water exposure (a threshold voltage shift of +0.8 V upon 3600 s of water soaking), which is attributed to the hydrophobicity of the FPR passivation layer. Here, we discuss the origin of the current instability caused by the liquid-contact electrification as well as various static and dynamic stability tests for IGZO TFTs. On the basis of our findings, we believe that the use of a thin, solution-processed FPR passivation layer is effective in suppressing the static and dynamic water motion-induced instabilities, which may enable the realization of high-performance and environment-stable oxide TFTs for emerging wearable and skin-like electronics.

Can shallow-layer measurements at a single location be used to predict deep soil water storage at the slope scale?

NASA Astrophysics Data System (ADS)

Gao, Lei; Lv, Yujuan; Wang, Dongdong; Tahir, Muhammad; Peng, Xinhua

2015-12-01

Knowing the amount of soil water storage (SWS) in agricultural soil profiles is important for understanding physical, chemical, and biological soil processes. However, measuring the SWS in deep soil layers is more expensive and time consuming than in shallower layers. Whether deep SWS can be predicted from shallow-layer measurements through temporal stability analysis (TSA) remains unclear. To address this issue, the soil water content was measured at depths of 0-1.6 m (0.2-m depth intervals) at 79 locations along an agricultural slope on 28 occasions between July 2013 and October 2014. SWSs values were then calculated for the 0-0.4, 0.4-0.8, 0.8-1.2, 1.2-1.6, and 0-1.6 m soil layers. The SWS exhibited strong temporal stability, with mean Spearman's ranking coefficients (rs) of 0.83, 0.92, 0.83, and 0.79 in the 0-0.4, 0.4-0.8, 0.8-1.2, and 1.2-1.6 m soil layers, respectively. As expected, the most temporally stable location (MTSL1) accurately predicted the average SWS of the corresponding soil layer, and the values of absolute bias relative to mean (ARB) were lower than 3% for all of the investigated soil layers. Using TSA, deep-layer SWS information could be predicted using a single-location measurement in the 0-0.4 m soil layer. The mean ARB values between the observed and predicted mean SWS values were 2.9%, 4.3%, 3.9%, and 2.7% in the 0.4-0.8, 0.8-1.2, 1.2-1.6, and 0-1.6 m soil layers, respectively. The prediction accuracy of the spatial distribution generally decreased with increasing depth, with linear determination coefficients (R2) of 0.93, 0.79, 0.72, and 0.84 for the four soil layers, respectively. The proposed method could further expand the application of the temporal stability technique in the estimation of SWS.

Enzyme microheterogeneous hydration and stabilization in supercritical carbon dioxide.

PubMed

Silveira, Rodrigo L; Martínez, Julian; Skaf, Munir S; Martínez, Leandro

2012-05-17

Supercritical carbon dioxide is a promising green-chemistry solvent for many enzyme-catalyzed chemical reactions, yet the striking stability of some enzymes in such unconventional environments is not well understood. Here, we investigate the stabilization of the Candida antarctica Lipase B (CALB) in supercritical carbon dioxide-water biphasic systems using molecular dynamics simulations. The preservation of the enzyme structure and optimal activity depend on the presence of small amounts of water in the supercritical dispersing medium. When the protein is at least partially hydrated, water molecules bind to specific sites on the enzyme surface and prevent carbon dioxide from penetrating its catalytic core. Strikingly, water and supercritical carbon dioxide cover the protein surface quite heterogeneously. In the first solvation layer, the hydrophilic residues at the surface of the protein are able to pin down patches of water, whereas carbon dioxide solvates preferentially hydrophobic surface residues. In the outer solvation shells, water molecules tend to cluster predominantly on top of the larger water patches of the first solvation layer instead of spreading evenly around the remainder of the protein surface. For CALB, this exposes the substrate-binding region of the enzyme to carbon dioxide, possibly facilitating diffusion of nonpolar substrates into the catalytic funnel. Therefore, by means of microheterogeneous solvation, enhanced accessibility of hydrophobic substrates to the active site can be achieved, while preserving the functional structure of the enzyme. Our results provide a molecular picture on the nature of the stability of proteins in nonaqueous media.

Experimental investigation of convective stability in a superposed fluid and porous layer when heated from below

NASA Technical Reports Server (NTRS)

Chen, Falin; Chen, C. F.

1989-01-01

Experiments have been carried out in a horizontal superposed fluid and porous layer contained in a test box 24 cm x 12 cm x 4 cm high. The porous layer consisted of 3 mm diameter glass beads, and the fluids used were water, 60 and 90 percent glycerin-water solutions, and 100 percent glycerin. The depth ratio d, which is the ratio of the thickness of the fluid layer to that of the porous layer, varied from 0 to 1.0. Fluids of increasingly higher viscosity were used for cases with larger d in order to keep the temperature difference across the tank within reasonable limits. The size of the convection cells was inferred from temperature measurements made with embedded thermocouples and from temperature distributions at the top of the layer by use of liquid crystal film. The experimental results showed: (1) a precipitous decrease in the critical Rayleigh number as the depth of the fluid layer was increased from zero, and (2) an eightfold decrease in the critical wavelength between d = 0.1 and 0.2. Both of these results were predicted by the linear stability theory reported earlier (Chen and Chen, 1988).

Multi-Layer Self-Nanoemulsifying Pellets: an Innovative Drug Delivery System for the Poorly Water-Soluble Drug Cinnarizine.

PubMed

Shahba, Ahmad Abdul-Wahhab; Ahmed, Abid Riaz; Alanazi, Fars Kaed; Mohsin, Kazi; Abdel-Rahman, Sayed Ibrahim

2018-04-25

Beside their solubility limitations, some poorly water-soluble drugs undergo extensive degradation in aqueous and/or lipid-based formulations. Multi-layer self-nanoemulsifying pellets (ML-SNEP) introduce an innovative delivery system based on isolating the drug from the self-nanoemulsifying layer to enhance drug aqueous solubility and minimize degradation. In the current study, various batches of cinnarizine (CN) ML-SNEP were prepared using fluid bed coating and involved a drug-free self-nanoemulsifying layer, protective layer, drug layer, moisture-sealing layer, and/or an anti-adherent layer. Each layer was optimized based on coating outcomes such as coating recovery and mono-pellets%. The optimized ML-SNEP were characterized using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), X-ray diffraction (XRD), in vitro dissolution, and stability studies. The optimized ML-SNEP were free-flowing, well separated with high coating recovery. SEM showed multiple well-defined coating layers. The acidic polyvinylpyrrolidone:CN (4:1) solution presented excellent drug-layering outcomes. DSC and XRD confirmed CN transformation into amorphous state within the drug layer. The isolation between CN and self-nanoemulsifying layer did not adversely affect drug dissolution. CN was able to spontaneously migrate into the micelles arising from the drug-free self-nanoemulsifying layer. ML-SNEP showed superior dissolution compared to Stugeron® tablets at pH 1.2 and 6.8. Particularly, on shifting to pH 6.8, ML-SNEP maintained > 84% CN in solution while Stugeron® tablets showed significant CN precipitation leaving only 7% CN in solution. Furthermore, ML-SNEP (comprising Kollicoat® Smartseal 30D) showed robust stability and maintained > 97% intact CN within the accelerated storage conditions. Accordingly, ML-SNEP offer a novel delivery system that combines both enhanced solubilization and stabilization of unstable poorly soluble drugs.

Mechanical properties of protein adsorption layers at the air/water and oil/water interface: a comparison in light of the thermodynamical stability of proteins.

PubMed

Mitropoulos, Varvara; Mütze, Annekathrin; Fischer, Peter

2014-04-01

Over the last decades numerous studies on the interfacial rheological response of protein adsorption layers have been published. The comparison of these studies and the retrieval of a common parameter to compare protein interfacial activity are hampered by the fact that different boundary conditions (e.g. physico-chemical, instrumental, interfacial) were used. In the present work we review previous studies and attempt a unifying approach for the comparison between bulk protein properties and their adsorption films. Among many common food grade proteins we chose bovine serum albumin, β-lactoglobulin and lysozyme for their difference in thermodynamic stability and studied their adsorption at the air/water and limonene/water interface. In order to achieve this we have i) systematically analyzed protein adsorption kinetics in terms of surface pressure rise using a drop profile analysis tensiometer and ii) we addressed the interfacial layer properties under shear stress using an interfacial shear rheometer under the same experimental conditions. We could show that thermodynamically less stable proteins adsorb generally faster and yield films with higher shear rheological properties at air/water interface. The same proteins showed an analog behavior when adsorbing at the limonene/water interface but at slower rates. Copyright © 2013 Elsevier B.V. All rights reserved.

A graded catalytic–protective layer for an efficient and stable water-splitting photocathode

DOE PAGES

Gu, Jing; Aguiar, Jeffery A.; Ferrere, Suzanne; ...

2017-01-09

Achieving solar-to-hydrogen efficiencies above 15% is key for the commercial success of photoelectrochemical water splitting devices. While tandem cells can reach those efficiencies, increasing the catalytic activity and long-term stability remains a significant challenge. We show that annealing a bilayer of amorphous titanium dioxide (TiO x) and molybdenum sulfide (MoS x) deposited onto GaInP 2 results in a photocathode with high catalytic activity (current density of 11 mA/cm -2 at 0 V vs. the reversible hydrogen electrode under 1 sun illumination) and stability (retention of 80% of initial photocurrent density over a 20 h durability test) for the hydrogen evolutionmore » reaction. Microscopy and spectroscopy reveal that annealing results in a graded MoS x/MoO x/TiO 2 layer that retains much of the high catalytic activity of amorphous MoS x but with stability similar to crystalline MoS 2. These findings demonstrate the potential of utilizing a hybridized, heterogeneous surface layer as a cost-effective catalytic and protective interface for solar hydrogen production.« less

Long-term stability of crystal-stabilized water-in-oil emulsions.

PubMed

Ghosh, Supratim; Pradhan, Mamata; Patel, Tejas; Haj-Shafiei, Samira; Rousseau, Dérick

2015-12-15

The impact of cooling rate and mixing on the long-term kinetic stability of wax-stabilized water-in-oil emulsions was investigated. Four cooling/mixing protocols were investigated: cooling from 45°C to either 25°C or 4°C with/without stirring and two cooling rates - slow (1°C/min) and fast (5°C/min). The sedimentation behaviour of the emulsions was significantly affected by cooling protocol. Stirring was critical to the stability of all emulsions, with statically-cooled (no stirring) emulsions suffering from extensive aqueous phase separation. Emulsions stirred while cooling showed sedimentation of a waxy emulsion layer leaving a clear oil layer at the top, with a smaller separation and droplet size distribution at 4°C compared to 25°C, indicating the importance of the amount of crystallized wax on emulsion stability. Light microscopy revealed that crystallized wax appeared both on the droplet surface and in the continuous phase, suggesting that stirring ensured dispersibility of the water droplets during cooling as the wax was crystallizing. Wax crystallization on the droplet surface provided stability against droplet coalescence while continuous phase wax crystals minimized inter-droplet collisions. The key novel aspect of this research is in the simplicity to tailor the spatial distribution of wax crystals, i.e., either at the droplet surface or in the continuous phase via use of a surfactant and judicious stirring and/or cooling. Knowledge gained from this research can be applied to develop strategies for long-term storage stability of crystal-stabilized W/O emulsions. Copyright © 2015 Elsevier Inc. All rights reserved.

Heat transfer and phase transitions of water in multi-layer cryolithozone-surface systems

NASA Astrophysics Data System (ADS)

Khabibullin, I. L.; Nigametyanova, G. A.; Nazmutdinov, F. F.

2018-01-01

A mathematical model for calculating the distribution of temperature and the dynamics of the phase transfor-mations of water in multilayer systems on permafrost-zone surface is proposed. The model allows one to perform calculations in the annual cycle, taking into account the distribution of temperature on the surface in warm and cold seasons. A system involving four layers, a snow or land cover, a top layer of soil, a layer of thermal-insulation materi-al, and a mineral soil, is analyzed. The calculations by the model allow one to choose the optimal thickness and com-position of the layers which would ensure the stability of structures built on the permafrost-zone surface.

Water Desalination Using Nanoporous Single-Layer Graphene with Tunable Pore Size

DOE PAGES

Surwade, Sumedh P.; Smirnov, Sergei N.; Vlassiouk, Ivan V.; ...

2015-03-23

Graphene has great potential to serve as a separation membrane due to its unique properties such as chemical and mechanical stability, flexibility and most importantly its one-atom thickness. In this study, we demonstrate first experimental evidence of the use of single-layer porous graphene as a desalination membrane. Nanometer-sized pores are introduced into single layer graphene using a convenient oxygen plasma etching process that permits tuning of the pore size. The resulting porous graphene membrane exhibited high rejection of salt ions and rapid water transport, thus functioning as an efficient water desalination membrane. Salt rejection selectivity of nearly 100% and exceptionallymore » high water fluxes exceeding 105 g m-2 s-1 at 40 C were measured using saturated water vapor as a driving force.« less

Liquid exfoliation of solvent-stabilized few-layer black phosphorus for applications beyond electronics

PubMed Central

Hanlon, Damien; Backes, Claudia; Doherty, Evie; Cucinotta, Clotilde S.; Berner, Nina C.; Boland, Conor; Lee, Kangho; Harvey, Andrew; Lynch, Peter; Gholamvand, Zahra; Zhang, Saifeng; Wang, Kangpeng; Moynihan, Glenn; Pokle, Anuj; Ramasse, Quentin M.; McEvoy, Niall; Blau, Werner J.; Wang, Jun; Abellan, Gonzalo; Hauke, Frank; Hirsch, Andreas; Sanvito, Stefano; O'Regan, David D.; Duesberg, Georg S.; Nicolosi, Valeria; Coleman, Jonathan N.

2015-01-01

Few-layer black phosphorus (BP) is a new two-dimensional material which is of great interest for applications, mainly in electronics. However, its lack of environmental stability severely limits its synthesis and processing. Here we demonstrate that high-quality, few-layer BP nanosheets, with controllable size and observable photoluminescence, can be produced in large quantities by liquid phase exfoliation under ambient conditions in solvents such as N-cyclohexyl-2-pyrrolidone (CHP). Nanosheets are surprisingly stable in CHP, probably due to the solvation shell protecting the nanosheets from reacting with water or oxygen. Experiments, supported by simulations, show reactions to occur only at the nanosheet edge, with the rate and extent of the reaction dependent on the water/oxygen content. We demonstrate that liquid-exfoliated BP nanosheets are potentially useful in a range of applications from ultrafast saturable absorbers to gas sensors to fillers for composite reinforcement. PMID:26469634

Molybdenum Disulfide as a Protection Layer and Catalyst for Gallium Indium Phosphide Solar Water Splitting Photocathodes

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

Britto, Reuben J.; Benck, Jesse D.; Young, James L.

2016-06-02

Gallium indium phosphide (GaInP2) is a semiconductor with promising optical and electronic properties for solar water splitting, but its surface stability is problematic as it undergoes significant chemical and electrochemical corrosion in aqueous electrolytes. Molybdenum disulfide (MoS2) nanomaterials are promising to both protect GaInP2 and to improve catalysis since MoS2 is resistant to corrosion and also possesses high activity for the hydrogen evolution reaction (HER). In this work, we demonstrate that GaInP2 photocathodes coated with thin MoS2 surface protecting layers exhibit excellent activity and stability for solar hydrogen production, with no loss in performance (photocurrent onset potential, fill factor, andmore » light limited current density) after 60 hours of operation. This represents a five-hundred fold increase in stability compared to bare p-GaInP2 samples tested in identical conditions.« less

Integration of textile fabric and coconut shell in particleboard

NASA Astrophysics Data System (ADS)

Misnon, M. I.; Bahari, S. A.; Islam, M. M.; Epaarachchi, J. A.

2013-08-01

In this study, cotton fabric and coconut shell were integrated in particleboard to reduce the use of wood. Particleboards containing mixed rubberwood and coconut shell with an equal weight ratio have been integrated with various layers of cotton fabric. These materials were bonded by urea formaldehyde with a content level of 12% by weight. Flexural and water absorption tests were conducted to analyze its mechanical properties and dimensional stability. Results of flexural test showed an increment at least double strength values in fabricated materials as compared to control sample. The existence of fabric in the particleboard system also improved the dimensional stability of the produced material. Enhancement of at least 39% of water absorption could help the dimensional stability of the produced material. Overall, these new particleboards showed better results with the incorporation of cotton fabric layers and this study provided better understanding on mechanical and physical properties of the fabricated particleboard.

Effect of layer-by-layer coatings and localization of antioxidant on oxidative stability of a model encapsulated bioactive compound in oil-in-water emulsions.

PubMed

Pan, Yuanjie; Nitin, N

2015-11-01

Oxidation of encapsulated bioactives in emulsions is one of the key challenges that limit shelf-life of many emulsion containing products. This study seeks to quantify the role of layer-by-layer coatings and localization of antioxidant molecules at the emulsion interface in influencing oxidation of the encapsulated bioactives. Oxidative barrier properties of the emulsions were simulated by measuring the rate of reaction of peroxyl radicals generated in the aqueous phase with the encapsulated radical sensitive dye in the lipid core of the emulsions. The results of peroxyl radical permeation were compared to the stability of encapsulated retinol (model bioactive) in emulsions. To evaluate the role of layer-by-layer coatings in influencing oxidative barrier properties, radical permeation rates and retinol stability were evaluated in emulsion formulations of SDS emulsion and SDS emulsion with one or two layers of polymers (ϵ-polylysine and dextran sulfate) coated at the interface. To localize antioxidant molecules to the interface, gallic acid (GA) was chemically conjugated with ϵ-polylysine and subsequently deposited on SDS emulsion based on electrostatic interactions. Emulsion formulations with localized GA molecules at the interface were compared with SDS emulsion with GA molecules in the bulk aqueous phase. The results of this study demonstrate the advantage of localization of antioxidant at the interface and the limited impact of short chain polymer coatings at the interface of emulsions in reducing permeation of radicals and oxidation of a model encapsulated bioactive in oil-in-water emulsions. Copyright © 2015 Elsevier B.V. All rights reserved.

Multiwalled Carbon Nanotubes at the Interface of Pickering Emulsions.

PubMed

Briggs, Nicholas M; Weston, Javen S; Li, Brian; Venkataramani, Deepika; Aichele, Clint P; Harwell, Jeffrey H; Crossley, Steven P

2015-12-08

Carbon nanotubes exhibit very unique properties in biphasic systems. Their interparticle attraction leads to reduced droplet coalescence rates and corresponding improvements in emulsion stability. Here we use covalent and noncovalent techniques to modify the hydrophilicity of multiwalled carbon nanotubes (MWCNTs) and study their resulting behavior at an oil-water interface. By using both paraffin wax/water and dodecane/water systems, the thickness of the layer of MWNTs at the interface and resulting emulsion stability are shown to vary significantly with the approach used to modify the MWNTs. Increased hydrophilicity of the MWNTs shifts the emulsions from water-in-oil to oil-in-water. The stability of the emulsion is found to correlate with the thickness of nanotubes populating the oil-water interface and relative strength of the carbon nanotube network. The addition of a surfactant decreases the thickness of nanotubes at the interface and enhances the overall interfacial area stabilized at the expense of increased droplet coalescence rates. To the best of our knowledge, this is the first time the interfacial thickness of modified carbon nanotubes has been quantified and correlated to emulsion stability.

Stabilizing hybrid perovskites against moisture and temperature via non-hydrolytic atomic layer deposited overlayers

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

Kim, In Soo; Martinson, Alex B. F.

2015-09-14

We utilized a novel non-hydrolytic (nh) surface chemistry to allow the direct synthesis of pinhole-fee oxide overlayers directly on conventional hybrid perovskite halide absorbers without damage. By utilizing water- free ALD Al 2O 3 passivation, a minimum of ten-fold increase in stability against relative humidity (RH) 85% was achieved along with a dramatically improved thermal resistance (up to 250 °C). We extend this approach to synthesize nh-TiO 2 directly on hybrid perovskites to establish its potential in inverted photovoltaic devices as a dual stabilizing and electron accepting layer, as evidenced by photoluminescence (PL) quenching.

SiC Composite for Fuel Structure Applications

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

Yueh, Ken

Extensive evaluation was performed to determine the suitability of using SiC composite as a boiling water reactor (BWR) fuel channel material. A thin walled SiC composite box, 10 cm in dimension by approximately 1.5 mm wall thickness was fabricated using chemical vapor deposition (CVD) for testing. Mechanical test results and performance evaluations indicate the material could meet BWR channel mechanical design requirement. However, large mass loss of up to 21% was measured in in-pile corrosion test under BWR-like conditions in under 3 months of irradiation. A fresh sister sample irradiated in a follow-up cycle under PWR conditions showed no measureablemore » weight loss and thus supports the hypothesis that the oxidizing condition of the BWR-like coolant chemistry was responsible for the high corrosion rate. A thermodynamic evaluation showed SiC is not stable and the material may oxidize to form SiO 2 and CO 2. Silica has demonstrated stability in high temperature steam environment and form a protective oxide layer under severe accident conditions. However, it does not form a protective layer in water under normal BWR operational conditions due to its high solubility. Corrosion product stabilization by modifying the SiC CVD surface is an approach evaluated in this study to mitigate the high corrosion rate. Titanium and zirconium have been selected as stabilizing elements since both TiSiO 4 and ZrSiO 4 are insoluble in water. Corrosion test results in oxygenated water autoclave indicate TiSiO4 does not form a protective layer. However, zirconium doped test samples appear to form a stable continuous layer of ZrSiO 4 during the corrosion process. Additional process development is needed to produce a good ZrSiC coating to verify functionality of the mitigation concept.« less

Role of ground ice dynamics and ecological feedbacks in recent ice wedge degradation and stabilization

USGS Publications Warehouse

Mark Torre Jorgenson,; Mikhail Kanevskiy,; Yuri Shur,; Natalia Moskalenko,; Dana Brown,; Wickland, Kimberly P.; Striegl, Robert G.; Koch, Joshua C.

2015-01-01

Ground ice is abundant in the upper permafrost throughout the Arctic and fundamentally affects terrain responses to climate warming. Ice wedges, which form near the surface and are the dominant type of massive ice in the Arctic, are particularly vulnerable to warming. Yet processes controlling ice wedge degradation and stabilization are poorly understood. Here we quantified ice wedge volume and degradation rates, compared ground ice characteristics and thermal regimes across a sequence of five degradation and stabilization stages and evaluated biophysical feedbacks controlling permafrost stability near Prudhoe Bay, Alaska. Mean ice wedge volume in the top 3 m of permafrost was 21%. Imagery from 1949 to 2012 showed thermokarst extent (area of water-filled troughs) was relatively small from 1949 (0.9%) to 1988 (1.5%), abruptly increased by 2004 (6.3%) and increased slightly by 2012 (7.5%). Mean annual surface temperatures varied by 4.9°C among degradation and stabilization stages and by 9.9°C from polygon center to deep lake bottom. Mean thicknesses of the active layer, ice-poor transient layer, ice-rich intermediate layer, thermokarst cave ice, and wedge ice varied substantially among stages. In early stages, thaw settlement caused water to impound in thermokarst troughs, creating positive feedbacks that increased net radiation, soil heat flux, and soil temperatures. Plant growth and organic matter accumulation in the degraded troughs provided negative feedbacks that allowed ground ice to aggrade and heave the surface, thus reducing surface water depth and soil temperatures in later stages. The ground ice dynamics and ecological feedbacks greatly complicate efforts to assess permafrost responses to climate change.

Role of ground ice dynamics and ecological feedbacks in recent ice wedge degradation and stabilization

NASA Astrophysics Data System (ADS)

Jorgenson, M. T.; Kanevskiy, M.; Shur, Y.; Moskalenko, N.; Brown, D. R. N.; Wickland, K.; Striegl, R.; Koch, J.

2015-11-01

Ground ice is abundant in the upper permafrost throughout the Arctic and fundamentally affects terrain responses to climate warming. Ice wedges, which form near the surface and are the dominant type of massive ice in the Arctic, are particularly vulnerable to warming. Yet processes controlling ice wedge degradation and stabilization are poorly understood. Here we quantified ice wedge volume and degradation rates, compared ground ice characteristics and thermal regimes across a sequence of five degradation and stabilization stages and evaluated biophysical feedbacks controlling permafrost stability near Prudhoe Bay, Alaska. Mean ice wedge volume in the top 3 m of permafrost was 21%. Imagery from 1949 to 2012 showed thermokarst extent (area of water-filled troughs) was relatively small from 1949 (0.9%) to 1988 (1.5%), abruptly increased by 2004 (6.3%) and increased slightly by 2012 (7.5%). Mean annual surface temperatures varied by 4.9°C among degradation and stabilization stages and by 9.9°C from polygon center to deep lake bottom. Mean thicknesses of the active layer, ice-poor transient layer, ice-rich intermediate layer, thermokarst cave ice, and wedge ice varied substantially among stages. In early stages, thaw settlement caused water to impound in thermokarst troughs, creating positive feedbacks that increased net radiation, soil heat flux, and soil temperatures. Plant growth and organic matter accumulation in the degraded troughs provided negative feedbacks that allowed ground ice to aggrade and heave the surface, thus reducing surface water depth and soil temperatures in later stages. The ground ice dynamics and ecological feedbacks greatly complicate efforts to assess permafrost responses to climate change.

Improved water resistance of SrAl2O4: Eu2+, Dy3+ phosphor directly achieved in a water-containing medium

NASA Astrophysics Data System (ADS)

Qi, Tonggang; Xia, Haofu; Zhang, Zhanhui; Kong, Shijin; Peng, Weikang; Zhao, Qi; Huang, Zhiliang

2017-03-01

In this paper, a heterogeneous precipitation method utilizing urea hydrolysis was adopted to coat a SiO2 layer on the surface of SrAl2O4:Eu2+, Dy3+ long persistence phosphors. To avoid phosphor hydrolysis in a water-containing coating medium, the hydrolysis and polymerization reactions of tetraethyl orthosilicate (TEOS) were concerned and carried out. The crystal phases, surface morphologies, hydrolysis stability and water resistance on afterglow properties of coated phosphors were investigated. Scanning electron microscopy, energy dispersive spectrum analysis, transmission electron microscope and Fourier transform infrared spectrum results confirmed that a continuous, uniform and compact SiO2 coating layer was successfully obtained on the phosphors surface. A theoretical coating amount of 5% or higher was found to be good for hydrolysis stability. Photoluminescence results revealed the coated phosphors showed much better water resistance on afterglow properties than the uncoated phosphor. We also discussed and proposed the hydrolysis restriction mechanism of SrAl2O4:Eu2+, Dy3+ in the water-containing coating medium.

Structure analysis of aqueous ferrofluids at interface with silicon: neutron reflectometry data

NASA Astrophysics Data System (ADS)

Gapon, I. V.; Petrenko, V. I.; Bulavin, L. A.; Balasoiu, M.; Kubovcikova, M.; Zavisova, V.; Koneracka, M.; Kopcansky, P.; Chiriac, H.; Avdeev, M. V.

2017-05-01

Adsorption of nanoparticles from aqueous ferrofluids (FFs) on solid surface (crystalline silicon) was studied by neutron reflectometry (NR). Two kinds of FFs were considered. First kind was heavy water-based ferrofluids with magnetite nanoparticles coated by double layer of sodium oleate. Second one FF was cobalt ferrite nanoparticles stabilized by lauric acid/sodium n-dodecylsulphate layer and dispersed in water. It was obtained only a single adsorption layer for two types of ferrofluids. The impact of the magnetic nanoparticles concentration and geometry was considered in frame of the adsorption characteristic of FFs.

Study of interface chemistry between the carrier-transporting layers and their influences on the stability and performance of organic solar cells

NASA Astrophysics Data System (ADS)

Hilal, Muhammad; Han, Jeong In

2018-06-01

This is the first study that described how the interface interactions of graphene oxide (GO) with poly(3-hexylthiophene): 3'H-cyclopropa [8,25] [5,6] fullerene-C60-D5h(6)-3'-butanoic acid 3'-phenyl methyl ester (PCBM) and with poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS) are influencing the stability and performance of poly(3-hexylthiophene): poly(3-hexylthiophene) (P3HT) (P3HT:PCBM)-based organic solar cell. The interface functionalization of these carrier-transporting layers was confirmed by XRD pattern, XPS analysis, and Raman spectroscopy. These interfaces chemical bond formation helped to firmly attach the GO layer with PCBM and PEDOT:PSS layers, forming a strong barrier against water molecule absorption and also provided an easy pathway for fast transfer of free carriers between P3HT:PCBM layer and metal electrodes via the backbone of the conjugated GO sheets. Because of these interface interactions, the device fabricated with PCBM/GO composite as an electron transport layer and GO/PEDOT:PSS composite as hole transport layer demonstrated a remarkable improvement in the value of power conversion efficiency (5.34%) and reproducibility with a high degree of control over the environmental stability (600 h). This study is paving a way for a new technique to further improve the stability and PCE for the commercialization of OSCs.

Mixed layers of sodium caseinate + dextran sulfate: influence of order of addition to oil-water interface.

PubMed

Jourdain, Laureline S; Schmitt, Christophe; Leser, Martin E; Murray, Brent S; Dickinson, Eric

2009-09-01

We report on the interfacial properties of electrostatic complexes of protein (sodium caseinate) with a highly sulfated polysaccharide (dextran sulfate). Two routes were investigated for preparation of adsorbed layers at the n-tetradecane-water interface at pH = 6. Bilayers were made by the layer-by-layer deposition technique whereby polysaccharide was added to a previously established protein-stabilized interface. Mixed layers were made by the conventional one-step method in which soluble protein-polysaccharide complexes were adsorbed directly at the interface. Protein + polysaccharide systems gave a slower decay of interfacial tension and stronger dilatational viscoelastic properties than the protein alone, but there was no significant difference in dilatational properties between mixed layers and bilayers. Conversely, shear rheology experiments exhibited significant differences between the two kinds of interfacial layers, with the mixed system giving much stronger interfacial films than the bilayer system, i.e., shear viscosities and moduli at least an order of magnitude higher. The film shear viscoelasticity was further enhanced by acidification of the biopolymer mixture to pH = 2 prior to interface formation. Taken together, these measurements provide insight into the origin of previously reported differences in stability properties of oil-in-water emulsions made by the bilayer and mixed layer approaches. Addition of a proteolytic enzyme (trypsin) to both types of interfaces led to a significant increase in the elastic modulus of the film, suggesting that the enzyme was adsorbed at the interface via complexation with dextran sulfate. Overall, this study has confirmed the potential of shear rheology as a highly sensitive probe of associative electrostatic interactions and interfacial structure in mixed biopolymer layers.

Specific effects of Ca2+ ions and molecular structure of β-lactoglobulin interfacial layers that drive macroscopic foam stability† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sm00636a Click here for additional data file.

PubMed Central

Schulze-Zachau, Felix; Nagel, Eva; Engelhardt, Kathrin; Stoyanov, Stefan; Gochev, Georgi; Khristov, Khr.; Mileva, Elena; Exerowa, Dotchi; Miller, Reinhard; Peukert, Wolfgang

2016-01-01

β-Lactoglobulin (BLG) adsorption layers at air–water interfaces were studied in situ with vibrational sum-frequency generation (SFG), tensiometry, surface dilatational rheology and ellipsometry as a function of bulk Ca2+ concentration. The relation between the interfacial molecular structure of adsorbed BLG and the interactions with the supporting electrolyte is additionally addressed on higher length scales along the foam hierarchy – from the ubiquitous air–water interface through thin foam films to macroscopic foam. For concentrations <1 mM, a strong decrease in SFG intensity from O–H stretching bands and a slight increase in layer thickness and surface pressure are observed. A further increase in Ca2+ concentrations above 1 mM causes an apparent change in the polarity of aromatic C–H stretching vibrations from interfacial BLG which we associate to a charge reversal at the interface. Foam film measurements show formation of common black films at Ca2+ concentrations above 1 mM due to considerable decrease of the stabilizing electrostatic disjoining pressure. These observations also correlate with a minimum in macroscopic foam stability. For concentrations >30 mM Ca2+, micrographs of foam films show clear signatures of aggregates which tend to increase the stability of foam films. Here, the interfacial layers have a higher surface dilatational elasticity. In fact, macroscopic foams formed from BLG dilutions with high Ca2+ concentrations where aggregates and interfacial layers with higher elasticity are found, showed the highest stability with much smaller bubble sizes. PMID:27337699

Ionically Paired Layer-by-Layer Hydrogels: Water and Polyelectrolyte Uptake Controlled by Deposition Time

DOE PAGES

Selin, Victor; Ankner, John Francis; Sukhishvili, Svetlana

2018-01-11

Despite intense recent interest in weakly bound nonlinear (“exponential”) multilayers, the underlying structure-property relationships of these films are still poorly understood. This study explores the effect of time used for deposition of individual layers of nonlinearly growing layer-by-layer (LbL) films composed of poly(methacrylic acid) (PMAA) and quaternized poly-2-(dimethylamino)ethyl methacrylate (QPC) on film internal structure, swelling, and stability in salt solution, as well as the rate of penetration of invading polyelectrolyte chains. Thicknesses of dry and swollen films were measured by spectroscopic ellipsometry, film internal structure—by neutron reflectometry (NR), and degree of PMAA ionization—by Fourier-transform infrared spectroscopy (FTIR). The results suggestmore » that longer deposition times resulted in thicker films with higher degrees of swelling (up to swelling ratio as high as 4 compared to dry film thickness) and stronger film intermixing. The stronger intermixed films were more swollen in water, exhibited lower stability in salt solutions, and supported a faster penetration rate of invading polyelectrolyte chains. These results can be useful in designing polyelectrolyte nanoassemblies for biomedical applications, such as drug delivery coatings for medical implants or tissue engineering matrices.« less

Ionically Paired Layer-by-Layer Hydrogels: Water and Polyelectrolyte Uptake Controlled by Deposition Time

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

Selin, Victor; Ankner, John Francis; Sukhishvili, Svetlana

Despite intense recent interest in weakly bound nonlinear (“exponential”) multilayers, the underlying structure-property relationships of these films are still poorly understood. This study explores the effect of time used for deposition of individual layers of nonlinearly growing layer-by-layer (LbL) films composed of poly(methacrylic acid) (PMAA) and quaternized poly-2-(dimethylamino)ethyl methacrylate (QPC) on film internal structure, swelling, and stability in salt solution, as well as the rate of penetration of invading polyelectrolyte chains. Thicknesses of dry and swollen films were measured by spectroscopic ellipsometry, film internal structure—by neutron reflectometry (NR), and degree of PMAA ionization—by Fourier-transform infrared spectroscopy (FTIR). The results suggestmore » that longer deposition times resulted in thicker films with higher degrees of swelling (up to swelling ratio as high as 4 compared to dry film thickness) and stronger film intermixing. The stronger intermixed films were more swollen in water, exhibited lower stability in salt solutions, and supported a faster penetration rate of invading polyelectrolyte chains. These results can be useful in designing polyelectrolyte nanoassemblies for biomedical applications, such as drug delivery coatings for medical implants or tissue engineering matrices.« less

Assessing the dynamics of the upper soil layer relative to soil management practices

USDA-ARS?s Scientific Manuscript database

The upper layer of the soil is the critical interface between the soil and the atmosphere and is the most dynamic in response to management practices. One of the soil properties is the stability of the aggregates because this property controls infiltration of water and exchange of gases. An aggregat...

Improvement of water resistance and dimensional stability of wood through titanium dioxide coating

Treesearch

Qingfeng Sun; Haipeng Yu; Yixing Liu; Jian Li; Yun Lu; John F. Hunt

2010-01-01

Moisture absorption and dimensional distortion are the major drawbacks of wood utilization as building material. In this study, poplar wood coated with a thin layer of titanium dioxide (TiO2) was prepared by the cosolvent-controlled hydrothermal method. Subsequently, its moisture absorption and dimensional stability were examined. Scanning...

Reversible adapting layer produces robust single-crystal electrocatalyst for oxygen evolution.

PubMed

Tung, Ching-Wei; Hsu, Ying-Ya; Shen, Yen-Ping; Zheng, Yixin; Chan, Ting-Shan; Sheu, Hwo-Shuenn; Cheng, Yuan-Chung; Chen, Hao Ming

2015-08-28

Electrochemically converting water into oxygen/hydrogen gas is ideal for high-density renewable energy storage in which robust electrocatalysts for efficient oxygen evolution play crucial roles. To date, however, electrocatalysts with long-term stability have remained elusive. Here we report that single-crystal Co3O4 nanocube underlay with a thin CoO layer results in a high-performance and high-stability electrocatalyst in oxygen evolution reaction. An in situ X-ray diffraction method is developed to observe a strong correlation between the initialization of the oxygen evolution and the formation of active metal oxyhydroxide phase. The lattice of skin layer adapts to the structure of the active phase, which enables a reversible facile structural change that facilitates the chemical reactions without breaking the scaffold of the electrocatalysts. The single-crystal nanocube electrode exhibits stable, continuous oxygen evolution for >1,000 h. This robust stability is attributed to the complementary nature of defect-free single-crystal electrocatalyst and the reversible adapting layer.

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

Ok, Kyung-Chul; Park, Jin-Seong, E-mail: hkim-2@naver.com, E-mail: jsparklime@hanyang.ac.kr; Ko Park, Sang-Hee

We demonstrated the fabrication of flexible amorphous indium gallium zinc oxide thin-film transistors (TFTs) on high-temperature polyimide (PI) substrates, which were debonded from the carrier glass after TFT fabrication. The application of appropriate buffer layers on the PI substrates affected the TFT performance and stability. The adoption of the SiN{sub x}/AlO{sub x} buffer layers as water and hydrogen diffusion barriers significantly improved the device performance and stability against the thermal annealing and negative bias stress, compared to single SiN{sub x} or SiO{sub x} buffer layers. The substrates could be bent down to a radius of curvature of 15 mm and themore » devices remained normally functional.« less

Testing density-dependent groundwater models: Two-dimensional steady state unstable convection in infinite, finite and inclined porous layers

USGS Publications Warehouse

Weatherill, D.; Simmons, C.T.; Voss, C.I.; Robinson, N.I.

2004-01-01

This study proposes the use of several problems of unstable steady state convection with variable fluid density in a porous layer of infinite horizontal extent as two-dimensional (2-D) test cases for density-dependent groundwater flow and solute transport simulators. Unlike existing density-dependent model benchmarks, these problems have well-defined stability criteria that are determined analytically. These analytical stability indicators can be compared with numerical model results to test the ability of a code to accurately simulate buoyancy driven flow and diffusion. The basic analytical solution is for a horizontally infinite fluid-filled porous layer in which fluid density decreases with depth. The proposed test problems include unstable convection in an infinite horizontal box, in a finite horizontal box, and in an infinite inclined box. A dimensionless Rayleigh number incorporating properties of the fluid and the porous media determines the stability of the layer in each case. Testing the ability of numerical codes to match both the critical Rayleigh number at which convection occurs and the wavelength of convection cells is an addition to the benchmark problems currently in use. The proposed test problems are modelled in 2-D using the SUTRA [SUTRA-A model for saturated-unsaturated variable-density ground-water flow with solute or energy transport. US Geological Survey Water-Resources Investigations Report, 02-4231, 2002. 250 p] density-dependent groundwater flow and solute transport code. For the case of an infinite horizontal box, SUTRA results show a distinct change from stable to unstable behaviour around the theoretical critical Rayleigh number of 4??2 and the simulated wavelength of unstable convection agrees with that predicted by the analytical solution. The effects of finite layer aspect ratio and inclination on stability indicators are also tested and numerical results are in excellent agreement with theoretical stability criteria and with numerical results previously reported in traditional fluid mechanics literature. ?? 2004 Elsevier Ltd. All rights reserved.

H2O on Pt(111): structure and stability of the first wetting layer

NASA Astrophysics Data System (ADS)

Standop, Sebastian; Morgenstern, Markus; Michely, Thomas; Busse, Carsten

2012-03-01

We study the structure and stability of the first water layer on Pt(111) by variable-temperature scanning tunneling microscopy. We find that a high Pt step edge density considerably increases the long-range order of the equilibrium \\sqrt{37}\\times \\sqrt{37}{R25.3}°- and \\sqrt{39}\\times \\sqrt{39}{R16.1}°-superstructures, presumably due to the capability of step edges to trap residual adsorbates from the surface. Passivating the step edges with CO or preparing a flat metal surface leads to the formation of disordered structures, which still show the same structural elements as the ordered ones. Coadsorption of Xe and CO proves that the water layer covers the metal surface completely. Moreover, we determine the two-dimensional crystal structure of Xe on top of the chemisorbed water layer which exhibits an Xe-Xe distance close to the one in bulk Xe and a rotation angle of 90° between the close-packed directions of Xe and the close-packed directions of the underlying water layer. CO is shown to replace H2O on the Pt(111) surface as has been deduced previously. In addition, we demonstrate that tunneling of electrons into the antibonding state or from the bonding state of H2O leads to dissociation of the molecules and a corresponding reordering of the adlayer into a \\sqrt{3}\\times \\sqrt{3}{R30}°-structure. Finally, a so far not understood restructuring of the adlayer by an increased tunneling current has been observed.

Water Transport in the Micro Porous Layer and Gas Diffusion Layer of a Polymer Electrolyte Fuel Cell

NASA Astrophysics Data System (ADS)

Qin, C.; Hassanizadeh, S. M.

2015-12-01

In this work, a recently developed dynamic pore-network model is presented [1]. The model explicitly solves for both water pressure and capillary pressure. A semi-implicit scheme is used in updating water saturation in each pore body, which considerably increases the numerical stability at low capillary number values. Furthermore, a multiple-time-step algorithm is introduced to reduce the computational effort. A number of case studies of water transport in the micro porous layer (MPL) and gas diffusion layer (GDL) are conducted. We illustrate the role of MPL in reducing water flooding in the GDL. Also, the dynamic water transport through the MPL-GDL interface is explored in detail. This information is essential to the reduced continua model (RCM), which was developed for multiphase flow through thin porous layers [2, 3]. C.Z. Qin, Water transport in the gas diffusion layer of a polymer electrolyte fuel cell: dynamic pore-network modeling, J Electrochimical. Soci., 162, F1036-F1046, 2015. C.Z. Qin and S.M. Hassanizadeh, Multiphase flow through multilayers of thin porous media: general balance equations and constitutive relationships for a solid-gas-liquid three-phase system, Int. J. Heat Mass Transfer, 70, 693-708, 2014. C.Z. Qin and S.M. Hassanizadeh, A new approach to modeling water flooding in a polymer electrolyte fuel cell, Int. J. Hydrogen Energy, 40, 3348-3358, 2015.

Recent progress in degradation and stabilization of organic solar cells

NASA Astrophysics Data System (ADS)

Cao, Huanqi; He, Weidong; Mao, Yiwu; Lin, Xiao; Ishikawa, Ken; Dickerson, James H.; Hess, Wayne P.

2014-10-01

Stability is of paramount importance in organic semiconductor devices, especially in organic solar cells (OSCs). Serious degradation in air limits wide applications of these flexible, light-weight and low-cost power-generation devices. Studying the stability of organic solar cells will help us understand degradation mechanisms and further improve the stability of these devices. There are many investigations into the efficiency and stability of OSCs. The efficiency and stability of devices even of the same photoactive materials are scattered in different papers. In particular, the extrinsic degradation that mainly occurs near the interface between the organic layer and the cathode is a major stability concern. In the past few years, researchers have developed many new cathodes and cathode buffer layers, some of which have astonishingly improved the stability of OSCs. In this review article, we discuss the recent developments of these materials and summarize recent progresses in the study of the degradation/stability of OSCs, with emphasis on the extrinsic degradation/stability that is related to the intrusion of oxygen and water. The review provides detailed insight into the current status of research on the stability of OSCs and seeks to facilitate the development of highly-efficient OSCs with enhanced stability.

Attachment of a hydrophobically modified biopolymer at the oil-water interface in the treatment of oil spills.

PubMed

Venkataraman, Pradeep; Tang, Jingjian; Frenkel, Etham; McPherson, Gary L; He, Jibao; Raghavan, Srinivasa R; Kolesnichenko, Vladimir; Bose, Arijit; John, Vijay T

2013-05-01

The stability of crude oil droplets formed by adding chemical dispersants can be considerably enhanced by the use of the biopolymer, hydrophobically modified chitosan. Turbidimetric analyses show that emulsions of crude oil in saline water prepared using a combination of the biopolymer and the well-studied chemical dispersant (Corexit 9500A) remain stable for extended periods in comparison to emulsions stabilized by the dispersant alone. We hypothesize that the hydrophobic residues from the polymer preferentially anchor in the oil droplets, thereby forming a layer of the polymer around the droplets. The enhanced stability of the droplets is due to the polymer layer providing an increase in electrostatic and steric repulsions and thereby a large barrier to droplet coalescence. Our results show that the addition of hydrophobically modified chitosan following the application of chemical dispersant to an oil spill can potentially reduce the use of chemical dispersants. Increasing the molecular weight of the biopolymer changes the rheological properties of the oil-in-water emulsion to that of a weak gel. The ability of the biopolymer to tether the oil droplets in a gel-like matrix has potential applications in the immobilization of surface oil spills for enhanced removal.

Design of water-repellant coating using dual scale size of hybrid silica nanoparticles on polymer surface

NASA Astrophysics Data System (ADS)

Conti, J.; De Coninck, J.; Ghazzal, M. N.

2018-04-01

The dual-scale size of the silica nanoparticles is commonly aimed at producing dual-scale roughness, also called hierarchical roughness (Lotus effect). In this study, we describe a method to build a stable water-repellant coating with controlled roughness. Hybrid silica nanoparticles are self-assembled over a polymeric surface by alternating consecutive layers. Each one uses homogenously distributed silica nanoparticles of a particular size. The effect of the nanoparticle size of the first layer on the final roughness of the coating is studied. The first layer enables to adjust the distance between the silica nanoparticles of the upper layer, leading to a tuneable and controlled final roughness. An optimal size nanoparticle has been found for higher water-repellency. Furthermore, the stability of the coating on polymeric surface (Polycarbonate substrate) is ensured by photopolymerization of hybridized silica nanoparticles using Vinyl functional groups.

Structural characterization of the phospholipid stabilizer layer at the solid-liquid interface of dispersed triglyceride nanocrystals with small-angle x-ray and neutron scattering

NASA Astrophysics Data System (ADS)

Schmiele, Martin; Schindler, Torben; Unruh, Tobias; Busch, Sebastian; Morhenn, Humphrey; Westermann, Martin; Steiniger, Frank; Radulescu, Aurel; Lindner, Peter; Schweins, Ralf; Boesecke, Peter

2013-06-01

Dispersions of crystalline nanoparticles with at least one sufficiently large unit cell dimension can give rise to Bragg reflections in the small-angle scattering range. If the nanocrystals possess only a small number of unit cells along these particular crystallographic directions, the corresponding Bragg reflections will be broadened. In a previous study of phospholipid stabilized dispersions of β-tripalmitin platelets [Unruh, J. Appl. Crystallogr.JACGAR0021-889810.1107/S0021889807044378 40, 1008 (2007)], the x-ray powder pattern simulation analysis (XPPSA) was developed. The XPPSA method facilitates the interpretation of the rather complicated small-angle x-ray scattering (SAXS) curves of such dispersions of nanocrystals. The XPPSA method yields the distribution function of the platelet thicknesses and facilitates a structural characterization of the phospholipid stabilizer layer at the solid-liquid interface between the nanocrystals and the dispersion medium from the shape of the broadened 001 Bragg reflection. In this contribution an improved and extended version of the XPPSA method is presented. The SAXS and small-angle neutron scattering patterns of dilute phospholipid stabilized tripalmitin dispersions can be reproduced on the basis of a consistent simulation model for the particles and their phospholipid stabilizer layer on an absolute scale. The results indicate a surprisingly flat arrangement of the phospholipid molecules in the stabilizer layer with a total thickness of only 12 Å. The stabilizer layer can be modeled by an inner shell for the fatty acid chains and an outer shell including the head groups and additional water. The experiments support a dense packing of the phospholipid molecules on the nanocrystal surfaces rather than isolated phospholipid domains.

Permeability test and slope stability analysis of municipal solid waste in Jiangcungou Landfill, Shaanxi, China.

PubMed

Yang, Rong; Xu, Zengguang; Chai, Junrui; Qin, Yuan; Li, Yanlong

2016-07-01

With the rapid increase of city waste, landfills have become a major method to deals with municipal solid waste. Thus, the safety of landfills has become a valuable research topic. In this paper, Jiangcungou Landfill, located in Shaanxi, China, was investigated and its slope stability was analyzed. Laboratory tests were used to obtain permeability coefficients of municipal solid waste. Based on the results, the distribution of leachate and stability in the landfill was computed and analyzed. These results showed: the range of permeability coefficient was from 1.0 × 10(-7) cm sec(-1) to 6.0 × 10(-3) cm sec(-1) on basis of laboratory test and some parameters of similar landfills. Owing to the existence of intermediate cover layers in the landfill, the perched water level appeared in the landfill with heavy rain. Moreover, the waste was filled with leachate in the top layer, and the range of leachate level was from 2 m to 5 m in depth under the waste surface in other layers. The closer it gets to the surface of landfill, the higher the perched water level of leachate. It is indicated that the minimum safety factors were 1.516 and 0.958 for winter and summer, respectively. Additionally, the slope failure may occur in summer. The research of seepage and stability in landfills may provide a less costly way to reduce accidents. Landslides often occur in the Jiangcungou Landfill because of the high leachate level. Some measures should be implemented to reduce the leachate level. This paper investigated seepage and slope stability of landfills by numerical methods. These results may provide the basis for increasing stability of landfills.

Layer-by-layer cell membrane assembly

NASA Astrophysics Data System (ADS)

Matosevic, Sandro; Paegel, Brian M.

2013-11-01

Eukaryotic subcellular membrane systems, such as the nuclear envelope or endoplasmic reticulum, present a rich array of architecturally and compositionally complex supramolecular targets that are as yet inaccessible. Here we describe layer-by-layer phospholipid membrane assembly on microfluidic droplets, a route to structures with defined compositional asymmetry and lamellarity. Starting with phospholipid-stabilized water-in-oil droplets trapped in a static droplet array, lipid monolayer deposition proceeds as oil/water-phase boundaries pass over the droplets. Unilamellar vesicles assembled layer-by-layer support functional insertion both of purified and of in situ expressed membrane proteins. Synthesis and chemical probing of asymmetric unilamellar and double-bilayer vesicles demonstrate the programmability of both membrane lamellarity and lipid-leaflet composition during assembly. The immobilized vesicle arrays are a pragmatic experimental platform for biophysical studies of membranes and their associated proteins, particularly complexes that assemble and function in multilamellar contexts in vivo.

Calorimetric Determination of Thermodynamic Stability of MAX and MXene Phases

DOE PAGES

Sharma, Geetu; Naguib, Michael; Feng, Dawei; ...

2016-11-19

MXenes are layered two dimensional materials with exciting properties useful to a wide range of energy applications. They are derived from ceramics (MAX phases) by leaching and their properties reflect their resulting complex compositions which include intercalating cations and anions and water. Their thermodynamic stability is likely linked to these functional groups but has not yet been addressed by quantitative experimental measurements. We report enthalpies of formation from the elements at 25 °C measured using high temperature oxide melt solution calorimetry for a layered Ti-Al-C MAX phase, and the corresponding Ti-C based MXene. The thermodynamic stability of the Ti 3Cmore » 2T x MXene (Tx stands for anionic surface moieties, and intercalated cations) was assessed by calculating the enthalpy of reaction of the MAX phase (ideal composition Ti 3AlC 2) to form MXene, The very exothermic enthalpy of reaction confirms the stability of MXene in an aqueous environment. The surface terminations (O, OH and F) and cations (Li) chemisorbed on the surface and intercalated in the interlayers play a major role in the thermodynamic stabilization of MXene. These findings help to understand and potentially improve properties and performance by characterizing the energetics of species binding to MXene surfaces during synthesis and in energy storage, water desalination and other applications.« less

Effect of ionic strength on the interfacial viscoelasticity and stability of silk fibroin at the oil/water interface.

PubMed

Tang, Xiaoxiao; Qiao, Xiuying; Miller, Reinhard; Sun, Kang

2016-12-01

The amphiphilic character and surface activity endows silk fibroin with the ability to reside at fluid interfaces and effectively stabilize emulsions. However, the influence of relevant factors and their actual effect on the interfacial viscoelasticity and stability of silk fibroin at the oil/water interface has received less attention. In the present study, the effect of ionic strength on the interfacial viscoelasticity, emulsification effectiveness and stability of silk fibroin at the oil/water interface was investigated in detail. A higher ion concentration facilitates greater adsorption, stronger molecular interaction and faster structure reorganization of silk fibroin at the oil/water interface, thus causing quicker interfacial saturation adsorption, greater interfacial strength and lower interfacial structural fracture on large deformation. However, the presence of concentrated ions screens the charges in silk fibroin molecules and the zeta potential decreases as a result of electrostatic screening and ion-binding effects, which may result in emulsion droplet coalescence and a decrease in emulsion stability. The positively-charged ions significantly affect the interfacial elasticity and stability of silk fibroin layers at the oil/water interface as a result of the strong electrostatic interactions between counter-ions and the negatively-charged groups of silk fibroin. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Stabilized CdSe-CoPi composite photoanode for light-assisted water oxidation by transformation of a CdSe/cobalt metal thin film.

PubMed

Costi, Ronny; Young, Elizabeth R; Bulović, Vladimir; Nocera, Daniel G

2013-04-10

Integration of water splitting catalysts with visible-light-absorbing semiconductors would enable direct solar-energy-to-fuel conversion schemes such as those based on water splitting. A disadvantage of some common semiconductors that possess desirable optical bandgaps is their chemical instability under the conditions needed for oxygen evolution reaction (OER). In this study, we demonstrate the dual benefits gained from using a cobalt metal thin-film as the precursor for the preparation of cobalt-phosphate (CoPi) OER catalyst on cadmium chalcogenide photoanodes. The cobalt layer protects the underlying semiconductor from oxidation and degradation while forming the catalyst and simultaneously facilitates the advantageous incorporation of the cadmium chalcogenide layer into the CoPi layer during continued processing of the electrode. The resulting hybrid material forms a stable photoactive anode for light-assisted water splitting.

A comparison of corn fiber gum, hydrophobically modified starch, gum arabic and soybean soluble polysaccharide: interfacial dynamics, viscoelastic response at oil/water interfaces and emulsion stabilization mechanisms

USDA-ARS?s Scientific Manuscript database

The interfacial rheology of polysaccharide adsorption layers of corn fiber gum (CFG), octenyl succinate anhydride-modified starch (OSA-s), gum arabic (GA) and soybean soluble polysaccharides (SSPS) at the oil/water interface and their emulsifying properties in oil-in-water (O/W) emulsions were compa...

Lessons from the Hayman Fire: Forest understory responses to the scarify-and-seed postfire rehabilitation treatment

Treesearch

Paula J. Fornwalt

2009-01-01

In unburned forests, organic plant litter and live vegetation help stabilize the soil and promote water infiltration. Much of this plant material is consumed during severe wildfires, leaving the bare ground susceptible to elevated postfire water runoff and soil erosion (Shakesby and Doerr 2006). Severe wildfires can also produce a water-repellant layer in the soil that...

X-ray and Neutron Scattering Study of the Formation of Core–Shell-Type Polyoxometalates

DOE PAGES

Yin, Panchao; Wu, Bin; Mamontov, Eugene; ...

2016-02-05

A typical type of core-shell polyoxometalates can be obtained through the Keggin-type polyoxometalate-templated growth of a layer of spherical shell structure of {Mo 72Fe 30}. Small angle X-ray scattering is used to study the structural features and stability of the core-shell structures in aqueous solutions. Time-resolved small angle X-ray scattering is applied to monitor the synthetic reactions and a three-stage formation mechanism is proposed to describe the synthesis of the core-shell polyoxometalates based on the monitoring results. Quasi-elastic and inelastic neutron scattering are used to probe the dynamics of water molecules in the core-shell structures and two different types ofmore » water molecules, the confined and structured water, are observed. These water molecules play an important role in bridging core and shell structures and stabilizing the cluster structures. A typical type of core shell polyoxometalates can be obtained through the Keggin-type polyoxometalate-templated growth of a layer of spherical shell structure of {Mo 72Fe 30}. Small-angle X-ray scattering is used to study the structural features and stability of the core shell structures in aqueous solutions. Time-resolved small-angle X-ray scattering is applied to monitor the synthetic reactions, and a three-stage formation mechanism is proposed to describe the synthesis of the core shell polyoxometalates based on the monitoring results. New protocols have been developed by fitting the X-ray data with custom physical models, which provide more convincing, objective, and completed data interpretation. Quasi-elastic and inelastic neutron scattering are used to probe the dynamics of water molecules in the core shell structures, and two different types of water molecules, the confined and structured water, are observed. These water molecules play an important role in bridging core and shell structures and stabilizing the cluster structures.« less

A SHALLOW WATER ISOBARIC BUOY.

DTIC Science & Technology

The genesis, development, and testing of an instrument for following currents in shallow waters is described. The volume of the ’shallow water ...isobaric buoy’ (SWIB) varies in response to pressure signals derived from the depth of the water in which the instrument floats. Mechanisms for auto...indicate the feasibility of the system. The instrument can hover in a relatively restricted horizontal layer. The instrument may find application as a water stability indicator as well as a shallow water current tag. (Author)

N-halamine biocidal coatings via a layer-by-layer assembly technique.

PubMed

Cerkez, Idris; Kocer, Hasan B; Worley, S D; Broughton, R M; Huang, T S

2011-04-05

Two N-halamine copolymer precursors, poly(2,2,6,6-tetramethyl-4-piperidyl methacrylate-co-acrylic acid potassium salt) and poly(2,2,6,6-tetramethyl-4-piperidyl methacrylate-co-trimethyl-2-methacryloxyethylammonium chloride) have been synthesized and successfully coated onto cotton fabric via a layer-by-layer (LbL) assembly technique. A multilayer thin film was deposited onto the fiber surfaces by alternative exposure to polyelectrolyte solutions. The coating was rendered biocidal by a dilute household bleach treatment. The biocidal efficacies of tested swatches composed of treated fibers were evaluated against Staphylococcus aureus and Escherichia coli. It was determined that chlorinated samples inactivated both S. aureus and E. coli O157:H7 within 15 min of contact time, whereas the unchlorinated control samples did not exhibit significant biocidal activities. Stabilities of the coatings toward washing and ultraviolet light exposure have also been studied. It was found that the stability toward washing was superior, whereas the UVA light stability was moderate compared to previously studied N-halamine moieties. The layer-by-layer assembly technique can be used to attach N-halamine precursor polymers onto cellulose surfaces without using covalently bonding tethering groups which limit the structure designs. In addition, ionic precursors are very soluble in water, thus promising for biocidal coatings without the use of organic solvents.

Spatial Atmospheric Pressure Atomic Layer Deposition of Tin Oxide as an Impermeable Electron Extraction Layer for Perovskite Solar Cells with Enhanced Thermal Stability.

PubMed

Hoffmann, Lukas; Brinkmann, Kai O; Malerczyk, Jessica; Rogalla, Detlef; Becker, Tim; Theirich, Detlef; Shutsko, Ivan; Görrn, Patrick; Riedl, Thomas

2018-02-14

Despite the notable success of hybrid halide perovskite-based solar cells, their long-term stability is still a key-issue. Aside from optimizing the photoactive perovskite, the cell design states a powerful lever to improve stability under various stress conditions. Dedicated electrically conductive diffusion barriers inside the cell stack, that counteract the ingress of moisture and prevent the migration of corrosive halogen species, can substantially improve ambient and thermal stability. Although atomic layer deposition (ALD) is excellently suited to prepare such functional layers, ALD suffers from the requirement of vacuum and only allows for a very limited throughput. Here, we demonstrate for the first time spatial ALD-grown SnO x at atmospheric pressure as impermeable electron extraction layers for perovskite solar cells. We achieve optical transmittance and electrical conductivity similar to those in SnO x grown by conventional vacuum-based ALD. A low deposition temperature of 80 °C and a high substrate speed of 2.4 m min -1 yield SnO x layers with a low water vapor transmission rate of ∼10 -4 gm -2 day -1 (at 60 °C/60% RH). Thereby, in perovskite solar cells, dense hybrid Al:ZnO/SnO x electron extraction layers are created that are the key for stable cell characteristics beyond 1000 h in ambient air and over 3000 h at 60 °C. Most notably, our work of introducing spatial ALD at atmospheric pressure paves the way to the future roll-to-roll manufacturing of stable perovskite solar cells.

[Soil moisture variation under different water and fertilization managements in apple orchard of Weibei dryland, China].

PubMed

Zhao, Zhi Yuan; Zheng, Wei; Liu, Jie; Ma, Peng Yi; Li, Zi Yan; Zhai, Bing Nian; Wang, Zhao Hui

2018-04-01

To evaluate the variations of soil moisture under different water and fertilizer treatments in apple orchard in the Weibei dryland, a field experiment was carried out in 2013-2016 at Tianjiawa Village, Baishui County, Shaanxi Province. There were three treatments, i.e., farmers traditional model (only addition of NPK chemical fertilizer, FM), extension model (swine manure and NPK chemical fertilizer combined with black plastic film in tree row space, EM), and optimized model (swine manure and NPK chemical fertilizer combined with black plastic film in tree row space and planting rape in the inter-row of apple trees, OM). The results showed that OM treatment significantly increased soil water storage capacity in 0-200 cm soil layer. Water content of 0-100 cm soil layer was increased by 5.6% and 15.3% in the dry season compared with FM and EM treatment, respectively. Moreover, the soil water relative deficit index of OM was lower than that of EM in 200-300 cm soil layer. The rainfall infiltration in the dry year could reach 300 cm depth under OM. Meanwhile, OM stabilized soil water content and efficiently alleviated the desiccation in deep soil layer. Compared with FM and EM, the 4-year average yield of OM was increased by 36.6% and 22.5%, respectively. In summary, OM could increase water use efficiency through increasing the contents of available soil water and improving the soil water condition in shallow and deep layers, which help alleviate the soil deficit in deep layer and increase yield.

A note on the effect of fault gouge composition on the stability of frictional sliding

USGS Publications Warehouse

Summers, R.; Byerlee, J.

1977-01-01

The frictional properties of fault gouge have been studied at confining pressures to 6 kbars. If the gouge is composed of strong materials such as crushed granite or quartz sand, the frictional strength is high, and violent stick-slip occurs at confining pressures above approximately 1.5 kbars. If the gouge is composed of minerals such as illite, kaolinite, chlorite, or antigorite, which have weak bonding forces between the structural layers, the frictional strength is slightly lower, but violent stick-slip still occurs under high confining pressure. The expanding clays, montmorillonite and vermiculite, which have free water between their structural layers, slide stably at confining pressures as high as 6.25 kbars and exhibit low friction. A similar stable behavior with lowered strength is observed in water-saturated quartz sand when the water is confined within the fault zone during deformation. The results of this series of experiments support water being the stabilizing influence when it is either (1) trapped within or between rocks of low permeability and can provide a high pore pressure when the rocks are deformed, or (2) loosely bonded in a mineral structure, as in the hydrated clays, where it can produce a pseudo-pore pressure when the clay is compressed. In both these cases, the effective stress can be reduced and the deformation stabilized. ?? 1977.

Characterization of nano-porosity in molecular layer deposited films.

PubMed

Perrotta, Alberto; Poodt, Paul; van den Bruele, F J Fieke; Kessels, W M M Erwin; Creatore, Mariadriana

2018-06-12

Molecular layer deposition (MLD) delivers (ultra-) thin organic and hybrid materials, with atomic-level thickness control. However, such layers are often reported to be unstable under ambient conditions, due to the interaction of water and oxygen with the hybrid structure, consequently limiting their applications. In this contribution, we investigate the impact of porosity in MLD layers on their degradation. Alucone layers were deposited by means of trimethylaluminium and ethylene glycol, adopting both temporal and spatial MLD and characterized by means of FT-IR spectroscopy, spectroscopic ellipsometry, and ellipsometric porosimetry. The highest growth per cycle (GPC) achieved by spatial MLD resulted in alucone layers with very low stability in ambient air, leading to their conversion to AlOx. Alucones deposited by means of temporal MLD, instead, showed a lower GPC and a higher ambient stability. Ellipsometric porosimetry showed the presence of open nano-porosity in pristine alucone layers. Pores with a diameter in the range of 0.42-2 nm were probed, with a relative content between 1.5% and 5%, respectively, which are attributed to the temporal and spatial MLD layers. We concluded that a correlation exists between the process GPC, the open-porosity relative content, and the degradation of alucone layers.

Superhydrophobicity of electrospray-synthesized fluorinated silica layers.

PubMed

Kim, Eun-Kyeong; Lee, Chul-Sung; Kim, Sang Sub

2012-02-15

The preparation of superhydrophobic SiO(2) layers through a combination of a nanoscale surface roughness and a fluorination treatment is reported. Electrospraying SiO(2) precursor solutions that had been prepared by a sol-gel chemical route produced very rough SiO(2) layers. Subsequent fluorination treatment with a solution containing trichloro(1H,1H,2H,2H-perfluorooctyl)silane resulted in highly rough, fluorinated SiO(2) layers. The fluorinated rough SiO(2) layers exhibited excellent repellency toward various liquid droplets. In particular, water repellency of 168° was observed. On the bases of Cassie-Baxter and Young-Dupre equations, the surface fraction and the work of adhesion of the rough, fluorinated SiO(2) layers were respectively estimated. In light of the durability in water, ultraviolet resistance, and thermal stability, the superhydrophobic SiO(2) layers prepared in this work hold promise in a range of practical applications. Copyright © 2011 Elsevier Inc. All rights reserved.

Combining slope stability and groundwater flow models to assess stratovolcano collapse hazard

NASA Astrophysics Data System (ADS)

Ball, J. L.; Taron, J.; Reid, M. E.; Hurwitz, S.; Finn, C.; Bedrosian, P.

2016-12-01

Flank collapses are a well-documented hazard at volcanoes. Elevated pore-fluid pressures and hydrothermal alteration are invoked as potential causes for the instability in many of these collapses. Because pore pressure is linked to water saturation and permeability of volcanic deposits, hydrothermal alteration is often suggested as a means of creating low-permeability zones in volcanoes. Here, we seek to address the question: What alteration geometries will produce elevated pore pressures in a stratovolcano, and what are the effects of these elevated pressures on slope stability? We initially use a finite element groundwater flow model (a modified version of OpenGeoSys) to simulate `generic' stratovolcano geometries that produce elevated pore pressures. We then input these results into the USGS slope-stability code Scoops3D to investigate the effects of alteration and magmatic intrusion on potential flank failure. This approach integrates geophysical data about subsurface alteration, water saturation and rock mechanical properties with data about precipitation and heat influx at Cascade stratovolcanoes. Our simulations show that it is possible to maintain high-elevation water tables in stratovolcanoes given specific ranges of edifice permeability (ideally between 10-15 and 10-16 m2). Low-permeability layers (10-17 m2, representing altered pyroclastic deposits or altered breccias) in the volcanoes can localize saturated regions close to the surface, but they may actually reduce saturation, pore pressures, and water table levels in the core of the volcano. These conditions produce universally lower factor-of-safety (F) values than at an equivalent dry edifice with the same material properties (lower values of F indicate a higher likelihood of collapse). When magmatic intrusions into the base of the cone are added, near-surface pore pressures increase and F decreases exponentially with time ( 7-8% in the first year). However, while near-surface impermeable layers create elevated water tables and pore pressures, they do not necessarily produce the largest or deepest collapses. This suggests that mechanical properties of both the edifice and layers still exert a significant control, and collapse volumes depend on a complex interplay of mechanical factors and layering.

Potential of mean force between two hydrophobic solutes in water.

PubMed

Southall, Noel T; Dill, Ken A

2002-12-10

We study the potential of mean force between two nonpolar solutes in the Mercedes Benz model of water. Using NPT Monte Carlo simulations, we find that the solute size determines the relative preference of two solute molecules to come into contact ('contact minimum') or to be separated by a single layer of water ('solvent-separated minimum'). Larger solutes more strongly prefer the contacting state, while smaller solutes have more tendency to become solvent-separated, particularly in cold water. The thermal driving forces oscillate with solute separation. Contacts are stabilized by entropy, whereas solvent-separated solute pairing is stabilized by enthalpy. The free energy of interaction for small solutes is well-approximated by scaled-particle theory. Copyright 2002 Elsevier Science B.V.

Effect of metal ion intercalation on the structure of MXene and water dynamics on its internal surfaces

DOE PAGES

Osti, Naresh C.; Naguib, Michael; Ostadhossein, Alireza; ...

2016-03-24

MXenes are a recently discovered class of 2D materials with an excellent potential for energy storage applications. Because MXene surfaces are hydrophilic and attractive interaction forces between the layers are relatively weak, water molecules can spontaneously intercalate at ambient humidity and significantly influence the key properties of this 2D material. Using complementary X-ray and neutron scattering techniques, we demonstrate that intercalation with potassium cations significantly improves structural homogeneity and water stability in MXenes. Furthermore, in agreement with molecular dynamics simulations, intercalated potassium ions reduce the water self-diffusion coefficient by 2 orders of magnitude, suggesting greater stability of hydrated MXene againstmore » changing environmental conditions.« less

A system of automated processing of deep water hydrological information

NASA Technical Reports Server (NTRS)

Romantsov, V. A.; Dyubkin, I. A.; Klyukbin, L. N.

1974-01-01

An automated system for primary and scientific analysis of deep water hydrological information is presented. Primary processing of the data in this system is carried out on a drifting station, which also calculates the parameters of vertical stability of the sea layers, as well as their depths and altitudes. Methods of processing the raw data are described.

Enhancement of thermal stability and water resistance in yttrium-doped GeO{sub 2}/Ge gate stack

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

Lu, Cimang, E-mail: cimang@adam.t.u-tokyo.ac.jp; Hyun Lee, Choong; Zhang, Wenfeng

2014-03-03

We have systematically investigated the material and electrical properties of yttrium-doped GeO{sub 2} (Y-GeO{sub 2}) on Germanium (Ge). A significant improvement of both thermal stability and water resistance were demonstrated by Y-GeO{sub 2}/Ge stack, compared to that of pure GeO{sub 2}/Ge stack. The excellent electrical properties of Y-GeO{sub 2}/Ge stacks with low D{sub it} were presented as well as enhancement of dielectric constant in Y-GeO{sub 2} layer, which is beneficial for further equivalent oxide thickness scaling of Ge gate stack. The improvement of thermal stability and water resistance are discussed both in terms of the Gibbs free energy lowering andmore » network modification of Y-GeO{sub 2}.« less

Design and Analysis of A Spin-Stabilized Projectile Experimental Apparatus

NASA Astrophysics Data System (ADS)

Siegel, Noah; Rodebaugh, Gregory; Elkins, Christopher; van Poppel, Bret; Benson, Michael; Cremins, Michael; Lachance, Austin; Ortega, Raymond; Vanderyacht, Douglas

2017-11-01

Spinning objects experience an effect termed `The Magnus Moment' due to an uneven pressure distribution based on rotation within a crossflow. Unlike the Magnus force, which is often small for spin-stabilized projectiles, the Magnus moment can have a strong detrimental effect on aerodynamic flight stability. Simulations often fail to accurately predict the Magnus moment in the subsonic flight regime. In an effort to characterize the conditions that cause the Magnus moment, researchers in this work employed Magnetic Resonance Velocimetry (MRV) techniques to measure three dimensional, three component, sub-millimeter resolution fluid velocity fields around a scaled model of a spinning projectile in flight. The team designed, built, and tested using a novel water channel apparatus that was fully MRI-compliant - water-tight and non-ferrous - and capable of spinning a projectile at a constant rotational speed. A supporting numerical simulation effort informed the design process of the scaled projectile to thicken the hydrodynamic boundary layer near the outer surface of the projectile. Preliminary testing produced two-dimensional and three-dimensional velocity data and revealed an asymmetric boundary layer around the projectile, which is indicative of the Magnus effect.

Chemical stabilization of subgrade soil for the strategic expeditionary landing field

NASA Astrophysics Data System (ADS)

Conaway, M. H.

1983-06-01

The Strategic Expeditionary Landing Field (SELF) is a military expeditionary-type airfield with an aluminum matted surface that is designed for sustained tactical and cargo airlift operations in an amphibious objective area. Because of the operational traffic parameters such as loads of the various types of aircraft, tire pressures and volume of traffic, a base layer must be constructed over subgrade soil support conditions which may be only marginal. The base layer could be constructed with conventional soil construction techniques (compaction) and yield the required strength. It would be difficult, however, to maintain this strength for the required one-year service life under many climatic conditions due to the degrading effects of water on the support capacity of many soils. Chemical soil stabilization with lime, portland cement and asphalt stabilizing agents could be used to treat the soil. These additives, when properly mixed with certain types of soils, initiate reactions which will increase soil support strength and enhance durability (resistance to the degrading effects of water). Technically, this procedure is quite viable but logistically, it may not be feasible.

Organic solar cells: evaluation of the stability of P3HT using time-delayed degradation

NASA Astrophysics Data System (ADS)

Poh, Chung-How; Poh, Chung-Kiak; Bryant, Glenn; Belcher, Warwick; Dastoor, Paul

2011-12-01

Despite the fact that the performance of organic solar cells is generally susceptible to degradation by moisture exposure, there has been suggestion that the photoactive layer (P3HT) is surprisingly resilient. This work attempts to confirm the stability of P3HT as an organic solar cell material by deliberately introducing water into the photoactive layer. A dramatic step drop in device performance during cell characterization is observed approximately one day after the device has been fabricated. The time-delayed step drop in output efficiency strongly suggests that moisture has little effect on the P3HT conducting polymer.

Dual role of TiO2 buffer layer in Pt catalyzed BiFeO3 photocathodes: Efficiency enhancement and surface protection

NASA Astrophysics Data System (ADS)

Shen, Huanyu; Zhou, Xiaoxue; Dong, Wen; Su, Xiaodong; Fang, Liang; Wu, Xi; Shen, Mingrong

2017-09-01

Polycrystalline ferroelectric BiFeO3 (BFO) films deposited on transparent indium tin oxide (ITO) electrodes have shown to be an interesting photocathode for photoelectrochemical (PEC) water splitting; however, its PEC performance and stability are far from perfection. Herein, we reported an amorphous TiO2 buffer layer, inserted between BFO and Pt catalyst, improves significantly both its PEC activity and stability. A photocathodic current density of -460 μA/cm2 at 0 V vs. reversible hydrogen electrode (RHE) and an onset potential of 1.25 V vs. RHE were obtained in ITO/BFO/TiO2/Pt photocathode under 100 mW/cm2 Xe-lamp illumination. TiO2 functions as a buffer layer to remove the upward barrier between BFO and Pt, and makes the photogenerated carriers separate efficiently. The photocathode also shows high stability in acid solution after a 10-h PEC continuous testing.

Towards a mechanistic understanding of carbon stabilization in manganese oxides

PubMed Central

Johnson, Karen; Purvis, Graham; Lopez-Capel, Elisa; Peacock, Caroline; Gray, Neil; Wagner, Thomas; März, Christian; Bowen, Leon; Ojeda, Jesus; Finlay, Nina; Robertson, Steve; Worrall, Fred; Greenwell, Chris

2015-01-01

Minerals stabilize organic carbon (OC) in sediments, thereby directly affecting global climate at multiple scales, but how they do it is far from understood. Here we show that manganese oxide (Mn oxide) in a water treatment works filter bed traps dissolved OC as coatings build up in layers around clean sand grains at 3%w/wC. Using spectroscopic and thermogravimetric methods, we identify two main OC fractions. One is thermally refractory (>550 °C) and the other is thermally more labile (<550 °C). We postulate that the thermal stability of the trapped OC is due to carboxylate groups within it bonding to Mn oxide surfaces coupled with physical entrapment within the layers. We identify a significant difference in the nature of the surface-bound OC and bulk OC . We speculate that polymerization reactions may be occurring at depth within the layers. We also propose that these processes must be considered in future studies of OC in natural systems. PMID:26194625

Conformation and dynamics of the ligand shell of a water-soluble Au102 nanoparticle.

PubMed

Salorinne, Kirsi; Malola, Sami; Wong, O Andrea; Rithner, Christopher D; Chen, Xi; Ackerson, Christopher J; Häkkinen, Hannu

2016-01-21

Inorganic nanoparticles, stabilized by a passivating layer of organic molecules, form a versatile class of nanostructured materials with potential applications in material chemistry, nanoscale physics, nanomedicine and structural biology. While the structure of the nanoparticle core is often known to atomic precision, gaining precise structural and dynamical information on the organic layer poses a major challenge. Here we report a full assignment of (1)H and (13)C NMR shifts to all ligands of a water-soluble, atomically precise, 102-atom gold nanoparticle stabilized by 44 para-mercaptobenzoic acid ligands in solution, by using a combination of multidimensional NMR methods, density functional theory calculations and molecular dynamics simulations. Molecular dynamics simulations augment the data by giving information about the ligand disorder and visualization of possible distinct ligand conformations of the most dynamic ligands. The method demonstrated here opens a way to controllable strategies for functionalization of ligated nanoparticles for applications.

Conformation and dynamics of the ligand shell of a water-soluble Au102 nanoparticle

PubMed Central

Salorinne, Kirsi; Malola, Sami; Wong, O. Andrea; Rithner, Christopher D.; Chen, Xi; Ackerson, Christopher J.; Häkkinen, Hannu

2016-01-01

Inorganic nanoparticles, stabilized by a passivating layer of organic molecules, form a versatile class of nanostructured materials with potential applications in material chemistry, nanoscale physics, nanomedicine and structural biology. While the structure of the nanoparticle core is often known to atomic precision, gaining precise structural and dynamical information on the organic layer poses a major challenge. Here we report a full assignment of 1H and 13C NMR shifts to all ligands of a water-soluble, atomically precise, 102-atom gold nanoparticle stabilized by 44 para-mercaptobenzoic acid ligands in solution, by using a combination of multidimensional NMR methods, density functional theory calculations and molecular dynamics simulations. Molecular dynamics simulations augment the data by giving information about the ligand disorder and visualization of possible distinct ligand conformations of the most dynamic ligands. The method demonstrated here opens a way to controllable strategies for functionalization of ligated nanoparticles for applications. PMID:26791253

Influence of long-range forces and capillarity on the function of underwater superoleophobic wrinkled surfaces.

PubMed

Owais, Ahmed; Smith-Palmer, Truis; Gentle, Angus; Neto, Chiara

2018-06-26

Underwater superoleophobic surfaces can be considered a particular type of lubricant-infused surface, that have anti-fouling properties by virtue of a trapped water layer that repels oils. However, as their function relies on a water layer being trapped in the surface roughness, it is crucial to understand the factors that determine the layer stability. In this work, the forces that are responsible for the stability of thin liquid films within structured surfaces were quantified, and the conclusions were tested against the performance of wrinkled surfaces as underwater superoleophobic coatings. Here, the system studied was a family of wrinkled surfaces made of hydrophilic poly(4-vinylpyridine) (P4VP), whereby the wrinkle width could be controllably tuned in the range 90 nm to 8000 nm. The van der Waals free energy was quantified and the capillary forces trapping water in the surface micro- and nano-wrinkle structure were estimated. P4VP surfaces with micro-scale wrinkles had underwater superoleophobic properties, and low adhesion to different oils with droplet roll-off angle below 6° ± 1°. Despite the van der Waals free energy of the system pointing to the dewetting of a water film under oil on top of a smooth P4VP film, the wrinkled structure is sufficient to induce a Cassie state with a trapped water layer. The micro-scale wrinkles (average width 4-12 μm) were found to be particularly effective in the trapping of the water in a Cassie non-adhesive state. The P4VP wrinkled surfaces are superamphiphobic, as when they were first infused with oil, and then exposed to a droplet of water under oil, they exhibited superhydrophobic behavior. The P4VP wrinkles have the additional useful feature of being transparent underwater, which makes them useful candidates for the protection of underwater cameras and sensors.

Drainage effects on the transient, near-surface hydrologic response of a steep hillslope to rainfall: Implications for slope stability, Edmonds, Washington, USA

USGS Publications Warehouse

Biavati, G.; Godt, J.W.; McKenna, J.P.

2006-01-01

Shallow landslides on steep (>25??) hillsides along Puget Sound have resulted in occasional loss of life and costly damage to property during intense or prolonged rainfall. As part of a larger project to assess landslide hazards in the Seattle area, the U.S. Geological Survey instrumented two coastal bluff sites in 2001 to observe the subsurface hydrologic response to rainfall. The instrumentation at one of these sites, near Edmonds, Washington, consists of two rain gauges, two water-content probes that measure volumetric water content at eight depths between 0.2 and 2.0 m, and two tensiometer nests that measure soil-water suction at six depths ranging from 0.2 to 1.5m. Measurements from these instruments are used to test one- and two-dimensional numerical models of infiltration and groundwater flow. Capillary-rise tests, performed in the laboratory on soil sample from the Edmonds site, are used to define the soil hydraulic properties for the wetting process. The field observations of water content and suction show an apparent effect of porosity variation with depth on the hydraulic response to rainfall. Using a range of physical properties consistent with our laboratory and field measurements, we perform sensitivity analyses to investigate the effects of variation in physical and hydraulic properties of the soil on rainfall infiltration, pore-pressure response, and, hence, slope stability. For a two-layer-system in which the hydraulic conductivity of the upper layer is at least 10 times greater than the conductivity of the lower layer, and the infiltration rate is greater than the conductivity of the lower layer, a perched water table forms above the layer boundary potentially destabilizing the upper layer of soil. Two-dimensional modeling results indicate that the addition of a simple trench drain to the same two-layer slope has differing effects on the hydraulic response depending on the initial pressure head conditions. For slope-parallel flow conditions, pressure head is significantly reduced near the drain; however, for transient, vertical infiltration in a partially saturated soil, conditions consistent with those observed during monitoring at the Edmonds site, the drain decreases the thickness of a perched water table by a small amount.

Polyaniline - Carrageenan - Polyvinyl Alcohol Composite Material Synthesized Via Interfacial Polymerization, its Morphological Characteristics and Enhanced Solubility in Water

NASA Astrophysics Data System (ADS)

Montalbo, R. C. K.; Marquez, M. C.

2017-09-01

In recent years, conducting polyaniline (PAni) has been a popular interest of research in the field of conducting polymers due to its relatively low cost, ease of production, good conductivity, and environmental stability. Many studies however, have focused on improving its short-comings such as its limited processability and solubility in common solvents. In this study, PAni, soluble in water was produced via interfacial polymerization with chloroform as the organic solvent. Poly(vinyl alcohol) (PVA) and kappa(κ), iota(ι) and lambda(λ) - carrageenan (κCGN, ιCGN, λCGN) were added to the aqueous layer to stabilize PAni in the medium. FTIR and UV-Vis absorption spectra of the solutions as well as the fabricated film confirmed the existence of PAni emeraldine salt (PAni-ES). FTIR spectrum also confirmed the peaks corresponding to the interaction of PAni with the CGNs. Moreover, PVA-CGN played a very large role on the stability of the PAni nanofibers integrated on the PVA-CGN matrix. The morphologies of the products were further investigated using SEM and TEM. Polymer electrolyte for supercapacitor or an interfacial layer for organic solar cell is being targeted as potential application of the synthesized water soluble PAni.

Orientation-dependent hydration structures at yttria-stabilized cubic zirconia surfaces

DOE PAGES

Hou, Binyang; Kim, Seunghyun; Kim, Taeho; ...

2016-11-30

Water interaction with surfaces is very important and plays key roles in many natural and technological processes. Because the experimental challenges that arise when studying the interaction water with specific crystalline surfaces, most studies on metal oxides have focused on powder samples, which averaged the interaction over different crystalline surfaces. As a result, studies on the crystal orientation-dependent interaction of water with metal oxides are rarely available in the literature. In this work, water adsorption at 8 mol % yttria-stabilized cubic single crystal zirconia (100) and (111) surfaces was studied in terms of interfacial hydration structures using high resolution X-raymore » reflectivity measurements. The interfacial electron density profiles derived from the structure factor analysis of the measured data show the existence of multiple layers of adsorbed water with additional peculiar metal adsorption near the oxide surfaces.Surface relaxation, depletion, and interaction between the adsorbed layers and bulk water are found to vary greatly between the two surfaces and are also different when compared to the previously studied (110) surface. The fractional ratio between chemisorbed and physisorbed water species were also quantitatively estimated, which turned out to vary dramatically from surface to surface. Finally, the result gives us a unique opportunity to reconsider the simplified 2:1 relation between chemisorption and physisorption, originally proposed by Morimoto et al. based on the adsorption isotherms of water on powder metal oxide samples.« less

Long-term stability of sodium caseinate-stabilized nanoemulsions.

PubMed

Yerramilli, Manispuritha; Ghosh, Supratim

2017-01-01

Oil-in-water (5 wt%) nanoemulsions were prepared with different concentration (2.5-10 wt%) of sodium caseinate as a sole emulsifier and their long-term storage stability was investigated for 6 months. Previous studies associated with sodium caseinate looked only into nanoemulsion formation; hence the challenges with long-term stability were not addressed. All nanoemulsions displayed an average droplet size <200 nm, which remained unchanged over 6 months. However, all of them displayed rapid creaming due to unabsorbed protein induced depletion flocculation, whose extent increased with protein concentration, although the cream layer formed was weak and re-dispersible upon gentle mixing. Microstructural analysis of the cream layer showed compaction of flocculated nanodroplet network with time leaving the aqueous phase out. Calculation of depletion interaction energy showed an increase in inter-droplet attraction with protein concentration and decrease with a reduction in droplet size, making the nanoemulsions more resistant to flocculation than conventional emulsions. This work aids in understanding the dependence of protein concentration on long-term stability of sodium caseinate-stabilized nanoemulsions.

Swelling properties of montmorillonite and beidellite clay minerals from molecular simulation: Comparison of temperature interlayer cation, and charge location effects

DOE PAGES

Teich-McGoldrick, Stephanie L.; Greathouse, Jeffery A.; Jove-Colon, Carlos F.; ...

2015-08-27

In this study, the swelling properties of smectite clay minerals are relevant to many engineering applications including environmental remediation, repository design for nuclear waste disposal, borehole stability in drilling operations, and additives for numerous industrial processes and commercial products. We used molecular dynamics and grand canonical Monte Carlo simulations to study the effects of layer charge location, interlayer cation, and temperature on intracrystalline swelling of montmorillonite and beidellite clay minerals. For a beidellite model with layer charge exclusively in the tetrahedral sheet, strong ion–surface interactions shift the onset of the two-layer hydrate to higher water contents. In contrast, for amore » montmorillonite model with layer charge exclusively in the octahedral sheet, weaker ion–surface interactions result in the formation of fully hydrated ions (two-layer hydrate) at much lower water contents. Clay hydration enthalpies and interlayer atomic density profiles are consistent with the swelling results. Water adsorption isotherms from grand canonical Monte Carlo simulations are used to relate interlayer hydration states to relative humidity, in good agreement with experimental findings.« less

Modulating surface rheology by electrostatic protein/polysaccharide interactions.

PubMed

Ganzevles, Renate A; Zinoviadou, Kyriaki; van Vliet, Ton; Cohen, Martien A; de Jongh, Harmen H

2006-11-21

There is a large interest in mixed protein/polysaccharide layers at air-water and oil-water interfaces because of their ability to stabilize foams and emulsions. Mixed protein/polysaccharide adsorbed layers at air-water interfaces can be prepared either by adsorption of soluble protein/polysaccharide complexes or by sequential adsorption of complexes or polysaccharides to a previously formed protein layer. Even though the final protein and polysaccharide bulk concentrations are the same, the behavior of the adsorbed layers can be very different, depending on the method of preparation. The surface shear modulus of a sequentially formed beta-lactoglobulin/pectin layer can be up to a factor of 6 higher than that of a layer made by simultaneous adsorption. Furthermore, the surface dilatational modulus and surface shear modulus strongly (up to factors of 2 and 7, respectively) depend on the bulk -lactoglobulin/pectin mixing ratio. On the basis of the surface rheological behavior, a mechanistic understanding of how the structure of the adsorbed layers depends on the protein/polysaccharide interaction in bulk solution, mixing ratio, ionic strength, and order of adsorption to the interface (simultaneous or sequential) is derived. Insight into the effect of protein/polysaccharide interactions on the properties of adsorbed layers provides a solid basis to modulate surface rheological behavior.

Mix design of asphalt mixture used for the waterproof and anti-cracking layer in the rainy area of South China.

PubMed

Liu, Fuming; Dong, Aixia; Liu, Chaoqun; Wu, Wenqing

2018-01-01

In this study, the asphalt mixture (porosity <2%) was tested for use between the upper and middle layers of the asphalt pavement to improve its interlayer structure and to enhance its related waterproof and anti-cracking ability. Considering the weather characteristics and traffic conditions in Jiangxi Province, appropriate raw materials were selected. Based on the technical indexes of the raw materials, expected porosity (<2%), and AC-5 standard for the asphalt mixture, experiments were conducted to determine the best gradation range of the waterproof and anti-cracking layer, and to obtain the optimum amount of the asphalt and fiber used based on Marshall tests. The high-temperature rutting test, low-temperature cracking test, and water stability test were conducted to evaluate the pavement performance of the waterproof and anti-cracking layer. A waterproof and anti-cracking layer was added between the upper and middle layers of the asphalt pavement, which has excellent performance for avoiding cracks and water damage.

A room temperature strategy towards enhanced performance and bias stability of oxide thin film transistor with a sandwich structure channel layer

NASA Astrophysics Data System (ADS)

Zeng, Yong; Ning, Honglong; Zheng, Zeke; Zhang, Hongke; Fang, Zhiqiang; Yao, Rihui; Xu, Miao; Wang, Lei; Lan, Linfeng; Peng, Junbiao; Lu, Xubing

2017-04-01

Thermal annealing is a conventional and effective way to improve the bias stress stability of oxide thin film transistors (TFT) on solid substrates. However, it is still a challenge for enhancing the bias stress stability of oxide TFTs on flexible substrates by high-temperature post-treatment due to the thermal sensitivity of flexible substrates. Here, a room temperature strategy is presented towards enhanced performance and bias stability of oxide TFTs by intentionally engineering a sandwich structure channel layer consisting of a superlattice with aluminum doped zinc oxide (AZO) and Al2O3 thin films. The Al2O3/AZO/Al2O3-TFTs not only exhibit a saturation mobility of 9.27 cm2 V-1 s-1 and a linear mobility of 11.38 cm2 V-1 s-1 but also demonstrate a better bias stress stability than AZO/Al2O3-TFT. Moreover, the underlying mechanism of this enhanced electrical performance of TFTs with a sandwich structure channel layer is that the bottom Al2O3 thin films can obviously improve the crystalline phase of AZO films while decreasing electrical trapping centers and adsorption sites for undesirable molecules such as water and oxygen.

Continuous shear rheometry of o/w emulsions; control of evaporation in cone/plate geometry.

PubMed

Orafidiya, L O

1989-05-01

Volatile solvents may evaporate during cone/plate viscometry so that false rheograms develop. This surface evaporation was prevented in a cod-liver oil-in-water emulsion stabilized with zanthoxylum gum by layering a film of cod-liver oil on the exposed surface of the emulsion test sample. The oil layer effectively prevented evaporation and did not alter significantly the rheological behaviour of the test material.

The stability of a thin water layer over a rotating disk revisited

NASA Astrophysics Data System (ADS)

Poncet, Sébastien

2014-08-01

The flow driven by a rotating disk of a thin fluid layer in a fixed cylindrical casing is studied by direct numerical simulation and experimental flow visualizations. The characteristics of the flow are first briefly discussed but the focus of this work is to understand the transition to the primary instability. The primary bifurcation is 3D and appears as spectacular sharp-cornered polygonal patterns located along the shroud. The stability diagram is established experimentally in a ( Re, G plane, where G is the aspect ratio of the cavity and Re the rotational Reynolds number and confirmed numerically. The number of vortices scales well with the Ekman number based on the water depth, which confirms the existence of a Stewartson layer along the external cylinder. The critical mixed Reynolds number is found to be constant as in other rotating flows involving a shear-layer instability. Hysteresis cycles are observed highlighting the importance of the spin-up and spin-down processes. In some particular cases, a crossflow instability appears under the form of high azimuthal wave number spiral patterns, similar to those observed in a rotor-stator cavity with throughflow and coexists with the polygons. The DNS calculations confirm the experimental results under the flat free surface hypothesis.

Understanding the Effect of Stratification on Vertical and Temporal Heterogenieties of Cyanobacteria Blooms in Lakes Using a Long Term in-situ Monitoring Station

NASA Astrophysics Data System (ADS)

Wilkinson, A.; Guala, M.; Hondzo, M.

2017-12-01

Harmful Algal Blooms (HAB) are made up of potentially toxic freshwater microorganisms called cyanobacteria, because of this they are a ecological and public health hazard. The occurrences of toxic HAB are unpredictable and highly spatially and temporary variable in freshwater ecosystems. To study the abiotic drivers for toxic HAB, a floating research station has been deployed in a hyper-eutrophic lake in Madison Lake, Minnesota, from June-October 2016. This research station provides full depth water quality (hourly) and meteorological monitoring (5 minutes). Water quality monitoring is performed by an autonomously traversed water quality sonde that provides chemical, physical and biological measurements; including phycocyanin, a photosynthetic pigment distinct to cyanobacteria. A bloom of cyanobacteria recorded in the epiliminion in mid-July was driven by prolonged strong thermal stratification in the water column, high surface water temperatures and high phosphate concentrations in the epiliminion. The high biovolume (BV) persisted until late September and was sustained below the surface after stratification weakened, when the thermocline did not confine cyanobacteria-rich layers any more, and cyanobacteria vertical heterogeneities decayed in the water column. High correlations among BV stratification, surface water temperature, and stratification stability informed the development of a quantitative relationship to determine how BV heterogeneities vary with thermal structure in the water column. The BV heterogeneity decreased with thermal stratification stability and surface water temperature, and the dynamic lake stability described by the Lake Number. Finally the location of maximum BV accumulation showed diurnal patterns ie. BV peaks were observed at 1 m depth during the day and deeper layers during the night, which followed patterns in light penetration and thermocline depth. These findings capture cyanobacteria vertical and temporal heterogeneities on a on full depth, seasonal scale and quantify BV distribution throughout the water column under different stratification conditions, which can be important for mitigating risks of contamination of drinking water and recreational exposure.

Innovative reuse of drinking water sludge in geo-environmental applications.

PubMed

Caniani, D; Masi, S; Mancini, I M; Trulli, E

2013-06-01

In recent years, the replacement of natural raw materials with new alternative materials, which acquire an economic, energetic and environmental value, has gained increasing importance. The considerable consumption of water has favoured the increase in the number of drinking water treatment plants and, consequently, the production of drinking water sludge. This paper proposes a protocol of analyses capable of evaluating chemical characteristics of drinking water sludge from surface water treatment plants. Thereby we are able to assess their possible beneficial use for geo-environmental applications, such as the construction of barrier layers for landfill and for the formation of "bio-soils", when mixed with the stabilized organic fraction of municipal solid waste. This paper reports the results of a study aimed at evaluating the quality and environmental aspects of reconstructed soils ("bio-soil"), which are used in much greater quantities than the usual standard, for "massive" applications in environmental actions such as the final cover of landfills. The granulometric, chemical and physical analyses of the sludge and the leaching test on the stabilized organic fraction showed the suitability of the proposed materials for reuse. The study proved that the reuse of drinking water sludge for the construction of barrier layers and the formation of "bio-soils" reduces the consumption of natural materials, the demand for landfill volumes, and offers numerous technological advantages. Copyright © 2013 Elsevier Ltd. All rights reserved.

A new nano-engineered hierarchical membrane for concurrent removal of surfactant and oil from oil-in-water nanoemulsion

PubMed Central

Qin, Detao; Liu, Zhaoyang; Bai, Hongwei; Sun, Darren Delai; Song, Xiaoxiao

2016-01-01

Surfactant stabilized oil-in-water nanoemulsions pose a severe threat to both the environment and human health. Recent development of membrane filtration technology has enabled efficient oil removal from oil/water nanoemulsion, however, the concurrent removal of surfactant and oil remains unsolved because the existing filtration membranes still suffer from low surfactant removal rate and serious surfactant-induced fouling issue. In this study, to realize the concurrent removal of surfactant and oil from nanoemulsion, a novel hierarchically-structured membrane is designed with a nanostructured selective layer on top of a microstructured support layer. The physical and chemical properties of the overall membrane, including wettability, surface roughness, electric charge, thickness and structures, are delicately tailored through a nano-engineered fabrication process, that is, graphene oxide (GO) nanosheet assisted phase inversion coupled with surface functionalization. Compared with the membrane fabricated by conventional phase inversion, this novel membrane has four times higher water flux, significantly higher rejections of both oil (~99.9%) and surfactant (as high as 93.5%), and two thirds lower fouling ratio when treating surfactant stabilized oil-in-water nanoemulsion. Due to its excellent performances and facile fabrication process, this nano-engineered membrane is expected to have wide practical applications in the oil/water separation fields of environmental protection and water purification. PMID:27087362

Generation of Subsurface Voids, Incubation Effect, and Formation of Nanoparticles in Short Pulse Laser Interactions with Bulk Metal Targets in Liquid: Molecular Dynamics Study

PubMed Central

2017-01-01

The ability of short pulse laser ablation in liquids to produce clean colloidal nanoparticles and unusual surface morphology has been employed in a broad range of practical applications. In this paper, we report the results of large-scale molecular dynamics simulations aimed at revealing the key processes that control the surface morphology and nanoparticle size distributions by pulsed laser ablation in liquids. The simulations of bulk Ag targets irradiated in water are performed with an advanced computational model combining a coarse-grained representation of liquid environment and an atomistic description of laser interaction with metal targets. For the irradiation conditions that correspond to the spallation regime in vacuum, the simulations predict that the water environment can prevent the complete separation of the spalled layer from the target, leading to the formation of large subsurface voids stabilized by rapid cooling and solidification. The subsequent irradiation of the laser-modified surface is found to result in a more efficient ablation and nanoparticle generation, thus suggesting the possibility of the incubation effect in multipulse laser ablation in liquids. The simulations performed at higher laser fluences that correspond to the phase explosion regime in vacuum reveal the accumulation of the ablation plume at the interface with the water environment and the formation of a hot metal layer. The water in contact with the metal layer is brought to the supercritical state and provides an environment suitable for nucleation and growth of small metal nanoparticles from metal atoms emitted from the hot metal layer. The metal layer itself has limited stability and can readily disintegrate into large (tens of nanometers) nanoparticles. The layer disintegration is facilitated by the Rayleigh–Taylor instability of the interface between the higher density metal layer decelerated by the pressure from the lighter supercritical water. The nanoparticles emerging from the layer disintegration are rapidly cooled and solidified due to the interaction with water environment, with a cooling rate of ∼2 × 1012 K/s observed in the simulations. The computational prediction of two distinct mechanisms of nanoparticle formation yielding nanoparticles with different characteristic sizes provides a plausible explanation for the experimental observations of bimodal nanoparticle size distributions in laser ablation in liquids. The ultrahigh cooling and solidification rates suggest the possibility for generation of nanoparticles featuring metastable phases and highly nonequilibrium structures. PMID:28798858

Method to predict seasonal high ground water table (SHGWT) [summary].

DOT National Transportation Integrated Search

2017-04-01

To help assure stability and long-term performance of pavement, a roadways base layer must : remain dry and be higher than the seasonal high groundwater table (SHGWT). Otherwise, the : roadways foundation can be weakened during certain times of...

The effect of bioadhesive on the interfacial compatibility and pervaporation performance of composite membranes by MD and GCMC simulation.

PubMed

Wang, Baohe; Nie, Yan; Ma, Jing

2018-03-01

Combing molecular dynamics (MD) and Grand Canonical Monte Carlo (GCMC) simulation, the effect of bioadhesive transition layer on the interfacial compatibility of the pervaporation composite membranes, and the pervaporation performance toward penetrant molecules were investigated. In our previous experimental study, the structural stability and permeability selectivity of the composite membranes were considerably enhanced by the introduction of bioadhesive carbopol (CP). In the present study, the interfacial compatibility and the interfacial energies between the chitosan (CS) separation layer, CP transition layer and the support layer were investigated, respectively. The mobility of polymer chains, free volume in bulk and interface regions were evaluated by the mean-square displacement (MSD) and free volume voids (FFV) analysis. The diffusion and sorption behavior of water/ethanol molecules in bulk and interface regions were characterized. The simulation results of membrane structure have good consistency, indicating that the introduction of CP transition layer improved the interfacial compatibility and interaction between the separation layer and the support layer. Comparing the bulk region of the separation layer, the mobility and free volume of the polymer chain in the interface region decreased and thus reduced the swelling of CS active layer, revealing the increased diffusion selectivity toward the permeated water and ethanol molecules. The strong hydrogen bonds interaction between the COOH of the CP transition layer and water molecules increased the adsorption of water molecules in the interface region. The simulation results were quite consistent with the experimental results. Copyright © 2018 Elsevier Inc. All rights reserved.

O electrolyte for bio-application

NASA Astrophysics Data System (ADS)

Naddaf, M.; Almariri, A.

2014-09-01

Porous silicon (PS) has been prepared in the dark by anodic etching of n+-type (111) silicon substrate in a HF:HCl:C2H5OH:H2O2:H2O electrolyte. The processed PS layer is characterized by means of photoluminescence (PL) spectroscopy, scanning electron microscope (SEM), water contact angle (CA) measurements, Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and micro-Raman scattering. The CA of fresh PS layer is found to be ~142°. On aging at ambient conditions, the CA decreases gently to reach ~133° after 3 month, and then it is stabilized for a prolonged time of aging. The visible PL emission from the PS layer also exhibits a good stability against aging time. The FTIR and XPS measurements and analysis show that the stable aged PS layer has rather SiO2-rich surface. The micro/nanostructure nature of the PS layer is revealed from SEM and micro-Raman results and correlated to CA results. Stable hydrophobic surface of oxidized PS layer is attractive for bio-applications. The efficiency of the produced PS layers as an entrapping template for specific immobilization of IgG2a antibody via physical absorption process is demonstrated.

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

Koo, Ja-Kong; Do, Nam-Young

The K site near Seoul began landfilling in 1992. The landfilled wastes include municipal solid waste (66.4%), construction residues (20.4%), water and wastewater sludges (trace levels), and hazardous waste (trace levels). The water content of the municipal solid waste is very high (47.3%); as a result, the leachate level (average E.L.) of the landfill, the design value of which is 7.0 m, was measured at 10.3 m in January 1995 and is increasing. The increase of leachate level in the landfill site causes a problem with slope stability. The leachate level at each disposal stage divided by the intermediate covermore » layer was calculated with the HELP (Hydrologic Evaluation of Landfill Performance) model and calibrated with the data measured from February 1993 to June 1995. Also, the hydraulic conductivities of the waste layer and the intermediate cover layer in each stage were calibrated continuously with HELP model analysis. To verify these results, the total water balance in the landfill site was calculated using the infiltration rate calculated from HELP modeling. The leachate level was E.L. 10.0 m, which was close to the measured leachate level. To estimate the change of the leachate level in the future, the total water balances with different leachate discharge rates of 3,000, 3,500, and 5,000 m{sup 3}/day were analyzed. When the leachate discharge rate was 5,000 ton/day and the initial water content was decreased below 25%, the average leachate level was 10.8 m. This result satisfies the safety factor requirements (=1.3) for landfill slope stability. 4 refs., 8 figs., 1 tab.« less

Degradation and stabilization of ice wedges: Implications for assessing risk of thermokarst in northern Alaska

NASA Astrophysics Data System (ADS)

Kanevskiy, Mikhail; Shur, Yuri; Jorgenson, Torre; Brown, Dana R. N.; Moskalenko, Nataliya; Brown, Jerry; Walker, Donald A.; Raynolds, Martha K.; Buchhorn, Marcel

2017-11-01

Widespread degradation of ice wedges has been observed during the last decades in numerous areas within the continuous permafrost zone of Eurasia and North America. To study ice-wedge degradation, we performed field investigations at Prudhoe Bay and Barrow in northern Alaska during 2011-2016. In each study area, a 250-m transect was established with plots representing different stages of ice-wedge degradation/stabilization. Field work included surveying ground- and water-surface elevations, thaw-depth measurements, permafrost coring, vegetation sampling, and ground-based LiDAR scanning. We described cryostratigraphy of frozen soils and stable isotope composition, analyzed environmental characteristics associated with ice-wedge degradation and stabilization, evaluated the vulnerability and resilience of ice wedges to climate change and disturbances, and developed new conceptual models of ice-wedge dynamics that identify the main factors affecting ice-wedge degradation and stabilization and the main stages of this quasi-cyclic process. We found significant differences in the patterns of ice-wedge degradation and stabilization between the two areas, and the patterns were more complex than those previously described because of the interactions of changing topography, water redistribution, and vegetation/soil responses that can interrupt or reinforce degradation. Degradation of ice wedges is usually triggered by an increase in the active-layer thickness during exceptionally warm and wet summers or as a result of flooding or disturbance. Vulnerability of ice wedges to thermokarst is controlled by the thickness of the intermediate layer of the upper permafrost, which overlies ice wedges and protects them from thawing. In the continuous permafrost zone, degradation of ice wedges rarely leads to their complete melting; and in most cases wedges eventually stabilize and can then resume growing, indicating a somewhat cyclic and reversible process. Stabilization of ice wedges after their partial degradation makes them better protected than before degradation because the intermediate layer is usually 2 to 3 times thicker on top of stabilized ice wedges than on top of initial ice wedges in undisturbed conditions. As a result, the likelihood of formation of large thaw lakes in the continuous permafrost zone triggered by ice-wedge degradation alone is very low.

Incorporating an Electrode Modification Layer with a Vertical Phase Separated Photoactive Layer for Efficient and Stable Inverted Nonfullerene Polymer Solar Cells.

PubMed

Shi, Zhenzhen; Liu, Hao; Wang, Yaping; Li, Jinyan; Bai, Yiming; Wang, Fuzhi; Bian, Xingming; Hayat, Tasawar; Alsaedi, Ahmed; Tan, Zhan'ao

2017-12-20

For bulk heterojunction polymer solar cells (PSCs), the donors and acceptors featuring specific phase separation and concentration distribution within the electron donor/acceptor blends crucially affect the exciton dissociation and charge transportation. Herein, efficient and stable nonfullerene inverted PSCs incorporating a phase separated photoactive layer and a titanium chelate electrode modification layer are demonstrated. Water contact angle (WCA), scanning kelvin probe microscopy (SKPM), and atomic force microscopy (AFM) techniques are implemented to characterize the morphology of photoactive layers. Compared with the control conventional device, the short-circuit current density (J sc ) is enhanced from 14.74 to 17.45 mAcm -2 . The power conversion efficiency (PCE) for the inverted PSCs with a titanium (diisopropoxide)-bis-(2,4-pentanedionate) (TIPD) layer increases from 9.67% to 11.69% benefiting from the declined exciton recombination and fairly enhanced charge transportation. Furthermore, the nonencapsulated inverted device with a TIPD layer demonstrates the best long-term stability, 85% of initial PCE remaining and an almost undecayed open-circuit voltage (V oc ) after 1440 h. Our results reveal that the titanium chelate is an excellent electrode modification layer to incorporate with a vertical phase separated photoactive layer for producing high-efficiency and high-stability inverted nonfullerene PSCs.

Transparent ALD-grown Ta2O5 protective layer for highly stable ZnO photoelectrode in solar water splitting.

PubMed

Li, Chengcheng; Wang, Tuo; Luo, Zhibin; Zhang, Dong; Gong, Jinlong

2015-04-30

This communication describes a highly stable ZnO/Ta2O5 photoanode with Ta2O5 deposited by atomic layer deposition. The ultrathin Ta2O5 protective layer prevents corrosion of ZnO and reduces surface carrier recombination, leading to a nearly two-fold increase of photo-conversion efficiency. The transparency of Ta2O5 to sunlight is identified as the main reason for the excellent stability of the photoelectrode for 5 hours.

Structural Properties, Order–Disorder Phenomena, and Phase Stability of Orotic Acid Crystal Forms

PubMed Central

2016-01-01

Orotic acid (OTA) is reported to exist in the anhydrous (AH), monohydrate (Hy1), and dimethyl sulfoxide monosolvate (SDMSO) forms. In this study we investigate the (de)hydration/desolvation behavior, aiming at an understanding of the elusive structural features of anhydrous OTA by a combination of experimental and computational techniques, namely, thermal analytical methods, gravimetric moisture (de)sorption studies, water activity measurements, X-ray powder diffraction, spectroscopy (vibrational, solid-state NMR), crystal energy landscape, and chemical shift calculations. The Hy1 is a highly stable hydrate, which dissociates above 135 °C and loses only a small part of the water when stored over desiccants (25 °C) for more than one year. In Hy1, orotic acid and water molecules are linked by strong hydrogen bonds in nearly perfectly planar arranged stacked layers. The layers are spaced by 3.1 Å and not linked via hydrogen bonds. Upon dehydration the X-ray powder diffraction and solid-state NMR peaks become broader, indicating some disorder in the anhydrous form. The Hy1 stacking reflection (122) is maintained, suggesting that the OTA molecules are still arranged in stacked layers in the dehydration product. Desolvation of SDMSO, a nonlayer structure, results in the same AH phase as observed upon dehydrating Hy1. Depending on the desolvation conditions, different levels of order–disorder of layers present in anhydrous OTA are observed, which is also suggested by the computed low energy crystal structures. These structures provide models for stacking faults as intergrowth of different layers is possible. The variability in anhydrate crystals is of practical concern as it affects the moisture dependent stability of AH with respect to hydration. PMID:26741914

Interfacial band-edge engineered TiO2 protection layer on Cu2O photocathodes for efficient water reduction reaction

NASA Astrophysics Data System (ADS)

Choi, Jaesuk; Song, Jun Tae; Jang, Ho Seong; Choi, Min-Jae; Sim, Dong Min; Yim, Soonmin; Lim, Hunhee; Jung, Yeon Sik; Oh, Jihun

2017-01-01

Photoelectrochemical (PEC) water splitting has emerged as a potential pathway to produce sustainable and renewable chemical fuels. Here, we present a highly active Cu2O/TiO2 photocathode for H2 production by enhancing the interfacial band-edge energetics of the TiO2 layer, which is realized by controlling the fixed charge density of the TiO2 protection layer. The band-edge engineered Cu2O/TiO2 (where TiO2 was grown at 80 °C via atomic layer deposition) enhances the photocurrent density up to -2.04 mA/cm2 at 0 V vs. RHE under 1 sun illumination, corresponding to about a 1,200% enhancement compared to the photocurrent density of the photocathode protected with TiO2 grown at 150 °C. Moreover, band-edge engineering of the TiO2 protection layer prevents electron accumulation at the TiO2 layer and enhances both the Faraday efficiency and the stability for hydrogen production during the PEC water reduction reaction. This facile control over the TiO2/electrolyte interface will also provide new insight for designing highly efficient and stable protection layers for various other photoelectrodes such as Si, InP, and GaAs. [Figure not available: see fulltext.

An advanced Ni-Fe layered double hydroxide electrocatalyst for water oxidation.

PubMed

Gong, Ming; Li, Yanguang; Wang, Hailiang; Liang, Yongye; Wu, Justin Z; Zhou, Jigang; Wang, Jian; Regier, Tom; Wei, Fei; Dai, Hongjie

2013-06-12

Highly active, durable, and cost-effective electrocatalysts for water oxidation to evolve oxygen gas hold a key to a range of renewable energy solutions, including water-splitting and rechargeable metal-air batteries. Here, we report the synthesis of ultrathin nickel-iron layered double hydroxide (NiFe-LDH) nanoplates on mildly oxidized multiwalled carbon nanotubes (CNTs). Incorporation of Fe into the nickel hydroxide induced the formation of NiFe-LDH. The crystalline NiFe-LDH phase in nanoplate form is found to be highly active for oxygen evolution reaction in alkaline solutions. For NiFe-LDH grown on a network of CNTs, the resulting NiFe-LDH/CNT complex exhibits higher electrocatalytic activity and stability for oxygen evolution than commercial precious metal Ir catalysts.

Behavior of sphingomyelin and ceramide in a tear film lipid layer model.

PubMed

Olżyńska, Agnieszka; Cwiklik, Lukasz

2017-03-01

Tear film lipid layer is a complex lipid mixture forming the outermost interface between eye and environment. Its key characteristics, such as surface tension and structural stability, are governed by the presence of polar lipids. The origin of these lipids and exact composition of the mixture are still elusive. We focus on two minor polar lipid components of the tear film lipid later: sphingomyelin and ceramide. By employing coarse grain molecular dynamics in silico simulations accompanied by Langmuir balance experiments we provide molecular-level insight into behavior of these two lipids in a tear film lipid layer model. Sphingomyelin headgroups are significantly exposed at the water-lipids boundary while ceramide molecules are incorporated between other lipids frequently interacting with nonpolar lipids. Even though these two lipids increase surface tension of the film, their molecular-level behavior suggests that they have a stabilizing effect on the tear film lipid layer. Copyright © 2016 Elsevier GmbH. All rights reserved.

DLVO Approximation Methods for Predicting the Attachment of Silver Nanoparticles to Ceramic Membranes.

PubMed

Mikelonis, Anne M; Youn, Sungmin; Lawler, Desmond F

2016-02-23

This article examines the influence of three common stabilizing agents (citrate, poly(vinylpyrrolidone) (PVP), and branched poly(ethylenimine) (BPEI)) on the attachment affinity of silver nanoparticles to ceramic water filters. Citrate-stabilized silver nanoparticles were found to have the highest attachment affinity (under conditions in which the surface potential was of opposite sign to the filter). This work demonstrates that the interaction between the electrical double layers plays a critical role in the attachment of nanoparticles to flat surfaces and, in particular, that predictions of double-layer interactions are sensitive to boundary condition assumptions (constant charge vs constant potential). The experimental deposition results can be explained when using different boundary condition assumptions for different stabilizing molecules but not when the same assumption was assumed for all three types of particles. The integration of steric interactions can also explain the experimental deposition results. Particle size was demonstrated to have an effect on the predicted deposition for BPEI-stabilized particles but not for PVP.

Spray Irrigation Effects on Surface-Layer Stability in an Experimental Citrus Orchard during Winter Freezes.

NASA Astrophysics Data System (ADS)

Cooper, Harry J.; Smith, Eric A.; Martsolf, J. David

1997-02-01

Observations taken by two surface radiation and energy budget stations deployed in the University of Florida/Institute for Food and Agricultural Service experimental citrus orchard in Gainesville, Florida, have been analyzed to identify the effects of sprayer irrigation on thermal stability and circulation processes within the orchard during three 1992 winter freeze episodes. Lapse rates of temperature observed from a micrometeorological tower near the center of the orchard were also recorded during periods of irrigation for incorporation into the analysis. Comparisons of the near-surface temperature lapse rates observed with the two energy budget stations show consistency between the two sites and with the tower-based lapse rates taken over a vertical layer from 1.5 to 15 m above ground level. A theoretical framework was developed that demonstrates that turbulent-scale processes originating within the canopy, driven by latent heat release associated with condensation and freezing processes from water vapor and liquid water released from sprayer nozzles, can destabilize lapse rates and promote warm air mixing above the orchard canopy. The orchard data were then analyzed in the context of the theory for evidence of local overturning and displacement of surface-layer air, with warmer air from aloft driven by locally buoyant plumes generated by water vapor injected into the orchard during the irrigation periods. It was found that surface-layer lapse rates were lower during irrigation periods than under similar conditions when irrigation was not occurring, indicating a greater degree of vertical mixing of surface-layer air with air from above treetops, as a result of local convective overturning induced by the condensation heating of water vapor released at the nozzles of the sprinklers. This provides an additional explanation to the well-accepted heat of fusion release effect, of how undertree irrigation of a citrus orchard during a freeze period helps protect crops against frost damage.

Assessing sea wave and spray effects on Marine Boundary Layer structure

NASA Astrophysics Data System (ADS)

Stathopoulos, Christos; Galanis, George; Patlakas, Platon; Kallos, George

2017-04-01

Air sea interface is characterized by several mechanical and thermodynamical processes. Heat, moisture and momentum exchanges increase the complexity in modeling the atmospheric-ocean system. Near surface atmospheric levels are subject to sea surface roughness and sea spray. Sea spray fluxes can affect atmospheric stability and induce microphysical processes such as sea salt particle formation and condensation/evaporation of water in the boundary layer. Moreover, presence of sea spray can alter stratification over the ocean surface with further insertion of water vapor. This can lead to modified stability conditions and to wind profiles that deviate significantly from the logarithmic approximation. To model these effects, we introduce a fully coupled system consisting of the mesoscale atmospheric model RAMS/ICLAMS and the wave model WAM. The system encompasses schemes for ocean surface roughness, sea salt aerosols and droplet thermodynamic processes and handles sea salt as predictive quantity. Numerical experiments using the developed atmospheric-ocean system are performed over the Atlantic and Mediterranean shoreline. Emphasis is given to the quantification of the improvement obtained in the description of the marine boundary layer, particularly in its lower part as well as in wave characteristics.

Molecular modeling of the dissociation of methane hydrate in contact with a silica surface.

PubMed

Bagherzadeh, S Alireza; Englezos, Peter; Alavi, Saman; Ripmeester, John A

2012-03-15

We use constant energy, constant volume (NVE) molecular dynamics simulations to study the dissociation of the fully occupied structure I methane hydrate in a confined geometry between two hydroxylated silica surfaces between 36 and 41 Å apart, at initial temperatures of 283, 293, and 303 K. Simulations of the two-phase hydrate/water system are performed in the presence of silica, with and without a 3 Å thick buffering water layer between the hydrate phase and silica surfaces. Faster decomposition is observed in the presence of silica, where the hydrate phase is prone to decomposition from four surfaces, as compared to only two sides in the case of the hydrate/water simulations. The existence of the water layer between the hydrate phase and the silica surface stabilizes the hydrate phase relative to the case where the hydrate is in direct contact with silica. Hydrates bound between the silica surfaces dissociate layer-by-layer in a shrinking core manner with a curved decomposition front which extends over a 5-8 Å thickness. Labeling water molecules shows that there is exchange of water molecules between the surrounding liquid and intact cages in the methane hydrate phase. In all cases, decomposition of the methane hydrate phase led to the formation of methane nanobubbles in the liquid water phase. © 2012 American Chemical Society

Engineering of acidic O/W emulsions with pectin.

PubMed

Alba, K; Sagis, L M C; Kontogiorgos, V

2016-09-01

Pectins with distinct molecular design were isolated by aqueous extraction at pH 2.0 or 6.0 and were examined in terms of their formation and stabilisation capacity of model n-alkane-in-water emulsions at acidic pH (pH 2.0). The properties and stability of the resulting emulsions were examined by means of droplet size distribution analysis, Lifshitz-Slyozov-Wagner modelling, bulk rheology, interfacial composition analysis, large-amplitude oscillatory surface dilatational rheology, electrokinetic analysis and fluorescence microscopy. Both pectin preparations were able to emulsify alkanes in water but exhibited distinct ageing characteristics. Emulsions prepared using pectin isolated at pH 6.0 were remarkably stable with respect to droplet growth after thirty days of ageing, while those prepared with pectin isolated at pH 2.0 destabilised rapidly. Examination of chemical composition of interfacial layers indicated multi-layered adsorption of pectins at the oil-water interface. The higher long-term stability of emulsions prepared with pectin isolated at high pH is attributed to mechanically stronger interfaces, the highly branched nature and the low hydrodynamic volume of the chains that result in effective steric stabilisation whereas acetyl and methyl contents do not contribute to the long-term stability. The present work shows that it is possible by tailoring the fine structure of pectin to engineer emulsions that operate in acidic environments. Copyright © 2016 Elsevier B.V. All rights reserved.

Potential sources of hydrogel stabilization of Florida Bay lime mud sediments and implications for organic matter preservation

USGS Publications Warehouse

Louda, J.W.; Loitz, J.W.; Melisiotis, A.; Orem, W.H.

2004-01-01

The fine grained carbonate mud sediments of central Florida Bay are resuspended quite easily. However, this disturbance is usually limited to the surficial ('floc') layer, as the underlying sediments appear to be stabilized by an hydrogelation involving the bulk organic matter. That gelation has occurred within these sediments is suggested from their physical behavior and an observed mathematical relationship between the percentages of organic carbon (C org) and water. Specifically, when extruded from a core barrel, the sediment maintains its integrity and has the consistency of a fine spackling compound. However, upon homogenization, as with a stirring rod prior to sieving, these sediments break into two distinct phases, 1/2-2/3 milky water and 1/3-1/2 sediment grains, by volume. The relationship observed between Corg and water was modeled as both linear (% water = (0.0777) Corg + 0.2984, R2 = 0.8664) and logarithmic (% water = 0.2489 Ln Corg + 0.2842, R2 = 0.9455) functions. As this relationship tends to be asymptotic at higher Corg (>3.5% dry)/water values (>60%) and given an higher correlation, the relationship appears better modeled as a logarithmic function. Values of C org from 1.2 to over 6.5%dry wt. and water contents from 30 to over 70%wt. were observed. The calculated intercept revealed that, without organic carbon (viz. hydrogel formation), these carbonates would likely contain only ???30% water by weight ('m' from linear model). This gelation is proposed to involve exopolymeric substances (EPS), likely polysaccharides, derived from diatoms and cyanobacteria of the microphytobenthos. A cyanobacterial-diatomaceous biofilm/mat underlain by purple sulfur bacteria was shown, by pigment based chemotaxonomy, to form the main components of the microphytobenthos. Additional water column detrital biomass, also mainly cyanobacteria and diatoms, is admixed with the living microphytobenthos in a flocculent/nephloid layer above the sediments prior to final incorporation into the gel-stabilized sediment column. Loss of seagrass cover appears to have allowed higher energy wave induced effects to reach the water-(nephloid)-sediment interface and increase overall turbidity in the bay. The effects of these gelatinized organics upon sediment stability, pore water chemistry and dissolved species flux in/out of the sediments are discussed as areas for future research which takes this (hydro-) gelation phenomenon into account.

Chlorophyll-a thin layers in the Magellan fjord system: The role of the water column stratification

NASA Astrophysics Data System (ADS)

Ríos, Francisco; Kilian, Rolf; Mutschke, Erika

2016-08-01

Fjord systems represent hotspots of primary productivity and organic carbon burial. However, the factors which control the primary production in mid-latitude fjords are poorly understood. In this context, results from the first fine-scale measurements of bio-oceanographic features in the water column of fjords associated with the Strait of Magellan are presented. A submersible fluorescence probe (FP) was used to measure the Chlorophyll-a (Chl-a) concentration in situ, along with conductivity, temperature, hydrostatic pressure (depth) and dissolved oxygen (CTD-O2) of the water column. The Austral spring results of 14 FP-CTD-O2 profiles were used to define the vertical and horizontal patches of the fluorescent pigment distribution and their spatial relations with respect to the observed hydrographic features. Three zones with distinct water structures were defined. In all zones, the 'brown' spectral group (diatoms and dinoflagellates) predominated accounting for >80 wt% of the phytoplankton community. Thin layers with high Chl-a concentration were detected in 50% of the profiles. These layers harbored a substantial amount (30-65 wt%) of the phytoplankton biomass. Stratification was positively correlated to the occurrence of Chl-a thin layers. In stable and highly stratified water columns the integrated Chl-a concentration was higher and frequently located within thin layers whereas well mixed water columns displayed lower values and more homogeneous vertical distribution of Chl-a. These results indicate that mixing/stability processes are important factors accounting to the vertical distribution of Chl-a in Magellan fjords.

Physical properties and stability evaluation of fish oil-in-water emulsions stabilized using thiol-modified β-lactoglobulin fibrils-chitosan complex.

PubMed

Chang, Hon Weng; Tan, Tai Boon; Tan, Phui Yee; Abas, Faridah; Lai, Oi Ming; Wang, Yong; Wang, Yonghua; Nehdi, Imededdine Arbi; Tan, Chin Ping

2018-03-01

Fish oil-in-water emulsions containing fish oil, thiol-modified β-lactoglobulin (β-LG) fibrils, chitosan and maltodextrin were fabricated using a high-energy method. The results showed that chitosan coating induced charge reversal; denoting successful biopolymers complexation. A significantly (p<0.05) larger droplet size and lower polydispersity index value, attributed to the thicker chitosan coating at the oil-water interface, were observed. At high chitosan concentrations, the cationic nature of chitosan strengthened the electrostatic repulsion between the droplets, thus conferring high oxidative stability and low turbidity loss rate to the emulsions. The apparent viscosity of emulsions stabilized using thiol-modified β-LG fibrils-chitosan complex was higher than those stabilized using β-LG fibrils alone, resulting in the former's higher creaming stability. Under thermal treatments (63°C and 100°C), emulsions stabilized using thiol-modified β-LG fibrils-chitosan complex possessed higher heat stability as indicated by the consistent droplet sizes observed. Chitosan provided a thicker protective layer that protected the oil droplets against high temperature. Bridging flocculation occurred at low chitosan concentration (0.1%, w/w), as revealed through microscopic observations which indicated the presence of large flocs. All in all, this work provided us with a better understanding of the application of protein fibrils-polysaccharide complex to produce stable emulsion. Copyright © 2017 Elsevier Ltd. All rights reserved.

Molecular Dynamics Studies of Overbased Detergents on a Water Surface.

PubMed

Bodnarchuk, M S; Dini, D; Heyes, D M; Breakspear, A; Chahine, S

2017-07-25

Molecular dynamics (MD) simulations are reported of model overbased detergent nanoparticles on a model water surface which mimic their behavior on a Langmuir trough or large water droplet in engine oil. The simulations predict that the structure of the nanoparticle on a water surface is different to when it is immersed in a bulk hydrophobic solvent. The surfactant tails are partly directed out of the water, while the carbonate core maximizes its extent of contact with the water. Umbrella sampling calculations of the potential of mean force between two particles showed that they are associated with varying degrees with a maximum binding free energy of ca. 10 k B T for the salicylate stabilized particle, ca. 8 k B T for a sulfurized alkyl phenate stabilized particle, and ca. 5 k B T for a sulfonate stabilized particle. The differences in the strength of attraction depend on the proximity of nearest approach and the energy penalty associated with the disruption of the hydration shell of water molecules around the calcium carbonate core when the two particles approach. This is greatest for the sulfonate particle, which partially loses the surfactant ions to the solution, and least for the salicylate, which forms the weakest water "cage". The particles are separated by a water hydration layer, even at the point of closest approach.

Morphology, mechanical stability, and protective properties of ultrathin gallium oxide coatings.

PubMed

Lawrenz, Frank; Lange, Philipp; Severin, Nikolai; Rabe, Jürgen P; Helm, Christiane A; Block, Stephan

2015-06-02

Ultrathin gallium oxide layers with a thickness of 2.8 ± 0.2 nm were transferred from the surface of liquid gallium onto solid substrates, including conjugated polymer poly(3-hexylthiophene) (P3HT). The gallium oxide exhibits high mechanical stability, withstanding normal pressures of up to 1 GPa in contact mode scanning force microscopy imaging. Moreover, it lowers the rate of photodegradation of P3HT by 4 orders of magnitude, as compared to uncovered P3HT. This allows us to estimate the upper limits for oxygen and water vapor transmission rates of 0.08 cm(3) m(-2) day(-1) and 0.06 mg m(-2) day(-1), respectively. Hence, similar to other highly functional coatings such as graphene, ultrathin gallium oxide layers can be regarded as promising candidates for protective layers in flexible organic (opto-)electronics and photovoltaics because they offer permeation barrier functionalities in conjunction with high optical transparency.

A new set of K3Fe3(PO4)4·yH2O (0 ≤ y ≤ 1) layered phases obtained by topotactic reactions

NASA Astrophysics Data System (ADS)

Trad, Khiem; Wattiaux, Alain; Ben Amara, Mongi; Delmas, Claude; Carlier, Dany

2018-06-01

K3Fe3(PO4)4·H2O powder was synthesized by Na+/K+ exchange reaction from Na3Fe3(PO4)4 in aqueous medium. The replacement of the sodium cations by the potassium larger ones and water molecules causes a structural distortion leading to P2/n monoclinic K3Fe3(PO4)4·H2O. This new layered phase was characterized by XRD, Mössbauer spectroscopy and magnetic measurements. The study of its thermal stability reveals that other new layered K3Fe3(PO4)4·yH2O with (0 ≤ y ≤ 1) phases can be stabilized up to 600 °C and finally at higher temperature a new K3Fe3(PO4)4 polymorph with a different structural type is irreversibility formed.

Analysis of Aircraft, Radiosonde and Radar Observations in Cirrus Clouds Observed During FIRE II: The Interactions Between Environmental Structure, Turbulence and Cloud Microphysical Properties

NASA Technical Reports Server (NTRS)

Smith, Samantha A.; DelGenio, Anthony D.

1999-01-01

Ways to determine the turbulence intensity and the horizontal variability in cirrus clouds have been investigated using FIRE-II aircraft, radiosonde and radar data. Higher turbulence intensities were found within some, but not all, of the neutrally stratified layers. It was also demonstrated that the stability of cirrus layers with high extinction values decrease in time, possibly as a result of radiative destabilization. However, these features could not be directly related to each other in any simple manner. A simple linear relationship was observed between the amount of horizontal variability in the ice water content and its average value. This was also true for the extinction and ice crystal number concentrations. A relationship was also suggested between the variability in cloud depth and the environmental stability across the depth of the cloud layer, which requires further investigation.

A GCM Recent History of the Northern Martian Polar Layered Deposits

NASA Technical Reports Server (NTRS)

Levrard, B.; Laskar, J.; Forget, F.; Montmessin, F.

2003-01-01

The polar layered deposits are thought to contain alternate layers of water and dust in different proportions resulting from the astronomical forcing of the martian climate. In particular, longterm variations in the orbital and axial elements of Mars are presumed to generate variations of the latitudes of surface water ice stability and of the amount of water exchanged in the polar areas. At high obliquity, simplified climate models and independent general circulation simulations suggest a transfer of water ice from the north polar region to tropical areas, whereas at lower and present obliquities, water ice is expected to be stable only at the poles. If so, over obliquity cycles, water ice may be redistributed between the surface water reservoirs leading to their incremental building or disintegration depending on the rates of water transfer. If only a relative limited amount of the available water is exchanged on orbital timescales, this may provide an efficient mechanism for the formation of the observed polar deposits. Within this context, GCM simulations of the martian water cycle have been performed for various obliquities ranging from 15 degrees to 45 degrees and for a large set of initial water ice locations to determine the rate of water exchange between the surface water reservoirs as a function of the obliquity. Propagating these rates over the last 10 Ma orbital history gives a possible recent evolution of these reservoirs.

The Influence of Upward Groundwater between Joints on the Stability and the Behavior of Dip Slope Failures

NASA Astrophysics Data System (ADS)

Weng, C. H.; Lin, M. L.; Hsieh, P. C.

2016-12-01

In recent years, landslides have attracted much attention in the engineering field in Taiwan. As previous studies, landslides are induced by earthquakes, rainfall, and groundwater. That groundwater flows into upper layer through vertical joints, upward groundwater, erodes the slope and reduces its stability. Nevertheless, in the literature, the impact of upward groundwater to the location of sliding surface and the behaviors of dip slope failure has not be investigated. In this study, physical model tests with water flow inclinometers are used to investigate the kinematics of dip slope failures under various conditions and to identify the failure modes of specimens (Fig. 1). Besides, the mechanics of one landslide case owing to upward groundwater is studied by numerical simulation. In the physical tests, the effects of upward groundwater on slope stability are investigated with different angles of inclinometers, different position of joints on specimens and different locations of upward seepage. The test results suggest that the upward water pressure becomes lower when the number of joints increases. As the water pressure increases to 3.8 times the weight of one block of the specimen, the block will slide. Another, when the specimen is covered by one granular content layer (see Fig. 2), the failure surface tends to develop at the granular content layer, and its kinematics is similar to debris slide; when the clay seam is below of the specimen, the translational slide occurs along the bottom of the blocks. Moreover, one dip slope case, Taiwan's National Highway No. 3 landslide event, are studied by numerical simulation. According to the results, some points are concluded: water pressure makes tension cracks on the top of the vertical joints on weathered sandstones; with anchor attenuation, the sandstone moves downslope, which makes the shear strain of the slope toe region increases (see Fig. 3). If friction angle of the slope decreases, the slide surface occurs along the weak surface, and it develops to the toe of the slope.

Assessing the dynamics of the upper soil layer relative to soil management practices

NASA Astrophysics Data System (ADS)

Hatfield, J.; Wacha, K.; Dold, C.

2017-12-01

The upper layer of the soil is the critical interface between the soil and the atmosphere and is the most dynamic in response to management practices. One of the soil properties most reflective to changes in management is the stability of the aggregates because this property controls infiltration of water and exchange of gases. An aggregation model has been developed based on the factors that control how aggregates form and the forces which degrade aggregates. One of the major factors for this model is the storage of carbon into the soil and the interaction with the soil biological component. To increase soil biology requires a stable microclimate that provides food, water, shelter, and oxygen which in turn facilitates the incorporation of organic material into forms that can be combined with soil particles to create stable aggregates. The processes that increase aggregate size and stability are directly linked the continual functioning of the biological component which in turn changes the physical and chemical properties of the soil. Soil aggregates begin to degrade as soon as there is no longer a supply of organic material into the soil. These processes can range from removal of organic material and excessive tillage. To increase aggregation of the upper soil layer requires a continual supply of organic material and the biological activity that incorporates organic material into substances that create a stable aggregate. Soils that exhibit stable soil aggregates at the surface have a prolonged infiltration rate with less runoff and a gas exchange that ensures adequate oxygen for maximum biological activity. Quantifying the dynamics of the soil surface layer provides a quantitative understanding of how management practices affect aggregate stability.

Multilayered silica-biopolymer nanocapsules with a hydrophobic core and a hydrophilic tunable shell thickness

NASA Astrophysics Data System (ADS)

Vecchione, Raffaele; Luciani, Giuseppina; Calcagno, Vincenzo; Jakhmola, Anshuman; Silvestri, Brigida; Guarnieri, Daniela; Belli, Valentina; Costantini, Aniello; Netti, Paolo A.

2016-04-01

Stable, biocompatible, multifunctional and multicompartment nanocarriers are much needed in the field of nanomedicine. Here, we report a simple, novel strategy to design an engineered nanocarrier system featuring an oil-core/hybrid polymer/silica-shell. Silica shells with a tunable thickness were grown in situ, directly around a highly mono-disperse and stable oil-in-water emulsion system, stabilized by a double bio-functional polyelectrolyte heparin/chitosan layer. Such silica showed a complete degradation in a physiological medium (SBF) in a time frame of three days. Moreover, the outer silica shell was coated with polyethyleneglycol (PEG) in order to confer antifouling properties to the final nanocapsule. The outer silica layer combined its properties (it is an optimal bio-interface for bio-conjugations and for the embedding of hydrophilic drugs in the porous structure) with the capability to stabilize the oil core for the confinement of high payloads of lipophilic tracers (e.g. CdSe quantum dots, Nile Red) and drugs. In addition, polymer layers - besides conferring stability to the emulsion while building the silica shell - can be independently exploited if suitably functionalized, as demonstrated by conjugating chitosan with fluorescein isothiocyanate. Such numerous features in a single nanocarrier system make it very intriguing as a multifunctional platform for smart diagnosis and therapy.Stable, biocompatible, multifunctional and multicompartment nanocarriers are much needed in the field of nanomedicine. Here, we report a simple, novel strategy to design an engineered nanocarrier system featuring an oil-core/hybrid polymer/silica-shell. Silica shells with a tunable thickness were grown in situ, directly around a highly mono-disperse and stable oil-in-water emulsion system, stabilized by a double bio-functional polyelectrolyte heparin/chitosan layer. Such silica showed a complete degradation in a physiological medium (SBF) in a time frame of three days. Moreover, the outer silica shell was coated with polyethyleneglycol (PEG) in order to confer antifouling properties to the final nanocapsule. The outer silica layer combined its properties (it is an optimal bio-interface for bio-conjugations and for the embedding of hydrophilic drugs in the porous structure) with the capability to stabilize the oil core for the confinement of high payloads of lipophilic tracers (e.g. CdSe quantum dots, Nile Red) and drugs. In addition, polymer layers - besides conferring stability to the emulsion while building the silica shell - can be independently exploited if suitably functionalized, as demonstrated by conjugating chitosan with fluorescein isothiocyanate. Such numerous features in a single nanocarrier system make it very intriguing as a multifunctional platform for smart diagnosis and therapy. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01192f

Subcritical Water Induced Complexation of Soy Protein and Rutin: Improved Interfacial Properties and Emulsion Stability.

PubMed

Chen, Xiao-Wei; Wang, Jin-Mei; Yang, Xiao-Quan; Qi, Jun-Ru; Hou, Jun-Jie

2016-09-01

Rutin is a common dietary flavonoid with important antioxidant and pharmacological activities. However, its application in the food industry is limited mainly because of its poor water solubility. The subcritical water (SW) treatment provides an efficient technique to solubilize and achieve the enrichment of rutin in soy protein isolate (SPI) by inducing their complexation. The physicochemical, interfacial, and emulsifying properties of the complex were investigated and compared to the mixtures. SW treatment had much enhanced rutin-combined capacity of SPI than that of conventional method, ascribing to the well-contacted for higher water solubility of rutin with stronger collision-induced hydrophobic interactions. Compared to the mixtures of rutin with proteins, the complex exhibited an excellent surface activity and improved the physical and oxidative stability of its stabilized emulsions. This improving effect could be attributed to the targeted accumulation of rutin at the oil-water interface accompanied by the adsorption of SPI resulting in the thicker interfacial layer, as evidenced by higher interfacial protein and rutin concentrations. This study provides a novel strategy for the design and enrichment of nanovehicle providing water-insoluble hydrophobic polyphenols for interfacial delivery in food emulsified systems. © 2016 Institute of Food Technologists®

Free energy barriers for escape of water molecules from protein hydration layer.

PubMed

Roy, Susmita; Bagchi, Biman

2012-03-08

Free energy barriers separating interfacial water molecules from the hydration layer at the surface of a protein to the bulk are obtained by using the umbrella sampling method of free energy calculation. We consider hydration layer of chicken villin head piece (HP-36) which has been studied extensively by molecular dynamics simulations. The free energy calculations reveal a strong sensitivity to the secondary structure. In particular, we find a region near the junction of first and second helix that contains a cluster of water molecules which are slow in motion, characterized by long residence times (of the order of 100 ps or more) and separated by a large free energy barrier from the bulk water. However, these "slow" water molecules constitute only about 5-10% of the total number of hydration layer water molecules. Nevertheless, they play an important role in stabilizing the protein conformation. Water molecules near the third helix (which is the important helix for biological function) are enthalpically least stable and exhibit the fastest dynamics. Interestingly, barrier height distributions of interfacial water are quite broad for water surrounding all the three helices (and the three coils), with the smallest barriers found for those near the helix-3. For the quasi-bound water molecules near the first and second helices, we use well-known Kramers' theory to estimate the residence time from the free energy surface, by estimating the friction along the reaction coordinate from the diffusion coefficient by using Einstein relation. The agreement found is satisfactory. We discuss the possible biological function of these slow, quasi-bound (but transient) water molecules on the surface.

Physically-based landslide assessment for railway infrastructure

NASA Astrophysics Data System (ADS)

Heyerdahl, Håkon; Høydal, Øyvind

2017-04-01

A new high-speed railway line in Eastern Norway passes through areas with Quaternary soil deposits where stability of natural slopes poses considerable challenges. The ground typically consist of thick layers of marine clay deposits, overlain by 8-10 m of silt and sand. Both shallow landslides in the top layers of silt and sand and deep-seated failures in clay must be accounted for. In one section of the railway, the potential for performing stabilizing measures is limited due to existing cultural heritage on top of the slope. Hence, the stability of a steep top section of the slope needs to be evaluated. Assessment of the slope stability for rainfall-triggered slides relies on many parameters. An approach based only on empirical relations will not comply with the design criteria, which only allows deterministic safety margins. From a classic geotechnical approach, the slope would also normally be considered unsafe. However, considerable suction is assumed to exist in the silty and sandy deposits above ground-water level, which will improve the stability. The stabilizing effect however is highly dependent on rainfall, infiltration and soil moisture, and thereby varies continuously. An unsaturated geomechanical approach was taken to assess the slope stability. Soil moisture sensors were installed to monitor changes of in situ water content in the vadose zone. Retention curves for silt/sand specimens samples were measured by pressure plate tests. Some triaxial tests soil strength were performed to check the effect of suction on soil shear strength (performed as drained constant water content tests on compacted specimens). Based on the performed laboratory tests, the unsaturated response of the slope will be modelled numerically and compared with measured soil moisture in situ. Work is still on-going. Initial conditions after respectively dry and wet periods need to be coupled with selected rainfall intensities and duration to see the effect on slope stability. The aim of the work is to reach a result informing the client about the probability of a landslide in the slope, based on expected critical rainfall. A strictly deterministic criterion for minimum safety margin may need to be replaced by scenarios for probability and geometry of potential failures for given return periods and rainfall events.

Present-day Exposures of Water Ice in the Northern Mid-latitudes of Mars

NASA Technical Reports Server (NTRS)

Allen, Carlton C.; Kanner, Lisa C.

2007-01-01

Water ice is exposed in the martian north polar cap, but is rarely exposed beyond the cap boundary. Orbital gamma ray spectrometry data strongly imply the presence of water ice within meters of the surface at latitudes north of approximately 60deg. We have examined mid-latitude areas of the northern plains displaying residual ice-rich layers, and report evidence of present-day surface exposures of water ice. These exposures, if confirmed, could con-strain the latitudinal and temporal stability of surface ice on Mars.

Exposure of Water Ice in the Northern Mid-lattitudes of Mars

NASA Technical Reports Server (NTRS)

Allen, Carlton C.; Kanner, Lisa C.

2007-01-01

Water ice is exposed in the martian north polar cap, and is occasionally exposed beyond the cap boundary. Orbital gamma ray spectrometry data strongly imply the presence of water ice within meters of the surface at latitudes north of approximately 60 deg. We have examined midlatitude areas of the northern plains displaying evidence of residual ice-rich layers, and report possible present-day exposures of ice. These exposures, if confirmed, could constrain the latitudinal and temporal stability of surface ice on Mars.

Fabrication of porous matrix membrane (PMM) using metal-organic framework as green template for water treatment.

PubMed

Lee, Jian-Yuan; Tang, Chuyang Y; Huo, Fengwei

2014-01-17

Pressure-driven membranes with high porosity can potentially be fabricated by removing template, such as low water stability metal-organic frameworks (MOFs) or other nanoparticles, in polymeric matrix. We report on the use of benign MOFs as green template to enhance porosity and interconnectivity of the water treatment membranes. Significantly enhanced separation performance was observed which might be attributed to the mass transfer coefficient of the substrate layer increased in ultrafiltration (UF) application.

Role of additives in formation of solid-electrolyte interfaces on carbon electrodes and their effect on high-voltage stability.

PubMed

Qu, Weiguo; Dorjpalam, Enkhtuvshin; Rajagopalan, Ramakrishnan; Randall, Clive A

2014-04-01

The in situ modification of a lithium hexafluorophosphate-based electrolyte using a molybdenum oxide catalyst and small amount of water (1 vol %) yields hydrolysis products such as mono-, di-, and alkylfluorophosphates. The electrochemical stability of ultrahigh-purity, high-surface-area carbon electrodes derived from polyfurfuryl alcohol was tested using the modified electrolyte. Favorable modification of the solid electrolyte interface (SEI) layer on the activated carbon electrode increased the cyclable electrochemical voltage window (4.8-1.2 V vs. Li/Li(+)). The chemical modification of the SEI layer induced by electrolyte additives was characterized by using X-ray photoelectron spectroscopy. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Atomically Thin Hexagonal Boron Nitride Nanofilm for Cu Protection: The Importance of Film Perfection.

PubMed

Khan, Majharul Haque; Jamali, Sina S; Lyalin, Andrey; Molino, Paul J; Jiang, Lei; Liu, Hua Kun; Taketsugu, Tetsuya; Huang, Zhenguo

2017-01-01

Outstanding protection of Cu by high-quality boron nitride nanofilm (BNNF) 1-2 atomic layers thick in salt water is observed, while defective BNNF accelerates the reaction of Cu toward water. The chemical stability, insulating nature, and impermeability of ions through the BN hexagons render BNNF a great choice for atomic-scale protection. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Properties, ageing behavior and stability of bipolar films containing nano-layers of allylamine and acrylic acid plasma polymers

NASA Astrophysics Data System (ADS)

Aziz, Gaelle; Asadian, Mahtab; Declercq, Heidi; Morent, Rino; De Geyter, Nathalie

2018-06-01

In this work, a dielectric barrier discharge (DBD) has been used for the deposition of bipolar films containing alternating nano-layers of plasma polymerized allylamine (PPAam) and acrylic acid (PPAac). Various films were obtained by varying the single-layer thickness of each plasma polymer while maintaining a constant total film thickness and two kinds of films were fabricated via different depositing sequences (PPAam/Aac and PPAac/Aam). Films properties, ageing in air and stability in water over a 7 days period were investigated. Results showed that, COO- and NH3+ polar entities, generated from the interaction of PPAam and PPAac, are present in the bipolar films. Concerning the films stability, the different reaction mechanisms involved in the formation of each kind of films resulted in a higher amount of polar groups in the PPAam/Aac films; this conferred these films a higher stability than PPAac/Aam. Concerning the films ageing behavior, all prepared samples underwent some kind of ageing which was found to be dependent on the deposition sequence. Results also showed that bipolar coatings exhibited better cell-material interactions compared to PPAam and PPAac films; with a better cell viability observed on PPAam/Aac coatings after 1 and 7 days culture.

Fabrication of ultrathin multilayered superomniphobic nanocoatings by liquid flame spray, atomic layer deposition, and silanization.

PubMed

Sorvali, Miika; Vuori, Leena; Pudas, Marko; Haapanen, Janne; Mahlberg, Riitta; Ronkainen, Helena; Honkanen, Mari; Valden, Mika; Mäkelä, Jyrki M

2018-05-04

Superomniphobic, i.e. liquid-repellent, surfaces have been an interesting area of research during recent years due to their various potential applications. However, producing such surfaces, especially on hard and resilient substrates like stainless steel, still remains challenging. We present a stepwise fabrication process of a multilayered nanocoating on a stainless steel substrate, consisting of a nanoparticle layer, a nanofilm, and a layer of silane molecules. Liquid flame spray was used to deposit a TiO 2 nanoparticle layer as the bottom layer for producing a suitable surface structure. The interstitial Al 2 O 3 nanofilm, fabricated by atomic layer deposition (ALD), stabilized the nanoparticle layer, and the topmost fluorosilane layer lowered the surface energy of the coating for enhanced omniphobicity. The coating was characterized with field emission scanning electron microscopy, focused ion beam scanning electron microscopy, x-ray photoelectron spectroscopy, contact angle (CA) and sliding angle (SA) measurements, and microscratch testing. The widely recognized requirements for superrepellency, i.e. CA > 150° and SA < 10°, were achieved for deioinized water, diiodomethane, and ethylene glycol. The mechanical stability of the coating could be varied by tuning the thickness of the ALD layer at the expense of repellency. To our knowledge, this is the thinnest superomniphobic coating reported so far, with the average thickness of about 70 nm.

Fabrication of ultrathin multilayered superomniphobic nanocoatings by liquid flame spray, atomic layer deposition, and silanization

NASA Astrophysics Data System (ADS)

Sorvali, Miika; Vuori, Leena; Pudas, Marko; Haapanen, Janne; Mahlberg, Riitta; Ronkainen, Helena; Honkanen, Mari; Valden, Mika; Mäkelä, Jyrki M.

2018-05-01

Superomniphobic, i.e. liquid-repellent, surfaces have been an interesting area of research during recent years due to their various potential applications. However, producing such surfaces, especially on hard and resilient substrates like stainless steel, still remains challenging. We present a stepwise fabrication process of a multilayered nanocoating on a stainless steel substrate, consisting of a nanoparticle layer, a nanofilm, and a layer of silane molecules. Liquid flame spray was used to deposit a TiO2 nanoparticle layer as the bottom layer for producing a suitable surface structure. The interstitial Al2O3 nanofilm, fabricated by atomic layer deposition (ALD), stabilized the nanoparticle layer, and the topmost fluorosilane layer lowered the surface energy of the coating for enhanced omniphobicity. The coating was characterized with field emission scanning electron microscopy, focused ion beam scanning electron microscopy, x-ray photoelectron spectroscopy, contact angle (CA) and sliding angle (SA) measurements, and microscratch testing. The widely recognized requirements for superrepellency, i.e. CA > 150° and SA < 10°, were achieved for deioinized water, diiodomethane, and ethylene glycol. The mechanical stability of the coating could be varied by tuning the thickness of the ALD layer at the expense of repellency. To our knowledge, this is the thinnest superomniphobic coating reported so far, with the average thickness of about 70 nm.

Effect of sulfate on the transformation of corrosion scale composition and bacterial community in cast iron water distribution pipes.

PubMed

Yang, Fan; Shi, Baoyou; Bai, Yaohui; Sun, Huifang; Lytle, Darren A; Wang, Dongsheng

2014-08-01

The chemical stability of iron corrosion scales and the microbial community of biofilm in drinking water distribution system (DWDS) can have great impact on the iron corrosion and corrosion product release, which may result in "red water" issues, particularly under the situation of source water switch. In this work, experimental pipe loops were set up to investigate the effect of sulfate on the dynamical transformation characteristics of iron corrosion products and bacterial community in old cast iron distribution pipes. All the test pipes were excavated from existing DWDS with different source water supply histories, and the test water sulfate concentration was in the range of 50-350 mg/L. Pyrosequencing of 16S rRNA was used for bacterial community analysis. The results showed that iron release increased markedly and even "red water" occurred for pipes with groundwater supply history when feed water sulfate elevated abruptly. However, the iron release of pipes with only surface water supply history changed slightly without noticeable color even the feed water sulfate increased multiply. The thick-layered corrosion scales (or densely distributed tubercles) on pipes with surface water supply history possessed much higher stability due to the larger proportion of stable constituents (mainly Fe3O4) in their top shell layer; instead, the rather thin and uniform non-layered corrosion scales on pipes with groundwater supply history contained relatively higher proportion of less stable iron oxides (e.g. β-FeOOH, FeCO3 and green rust). The less stable corrosion scales tended to be more stable with sulfate increase, which was evidenced by the gradually decreased iron release and the increased stable iron oxides. Bacterial community analysis indicated that when switching to high sulfate water, iron reducing bacteria (IRB) maintained dominant for pipes with stable corrosion scales, while significant increase of sulfur oxidizing bacteria (SOB), sulfate reducing bacteria (SRB) and iron oxidizing bacteria (IOB) was observed for pipes with less stable corrosion scales. Copyright © 2014 Elsevier Ltd. All rights reserved.

Polyaniline as a new type of hole-transporting material to significantly increase the solar water splitting performance of BiVO4 photoanodes

NASA Astrophysics Data System (ADS)

Wang, Xiaojun; Ye, Kai-Hang; Yu, Xiang; Zhu, Jiaqian; Zhu, Yi; Zhang, Yuanming

2018-07-01

Polyaniline (PANI), with its low cost, chemical stability and high conductivity, is used as a hole transporting layer to fabricate NiOOH/PANI/BiVO4 (NPB) photoanode, of which the photoelectrochemical (PEC) water splitting performance is significantly enhanced. The remarkable water oxidation photocurrent of NPB photoanode achieves 3.31 mA cm-2 at 1.23 V vs. RHE under AM 1.5G solar light irradiation, which is greatly increased compared with that of pristine BiVO4 (0.89 mA cm-2 under the same condition). The maximal incident photon-to-current conversion efficiency achieves 83.3% at 430 nm at 1.23 V vs. RHE and the maximal applied bias photo-to-current efficiency reaches 1.20% at 0.68 V vs. RHE, which are nearly five and ten times higher than that of pristine BiVO4 photoanode, respectively. This NPB photoanode exhibits excellent stability with about 97.22% Faraday efficiency after PEC water splitting for 3 h. The exciting results demonstrate that PANI shows great potential as a hole-transporting layer for photoanode and NPB is an efficient and stable photoanode material with a great potential application in PEC water splitting. Overall, this work provides an excellent reference on designing and fabricating photoanode materials for the future.

Water-mediated interactions between hydrophobic and ionic species in cylindrical nanopores

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

Vaitheeswaran, S.; Reddy, G.; Thirumalai, D.

2009-03-07

We use Metropolis Monte Carlo and umbrella sampling to calculate the free energies of interaction of two methane molecules and their charged derivatives in cylindrical water-filled pores. Confinement strongly alters the interactions between the nonpolar solutes and completely eliminates the solvent separated minimum (SSM) that is seen in bulk water. The free energy profiles show that the methane molecules are either in contact or at separations corresponding to the diameter and the length of the cylindrical pore. Analytic calculations that estimate the entropy of the solutes, which are solvated at the pore surface, qualitatively explain the shape of the freemore » energy profiles. Adding charges of opposite sign and magnitude 0.4e or e (where e is the electronic charge) to the methane molecules decreases their tendency for surface solvation and restores the SSM. We show that confinement induced ion-pair formation occurs whenever l{sub B}/D{approx}O(1), where l{sub B} is the Bjerrum length and D is the pore diameter. The extent of stabilization of the SSM increases with ion charge density as long as l{sub B}/D<1. In pores with D{<=}1.2 nm, in which the water is strongly layered, increasing the charge magnitude from 0.4e to e reduces the stability of the SSM. As a result, ion-pair formation that occurs with negligible probability in the bulk is promoted. In larger diameter pores that can accommodate a complete hydration layer around the solutes, the stability of the SSM is enhanced.« less

The roll-up and merging of coherent structures in shallow mixing layers

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

Lam, M. Y., E-mail: celmy@connect.ust.hk; Ghidaoui, M. S.; Kolyshkin, A. A.

2016-09-15

The current study seeks a fundamental explanation to the development of two-dimensional coherent structures (2DCSs) in shallow mixing layers. A nonlinear numerical model based on the depth-averaged shallow water equations is used to investigate the temporal evolution of shallow mixing layers, where the mapping from temporal to spatial results is made using the velocity at the center of the mixing layers. The flow is periodic in the streamwise direction. Transmissive boundary conditions are used in the cross-stream boundaries to prevent reflections. Numerical results are compared to linear stability analysis, mean-field theory, and secondary stability analysis. Results suggest that the onsetmore » and development of 2DCS in shallow mixing layers are the result of a sequence of instabilities governed by linear theory, mean-field theory, and secondary stability theory. The linear instability of the shearing velocity gradient gives the onset of 2DCS. When the perturbations reach a certain amplitude, the flow field of the perturbations changes from a wavy shape to a vortical (2DCS) structure because of nonlinearity. The development of the vertical 2DCS does not appear to follow weakly nonlinear theory; instead, it follows mean-field theory. After the formation of 2DCS, separate 2DCSs merge to form larger 2DCS. In this way, 2DCSs grow and shallow mixing layers develop and grow in scale. The merging of 2DCS in shallow mixing layers is shown to be caused by the secondary instability of the 2DCS. Eventually 2DCSs are dissipated by bed friction. The sequence of instabilities can cause the upscaling of the turbulent kinetic energy in shallow mixing layers.« less

Comparison of vertical discretization techniques in finite-difference models of ground-water flow; example from a hypothetical New England setting

USGS Publications Warehouse

Harte, Philip T.

1994-01-01

Proper discretization of a ground-water-flow field is necessary for the accurate simulation of ground-water flow by models. Although discretiza- tion guidelines are available to ensure numerical stability, current guidelines arc flexible enough (particularly in vertical discretization) to allow for some ambiguity of model results. Testing of two common types of vertical-discretization schemes (horizontal and nonhorizontal-model-layer approach) were done to simulate sloping hydrogeologic units characteristic of New England. Differences of results of model simulations using these two approaches are small. Numerical errors associated with use of nonhorizontal model layers are small (4 percent). even though this discretization technique does not adhere to the strict formulation of the finite-difference method. It was concluded that vertical discretization by means of the nonhorizontal layer approach has advantages in representing the hydrogeologic units tested and in simplicity of model-data input. In addition, vertical distortion of model cells by this approach may improve the representation of shallow flow processes.

Highly stable organic field-effect transistors with engineered gate dielectrics (Conference Presentation)

NASA Astrophysics Data System (ADS)

Kippelen, Bernard; Wang, Cheng-Yin; Fuentes-Hernandez, Canek; Yun, Minseong; Singh, Ankit K.; Dindar, Amir; Choi, Sangmoo; Graham, Samuel

2016-11-01

Organic field-effect transistors (OFETs) have the potential to lead to low-cost flexible displays, wearable electronics, and sensors. While recent efforts have focused greatly on improving the maximum charge mobility that can be achieved in such devices, studies about the stability and reliability of such high performance devices are relatively scarce. In this talk, we will discuss the results of recent studies aimed at improving the stability of OFETs under operation and their shelf lifetime. In particular, we will focus on device architectures where the gate dielectric is engineered to act simultaneously as an environmental barrier layer. In the past, our group had demonstrated solution-processed top-gate OFETs using TIPS-pentacene and PTAA blends as a semiconductor layer with a bilayer gate dielectric layer of CYTOP/Al2O3, where the oxide layer was fabricated by atomic layer deposition, ALD. Such devices displayed high operational stability with little degradation after 20,000 on/off scan cycles or continuous operation (24 h), and high environmental stability when kept in air for more than 2 years, with unchanged carrier mobility. Using this stable device geometry, simple circuits and sensors operating in aqueous conditions were demonstrated. However, the Al2O3 layer was found to degrade due to corrosion under prolonged exposure in aqueous solutions. In this talk, we will report on the use of a nanolaminate (NL) composed of Al2O3 and HfO2 by ALD to replace the Al2O3 single layer in the bilayer gate dielectric use in top-gate OFETs. Such OFETs were found to operate under harsh condition such as immersion in water at 95 °C. This work was funded by the Department of Energy (DOE) through the Bay Area Photovoltaics Consortium (BAPVC) under Award Number DE-EE0004946.

Structure, dynamics and stability of water/scCO2/mineral interfaces from ab initio molecular dynamics simulations.

PubMed

Lee, Mal-Soon; Peter McGrail, B; Rousseau, Roger; Glezakou, Vassiliki-Alexandra

2015-10-12

The boundary layer at solid-liquid interfaces is a unique reaction environment that poses significant scientific challenges to characterize and understand by experimentation alone. Using ab initio molecular dynamics (AIMD) methods, we report on the structure and dynamics of boundary layer formation, cation mobilization and carbonation under geologic carbon sequestration scenarios (T = 323 K and P = 90 bar) on a prototypical anorthite (001) surface. At low coverage, water film formation is enthalpically favored, but entropically hindered. Simulated adsorption isotherms show that a water monolayer will form even at the low water concentrations of water-saturated scCO2. Carbonation reactions readily occur at electron-rich terminal Oxygen sites adjacent to cation vacancies that readily form in the presence of a water monolayer. These results point to a carbonation mechanism that does not require prior carbonic acid formation in the bulk liquid. This work also highlights the modern capabilities of theoretical methods to address structure and reactivity at interfaces of high chemical complexity.

Slime coating of kaolinite on chalcopyrite in saline water flotation

NASA Astrophysics Data System (ADS)

Li, Zhi-li; Rao, Feng; Song, Shao-xian; Li, Yan-mei; Liu, Wen-biao

2018-05-01

In saline water flotation, the salinity can cause a distinguishable slime coating of clay minerals on chalcopyrite particles through its effect on their electrical double layers in aqueous solutions. In this work, kaolinite was used as a representative clay mineral for studying slime coating during chalcopyrite flotation. The flotation of chalcopyrite in the presence and absence of kaolinite in tap water, seawater, and gypsum-saturated water and the stability of chalcopyrite and kaolinite particles in slurries are presented. Zeta-potential distributions and scanning electron microscopy images were used to characterize and explain the different slime coating degrees and the different flotation performances. Kaolinite particles induced slime coating on chalcopyrite surfaces and reduced chalcopyrite floatability to the greatest extent when the pH value was in the alkaline range. At 0.24wt% of kaolinite, the chalcopyrite floatability was depressed by more than 10% at alkaline pH levels in tap water. Salinity in seawater and gypsum-saturated water compressed the electrical double layers and resulted in extensive slime coating.

Numerical studies of depressurization-induced gas production from an interbedded marine turbidite gas hydrate reservoir model

USGS Publications Warehouse

Myshakin, Evgeniy; Lin, Jeen-Shang; Uchida, Shun; Seol, Yongkoo; Collett, Timothy S.; Boswell, Ray

2017-01-01

The numerical simulation of thin hydrate-bearing sand layers interbedded with mud layers is investigated. In this model, the lowest hydrate layer occurs at the base of gas hydrate stability and overlies a thinly-interbedded saline aquifer. The predicted gas rates reach 6.25 MMscf/day (1.77 x 105 m3 /day) after 90 days of continuous depressurization with manageable water production. Development of horizontal dissociating interfaces between hydrate-bearing sand and mud layers is a primary determinant of reservoir performance. A set of simulations has been executed to assess uncertainty in in situ permeability and to determine the impact of the saline aquifer on productivity.

Model tests of living brush mattresses made of shrub and tree willows as bank protection at navigable waters

NASA Astrophysics Data System (ADS)

Sokopp, Manuel

2014-05-01

The embankment stability at navigable waters suffers from hydraulic loads, like strong ship induced waves, resulting hydropeaking and strong water-level fluctuations. Willow brush mattresses can reduce erosion at the embankments of rivers and increase bank stability. Due to experiences gained in the project "Alternative Technical-Biological Bank Protection on Inland Water-ways" the Federal Waterways Engineering and Research Institute commissioned a more detailed investigation of protective functions of willow brush mattresses respectively the differences between brush mattresses made of pure shrub (Salix viminalis) or tree willows (Salix alba) at water ways with high ship-induced hydraulic loads. This paper shows the upcoming research methods of the years 2014 to 2016. The protective functions of two different willow brush mattresses and the congruence between soil, hydraulics and willow sprouts movement will be investigated in a wave basin by measuring flow velocity with ADVs (Acoustic Doppler Velocimeters) installed near the soil surface and in different embankment areas, the pore water pressure with probes in different soil layers, the wave height with ultrasound probes and the willow movements with permanently installed cameras while flooding the basin as well as measuring the erosion afterwards. These flooding test series will be conducted two times during the vegetation period. The shear strength of the tree willow rooted soil will be examined in different soil layers with a shear load frame. The results will be compared with the data of shear strength tests of same aged brush mattresses made of shrub willows, which have already been carried out by the Federal Waterways Engineering and Research Institute. The filtering capability of the soil covering branches and the near surface willow roots will be investigated by growing willow brush mattresses in sample boxes. Those can be repeatedly moved up and down into a diving pool while measuring pore water pressure in different soil layers and flow velocity with ADVs.

Water-induced polaron formation at the pentacene surface: Quantum mechanical molecular mechanics simulations

NASA Astrophysics Data System (ADS)

Cramer, Tobias; Steinbrecher, Thomas; Koslowski, Thorsten; Case, David A.; Biscarini, Fabio; Zerbetto, Francesco

2009-04-01

Water is an omnipresent polar impurity that is expected to be the origin of many electric degradation phenomena observed in organic semiconductors. Here, we describe a microscopic model for polaron formation in the outermost layer of a pentacene crystal due to the polarization of a nearby water layer. The efficient coupling of a classical force field that describes the liquid with a tight-binding model that represents the π system of the organic layer permits the calculation of nanosecond length trajectories. The model predicts that the reorientation of water dipoles stabilizes positive charge carriers on average by 0.6 eV and thus leads to a polaron trap state at the liquid interface. Thermal fluctuations of the water molecules provoke two-dimensional diffusive hopping of the charge carrier parallel to the interface with mobilities of up to 0.6cm2s-1V-1 and lead to an amorphous broadening of the valence-band tail. As a consequence, water-filled nanocavities act as trapping sites in pentacene transistors. Instead, a complete wetting of the organic film is expected to result in fast thermally activated hopping transport. Polaron trapping is thus not expected to be a limiting factor for transistor-based sensors that operate under water.

Characteristic of the Nanoparticles Formed on the Carbon Steel Surface Contacting with 3d-Metal Water Salt Solutions in the Open-Air System.

PubMed

Lavrynenko, O M; Pavlenko, O Yu; Shchukin, Yu S

2016-12-01

The contact of a steel electrode with water dispersion medium in an open-air system leads to the development of various polymorphic iron oxides and oxyhydroxides on the steel surface. Whereas the usage of distilled water causes the obtaining of Fe(II)-Fe(III) layered double hydroxides (green rust) as a primary mineral phase, but in the presence of inorganic 3d-metal water salt solutions, mixed layered double hydroxides (LDHs) together with non-stoichiometric spinel ferrite nanoparticles are formed on the steel surface. Mixed LDHs keep stability against further oxidation and complicate the obtaining of spinel ferrite nanoparticles. Thermal treatment of mixed LDHs among other mineral phases formed via the rotation-corrosion dispergation process at certain temperatures permits to obtain homogenous nanoparticles of spinel ferrites as well as maghemite or hematite doped by 3d-metal cations.

Characteristic of the Nanoparticles Formed on the Carbon Steel Surface Contacting with 3d-Metal Water Salt Solutions in the Open-Air System

NASA Astrophysics Data System (ADS)

Lavrynenko, O. M.; Pavlenko, O. Yu; Shchukin, Yu S.

2016-02-01

The contact of a steel electrode with water dispersion medium in an open-air system leads to the development of various polymorphic iron oxides and oxyhydroxides on the steel surface. Whereas the usage of distilled water causes the obtaining of Fe(II)-Fe(III) layered double hydroxides (green rust) as a primary mineral phase, but in the presence of inorganic 3d-metal water salt solutions, mixed layered double hydroxides (LDHs) together with non-stoichiometric spinel ferrite nanoparticles are formed on the steel surface. Mixed LDHs keep stability against further oxidation and complicate the obtaining of spinel ferrite nanoparticles. Thermal treatment of mixed LDHs among other mineral phases formed via the rotation-corrosion dispergation process at certain temperatures permits to obtain homogenous nanoparticles of spinel ferrites as well as maghemite or hematite doped by 3d-metal cations.

Sustained ophthalmic delivery of highly soluble drug using pH-triggered inner layer-embedded contact lens.

PubMed

Zhu, Qiang; Cheng, Hongbo; Huo, Yingnan; Mao, Shirui

2018-06-10

In the present work the feasibility of using inner layer-embedded contact lenses (CLs) to achieve sustained release of highly water soluble drug, betaxolol hydrochloride (BH) on the ocular surface was investigated. Blend film of cellulose acetate and Eudragit S100 was selected as the inner layer, while silicone hydrogel was used as outer layer to construct inner layer-embedded contact lenses. Influence of polymer ratio in the blend film on in vitro drug release behavior in phosphate buffered solution or simulated tear fluid was studied and drug-polymer interaction, erosion and swelling of the blend film were characterized to better understand drug-release mechanism. Storage stability of the inner layer-embedded contact lenses in phosphate buffer solution was also conducted, with ignorable drug loss and negligible change in drug release pattern within 30 days. In vivo pharmacokinetic study in rabbits showed sustained drug release for over 240 h in tear fluid, indicating prolonged drug precorneal residence time. In conclusion, cellulose acetate/Eudragit S100 inner layer-embedded contact lenses are quite promising as controlled-release carrier of highly water soluble drug for ophthalmic delivery. Copyright © 2018 Elsevier B.V. All rights reserved.

Long-ranged electrostatic repulsion and crystallization of emulsion droplets in an ultralow dielectric medium supercritical carbon dioxide.

PubMed

Ryoo, Won; Webber, Stephen E; Bonnecaze, Roger T; Johnston, Keith P

2006-01-31

Electrostatic repulsion stabilizes micrometer-sized water droplets with spacings greater than 10 microm in an ultralow dielectric medium, CO2 (epsilon = 1.5), at elevated pressures. The morphology of the water/CO2 emulsion is characterized by optical microscopy and laser diffraction as a function of height. The counterions, stabilized with a nonionic, highly branched, stubby hydrocarbon surfactant, form an extremely thick double layer with a Debye screening length of 8.9 microm. As a result of the balance between electrostatic repulsion and the downward force due to gravity, the droplets formed a hexagonal crystalline lattice at the bottom of the high-pressure cell with spacings of over 10 microm. The osmotic pressure, calculated by solving the Poisson-Boltzmann equation in the framework of the Wigner-Seitz cell model, is in good agreement with that determined from the sedimentation profile measured by laser diffraction. Thus, the long-ranged stabilization of the emulsion may be attributed to electrostatic stabilization. The ability to form new types of colloids in CO2 with electrostatic stabilization is beneficial because steric stabilization is often unsatisfactory because of poor solvation of the stabilizers.

Accounting for pore water pressure and confined aquifers in assessing the stability of slopes: a Limit Equilibrium analysis carried out through the Minimum Lithostatic Deviation method

NASA Astrophysics Data System (ADS)

Ausilia Paparo, Maria; Tinti, Stefano

2015-04-01

The model we introduce is an implementation of the Minimum Lithostatic Deviation (MLD) method, developed by Tinti and Manucci (Tinti and Manucci 2006; 2008), that makes use of the limit equilibrium (LE) theory to estimate the stability of a slope. The main purpose here is to analyse the role of a confined aquifer on the value of the Safety Factor (F), the parameter that in the LE is used to determine if a slope is stable or unstable. The classical LE methods treat unconfined aquifers by including the water pore pressure in the Mohr-Coulomb failure formula: since the water decreases the friction shear strength, the soil above the sliding surface turns out to be more prone to instability. In case of a confined aquifer, however, due to a presence of impermeable layers, the water is not free to flow into the matrix of the overlying soil. We consider here the assumption of a permeable soil sliding over an impermeable layer, which is an occurrence that is found in several known landslide cases (e.g. Person, 2008; Strout and Tjeltja, 2008; Morgan et al., 2010 for offshore slides; and Palladino and Peck, 1972; Miller and Sias, 1998; Jiao et al. 2005; Paparo et al., 2013 for slopes in proximity of artificial or natural water basins) where clay beds form the potential sliding surface: the water, confined below, pushes along these layers and acts on the sliding body as an external bottom load. We modify the MLD method equations in order to take into account the load due to a confined aquifer and apply the new model to the Vajont case, where many have hypothesised the contribution of a confined aquifer to the failure. Our calculations show that the rain load i) infiltrating directly into the soil body and ii) penetrating into the confined aquifer below the clay layers, in addition with the lowering of the reservoir level, were key factors of destabilization of the Mt Toc flank and caused the disastrous landslide.

Layering of sustained vortices in rotating stratified fluids

NASA Astrophysics Data System (ADS)

Aubert, O.; Le Bars, M.; Le Gal, P.

2013-05-01

The ocean is a natural stratified fluid layer where large structures are influenced by the rotation of the planet through the Coriolis force. In particular, the ocean Meddies are long-lived anticyclonic pancake vortices of Mediterranean origin evolving in the Atlantic Ocean: they have a saltier and warmer core than the sourrounding oceanic water, their diameters go up to 100 km and they can survive for 2 to 3 years in the ocean. Their extensive study using seismic images revealed finestructures surrounding their core (Biescas et al., 2008; Ruddick et al., 2009) corresponding to layers of constant density which thickness is about 40 m and horizontal extent is more than 10 km. These layers can have different origins: salt fingers from a double-diffusive instabilities of salt and heat (Ruddick & Gargett, 2003), viscous overturning motions from a double-diffusive instabilities of salt and momentum (McIntyre, 1970) or global modes of the quasi-geostrophic instability (Nguyen et al., 2011)? As observed by Griffiths & Linden (1981), sustained laboratory anticyclonic vortices created via a continuous injection of isodense fluid in a rotating and linearly stratified layer of salty water are quickly surrounded by layers of constant density. In the continuity of their experiments, we systematically investigated the double-diffusive instability of McIntyre by varying the Coriolis parameter f and the buoyancy frequency N of the background both in experiments and in numerical simulations, and studied the influence of the Schmidt number in numerical simulations. Following McIntyre's approach, typical length and time scales of the instability are well described by a linear stability analysis based on a gaussian model that fits both laboratory and oceanic vortices. The instability appears to be favoured by high Rossby numbers and ratios f/N. We then apply these results to ocean Meddies and conclude about their stability.

Surface and Interface Chemistry for Gate Stacks on Silicon

NASA Astrophysics Data System (ADS)

Frank, M. M.; Chabal, Y. J.

This chapter addresses the fundamental silicon surface science associated with the continued progress of nanoelectronics along the path prescribed by Moore's law. Focus is on hydrogen passivation layers and on ultrathin oxide films encountered during silicon cleaning and gate stack formation in the fabrication of metal-oxide-semiconductor field-effect transistors (MOSFETs). Three main topics are addressed. (i) First, the current practices and understanding of silicon cleaning in aqueous solutions are reviewed, including oxidizing chemistries and cleans leading to a hydrogen passivation layer. The dependence of the final surface termination and morphology/roughness on reactant choice and pH and the influence of impurities such as dissolved oxygen or metal ions are discussed. (ii) Next, the stability of hydrogen-terminated silicon in oxidizing liquid and gas phase environments is considered. In particular, the remarkable stability of hydrogen-terminated silicon surface in pure water vapor is discussed in the context of atomic layer deposition (ALD) of high-permittivity (high-k) gate dielectrics where water is often used as an oxygen precursor. Evidence is also provided for co-operative action between oxygen and water vapor that accelerates surface oxidation in humid air. (iii) Finally, the fabrication of hafnium-, zirconium- and aluminum-based high-k gate stacks is described, focusing on the continued importance of the silicon/silicon oxide interface. This includes a review of silicon surface preparation by wet or gas phase processing and its impact on high-k nucleation during ALD growth, and the consideration of gate stack capacitance and carrier mobility. In conclusion, two issues are highlighted: the impact of oxygen vacancies on the electrical characteristics of high-k MOS devices, and the way alloyed metal ions (such as Al in Hf-based gate stacks) in contact with the interfacial silicon oxide layer can be used to control flatband and threshold voltages.

Revegetation of Acid Rock Drainage (ARD) Producing Slope Surface Using Phosphate Microencapsulation and Artificial Soil

NASA Astrophysics Data System (ADS)

Kim, Jae Gon

2017-04-01

Oxidation of sulfides produces acid rock drainage (ARD) upon their exposure to oxidation environment by construction and mining activities. The ARD causes the acidification and metal contamination of soil, surface water and groundwater, the damage of plant, the deterioration of landscape and the reduction of slope stability. The revegetation of slope surface is one of commonly adopted strategies to reduce erosion and to increase slope stability. However, the revegetation of the ARD producing slope surface is frequently failed due to its high acidity and toxic metal content. We developed a revegetation method consisting of microencapsualtion and artificial soil in the laboratory. The revegetation method was applied on the ARD producing slope on which the revegetation using soil coverage and seeding was failed and monitored the plant growth for one year. The phosphate solution was applied on sulfide containing rock to form stable Fe-phosphate mineral on the surface of sulfide, which worked as a physical barrier to prevent contacting oxidants such as oxygen and Fe3+ ion to the sulfide surface. After the microencapsulation, two artificial soil layers were constructed. The first layer containing organic matter, dolomite powder and soil was constructed at 2 cm thickness to neutralize the rising acidic capillary water from the subsurface and to remove the dissolved oxygen from the percolating rain water. Finally, the second layer containing seeds, organic matter, nutrients and soil was constructed at 3 cm thickness on the top. After application of the method, the pH of the soil below the artificial soil layer increased and the ARD production from the rock fragments reduced. The plant growth showed an ordinary state while the plant died two month after germination for the previous revegetation trial. No soil erosion occurred from the slope during the one year field test.

Impact of sludge layer geometry on the hydraulic performance of a waste stabilization pond.

PubMed

Ouedraogo, Faissal R; Zhang, Jie; Cornejo, Pablo K; Zhang, Qiong; Mihelcic, James R; Tejada-Martinez, Andres E

2016-08-01

Improving the hydraulic performance of waste stabilization ponds (WSPs) is an important management strategy to not only ensure protection of public health and the environment, but also to maximize the potential reuse of valuable resources found in the treated effluent. To reuse effluent from WSPs, a better understanding of the factors that impact the hydraulic performance of the system is needed. One major factor determining the hydraulic performance of a WSP is sludge accumulation, which alters the volume of the pond. In this study, computational fluid dynamics (CFD) analysis was applied to investigate the impact of sludge layer geometry on hydraulic performance of a facultative pond, typically used in many small communities throughout the developing world. Four waste stabilization pond cases with different sludge volumes and distributions were investigated. Results indicate that sludge distribution and volume have a significant impact on wastewater treatment efficiency and capacity. Although treatment capacity is reduced with accumulation of sludge, the latter may induce a baffling effect which causes the flow to behave closer to that of plug flow reactor and thus increase treatment efficiency. In addition to sludge accumulation and distribution, the impact of water surface level is also investigated through two additional cases. Findings show that an increase in water level while keeping a constant flow rate can result in a significant decrease in the hydraulic performance by reducing the sludge baffling effect, suggesting a careful monitoring of sludge accumulation and water surface level in WSP systems. Published by Elsevier Ltd.

Surface-stabilized gold nanocatalysts

DOEpatents

Dai, Sheng [Knoxville, TN; Yan, Wenfu [Oak Ridge, TN

2009-12-08

A surface-stabilized gold nanocatalyst includes a solid support having stabilizing surfaces for supporting gold nanoparticles, and a plurality of gold nanoparticles having an average particle size of less than 8 nm disposed on the stabilizing surfaces. The surface-stabilized gold nanocatalyst provides enhanced stability, such as at high temperature under oxygen containing environments. In one embodiment, the solid support is a multi-layer support comprising at least a first layer having a second layer providing the stabilizing surfaces disposed thereon, the first and second layer being chemically distinct.

Slope instability in complex 3D topography promoted by convergent 3D groundwater flow

NASA Astrophysics Data System (ADS)

Reid, M. E.; Brien, D. L.

2012-12-01

Slope instability in complex topography is generally controlled by the interaction between gravitationally induced stresses, 3D strengths, and 3D pore-fluid pressure fields produced by flowing groundwater. As an example of this complexity, coastal bluffs sculpted by landsliding commonly exhibit a progression of undulating headlands and re-entrants. In this landscape, stresses differ between headlands and re-entrants and 3D groundwater flow varies from vertical rainfall infiltration to lateral groundwater flow on lower permeability layers with subsequent discharge at the curved bluff faces. In plan view, groundwater flow converges in the re-entrant regions. To investigate relative slope instability induced by undulating topography, we couple the USGS 3D limit-equilibrium slope-stability model, SCOOPS, with the USGS 3D groundwater flow model, MODFLOW. By rapidly analyzing the stability of millions of potential failures, the SCOOPS model can determine relative slope stability throughout the 3D domain underlying a digital elevation model (DEM), and it can utilize both fully 3D distributions of pore-water pressure and material strength. The two models are linked by first computing a groundwater-flow field in MODFLOW, and then computing stability in SCOOPS using the pore-pressure field derived from groundwater flow. Using these two models, our analyses of 60m high coastal bluffs in Seattle, Washington showed augmented instability in topographic re-entrants given recharge from a rainy season. Here, increased recharge led to elevated perched water tables with enhanced effects in the re-entrants owing to convergence of groundwater flow. Stability in these areas was reduced about 80% compared to equivalent dry conditions. To further isolate these effects, we examined groundwater flow and stability in hypothetical landscapes composed of uniform and equally spaced, oscillating headlands and re-entrants with differing amplitudes. The landscapes had a constant slope for both headlands and re-entrants to minimize slope effects on stability. Despite these equal slopes, our analyses, given dry conditions, illustrated that the headlands can be 5-7% less stable than the re-entrants, owing to the geometry of the 3D failure mass with the lowest stability. We then simulated groundwater flow in these landscapes; flow was caused by recharge perching on a horizontal low permeability layer with discharge at the bluff faces. By systematically varying recharge, hydraulic conductivity of the material, and conductance at the bluffs, we created different 3D pore-pressure fields. Recharge rates and hydraulic conductivities controlled the height of the water table, whereas bluff conductance influenced the gradient of the water table near the bluff face. Given elevated water tables with steep gradients, bluffs in the re-entrants became unstable where flow converged. Thus, with progressively stronger effects from water flow, overall instability evolved from relatively unstable headlands to more uniform stability to relatively unstable re-entrants. Larger re-entrants led to more 3D flow convergence and greater localized instability. One- or two-dimensional models cannot fully characterize slope instability in complex topography.

Dendrimer ligands-capped CH3NH3PbBr3 perovskite nanocrystals with delayed halide exchange and record stability against both moisture and water.

PubMed

Xu, Yiren; Xu, Shuhong; Shao, Haibao; Jiang, Han; Cui, Yiping; Wang, Chunlei

2018-06-08

CH 3 NH 3 PbBr 3 perovskite nanocrystals (NCs) suffer from poor stability because of their high sensitivity to environmental moisture and water. To solve this problem, previous works mainly focus on embedding perovskite NCs into water-resistant matrix to form large composites (size of microns or larger). As an alternative solution without serious changing of NC size, enhancing the stability of perovskite NCs themselves by ligand engineering is rarely reported. In this work, we used hyperbranched polyamidoamine (PAMAM) dendrimers with two different generations (G0 and G4) to synthesize CH 3 NH 3 PbBr 3 perovskite NCs with high photoluminescence (PL) quantum yields (QY) above 70% and a new record stability. A novel dendrimers generation-dependent stability of perovskite NCs was observed. The water-resistance time is 18 h (27 h) for perovskite NCs capped by G0 (G4) generation of PAMAM, which is 7 times (11 times) longer than that of traditional oleic acid-capped NCs. Similar PAMAM generation-related stability is also observed in moisture-resistance tests. The stability time against moisture is 500 h (800 h) for G0 (G4) generation of PAMAM-capped perovskite NCs, which is a new record stability time against moisture for CH 3 NH 3 PbBr 3 perovskite NCs. In addition, our results also indicate that PAMAM ligands outside perovskite NCs can dramatically slow down the speed of halide exchange. Even for the mixture of perovskite NCs with two different halide composition, the original luminescence properties of PAMAM-capped perovskite NCs can retain after mixing. In view of slow halide exchange speed, excellent water and moisture stability, PAMAM dendrimers-capped perovskite NCs and their mixture are available as color conversion single layer in fabrication of light-emitting diodes (LED).

Dendrimer ligands-capped CH3NH3PbBr3 perovskite nanocrystals with delayed halide exchange and record stability against both moisture and water

NASA Astrophysics Data System (ADS)

Xu, Yiren; Xu, Shuhong; Shao, Haibao; Jiang, Han; Cui, Yiping; Wang, Chunlei

2018-06-01

CH3NH3PbBr3 perovskite nanocrystals (NCs) suffer from poor stability because of their high sensitivity to environmental moisture and water. To solve this problem, previous works mainly focus on embedding perovskite NCs into water-resistant matrix to form large composites (size of microns or larger). As an alternative solution without serious changing of NC size, enhancing the stability of perovskite NCs themselves by ligand engineering is rarely reported. In this work, we used hyperbranched polyamidoamine (PAMAM) dendrimers with two different generations (G0 and G4) to synthesize CH3NH3PbBr3 perovskite NCs with high photoluminescence (PL) quantum yields (QY) above 70% and a new record stability. A novel dendrimers generation-dependent stability of perovskite NCs was observed. The water-resistance time is 18 h (27 h) for perovskite NCs capped by G0 (G4) generation of PAMAM, which is 7 times (11 times) longer than that of traditional oleic acid-capped NCs. Similar PAMAM generation-related stability is also observed in moisture-resistance tests. The stability time against moisture is 500 h (800 h) for G0 (G4) generation of PAMAM-capped perovskite NCs, which is a new record stability time against moisture for CH3NH3PbBr3 perovskite NCs. In addition, our results also indicate that PAMAM ligands outside perovskite NCs can dramatically slow down the speed of halide exchange. Even for the mixture of perovskite NCs with two different halide composition, the original luminescence properties of PAMAM-capped perovskite NCs can retain after mixing. In view of slow halide exchange speed, excellent water and moisture stability, PAMAM dendrimers-capped perovskite NCs and their mixture are available as color conversion single layer in fabrication of light-emitting diodes (LED).

Fluorescence-tagged amphiphilic brush copolymer encapsulated Gd2O3 core-shell nanostructures for enhanced T 1 contrast effect and fluorescent imaging

NASA Astrophysics Data System (ADS)

Wang, Fenghe; Peng, Erwin; Liu, Feng; Li, Pingjing; Fong Yau Li, Sam; Xue, Jun Min

2016-10-01

To obtain suitable T 1 contrast agents for magnetic resonance imaging (MRI) application, aqueous Gd2O3 nanoparticles (NPs) with high longitudinal relativity (r 1) are demanded. High quality Gd2O3 NPs are usually synthesized through a non-hydrolytic route which requires post-synthetic modification to render the NPs water soluble. The current challenge is to obtain aqueous Gd2O3 NPs with high colloidal stability and enhanced r 1 relaxivity. To overcome this challenge, fluorescence-tagged amphiphilic brush copolymer (AFCP) encapsulated Gd2O3 NPs were proposed as suitable T 1 contrast agents. Such a coating layer provided (i) superior aqueous stability, (ii) biocompatibility, as well as (iii) multi-modality (conjugation with fluorescence dye). The polymeric coating layer thickness was simply adjusted by varying the phase-transfer parameters. By reducing the coating thickness, i.e. the distance between the paramagnetic centre and surrounding water protons, the r 1 relaxivity could be enhanced. In contrast, a thicker polymeric layer coating prevents Gd3+ ions leakage, thus improving its biocompatibility. Therefore, it is important to strike a balance between the biocompatibility and the r 1 relaxivity behaviour. Lastly, by conjugating fluorescence moiety, an additional imaging modality was enabled, as demonstrated from the cell-labelling experiment.

Molecular layer deposition of APTES on silicon nanowire biosensors: Surface characterization, stability and pH response

NASA Astrophysics Data System (ADS)

Liang, Yuchen; Huang, Jie; Zang, Pengyuan; Kim, Jiyoung; Hu, Walter

2014-12-01

We report the use of molecular layer deposition (MLD) for depositing 3-aminopropyltriethoxysilane (APTES) on a silicon dioxide surface. The APTES monolayer was characterized using spectroscopic ellipsometry, contact angle goniometry, and atomic force microscopy. Effects of reaction time of repeating pulses and simultaneous feeding of water vapor with APTES were tested. The results indicate that the synergistic effects of water vapor and reaction time are significant for the formation of a stable monolayer. Additionally, increasing the number of repeating pulses improved the APTES surface coverage but led to saturation after 10 pulses. In comparing MLD with solution-phase deposition, the APTES surface coverage and the surface quality were nearly equivalent. The hydrolytic stability of the resulting films was also studied. The results confirmed that the hydrolysis process was necessary for MLD to obtain stable surface chemistry. Furthermore, we compared the pH sensing results of Si nanowire field effect transistors (Si NWFETs) modified by both the MLD and solution methods. The highly repeatable pH sensing results reflected the stability of APTES monolayers. The results also showed an improved pH response of the sensor prepared by MLD compared to the one prepared by the solution treatment, which indicated higher surface coverage of APTES.

Organic carbon, water repellency and soil stability to slaking at aggregate and intra-aggregate scales

NASA Astrophysics Data System (ADS)

Jordán López, Antonio; García-Moreno, Jorge; Gordillo-Rivero, Ángel J.; Zavala, Lorena M.; Cerdà, Artemi; Alanís, Nancy; Jiménez-Compán, Elizabeth

2015-04-01

Water repellency (WR) is a property of some soils that inhibits or delays water infiltration between a few seconds and days or weeks. Inhibited or delayed infiltration contributes to ponding and increases runoff flow generation, often increasing soil erosion risk. In water-repellent soils, water infiltrates preferentially through cracks or macropores, causing irregular soil wetting patterns, the development of preferential flow paths and accelerated leaching of nutrients. Although low inputs of hydrophobic organic substances and high mineralization rates lead to low degrees of WR in cropped soils, it has been reported that conservative agricultural practices may induce soil WR. Although there are many studies at catchment, slope or plot scales very few studies have been carried out at particle or aggregate scale. Intra-aggregate heterogeneity of physical, biological and chemical properties conditions the transport of substances, microbial activity and biochemical processes, including changes in the amount, distribution and chemical properties of organic matter. Some authors have reported positive relationships between soil WR and aggregate stability, since it may delay the entry of water into aggregates, increase structural stability and contribute to reduce soil erosion risk. Organic C (OC) content, aggregate stability and WR are therefore strongly related parameters. In the case of agricultural soils, where both the type of management as crops can influence all these parameters, it is important to evaluate the interactions among them and their consequences. Studies focused on the intra-aggregate distribution of OC and WR are necessary to shed light on the soil processes at a detailed scale. It is extremely important to understand how the spatial distribution of OC in soil aggregates can protect against rapid water entry and help stabilize larger structural units or lead to preferential flow. The objectives of this research are to study [i] the OC content and the intensity of WR in aggregates of different sizes. [ii] the intra-aggregate distribution of OC and the intensity of WR and [iii] the structural stability of soil aggregates relative to the OC content and the intensity of WR in soils under different crops (apricot, citrus and wheat) and different treatments (conventional tilling and mulching). Soil samples were collected from an experimental area (Luvic Calcisols and Calcic Luvisols) in the province of Sevilla (Southern Spain) under different crops (apricot, citrus and wheat) and different management types (conventional tillage with moldboard plow) and mulching (no-tilling and addition of wheat residues at rates varying between 5 and 8 Mg/ha/year). At each sampling site, soil blocks (50 cm long × 50 cm wide × 10 cm deep) were carefully collected to avoid disturbance of aggregates as much as possible and transported to the laboratory. At field moist condition, undisturbed soil aggregates were separated by hand. In order to avoid possible interferences due to disturbance by handling, aggregates broken during this process were discarded. Individual aggregates were arranged in paper trays and air-dried during 7 days under laboratory standard conditions. After air-drying, part of each sample was carefully divided for different analyses: [i] part of the original samples was sieved (2 mm) to eliminate coarse soil particles and homogenized for characterization of OC and N contents, C/N ratio and texture; [ii] part of the aggregates were dry-sieved (0.25-0.5, 0.5-1 and 1-2 mm) or measured with a caliper (2-5, 5-10 and 10-15 mm) and separated in different sieve-size classes for determination of WR and OC content; [iii] aggregates 10-15 mm in size were selected for obtaining aggregate layers using a soil aggregate erosion (SAE) apparatus and WR and OC content were determined at each layer; finally, [iv] in order to study the relation between stability to slaking, WR and OC, these properties were determined in 90 air-dried aggregates (about 10 mm in size) selected per treatment (mulched or conventional tillage) and crop (apricot, citrus and wheat). In this case, every set of aggregates was randomly divided in three groups (n = 30) for assessing stability to slaking, WR and OC, respectively. OC content in the fine earth fraction of soils under different crops did not show important variations, although it increased significantly from conventionally tilled to mulched soils. The distribution of OC content in aggregates with different size varied among soils under different crops, generally increasing with decreasing size. At the intra-aggregate level, OC concentrated preferably in the exterior layer of differently sized aggregates and of aggregate coatings and interior from conventionally tilled soils, probably because of recent organic inputs or leachates. In the case of mulched soils, higher concentrations were observed, but no significant differences among aggregate regions were found. The intensity of water repellency, determined by the ethanol method, did not show great variations among differently sized aggregates under different crops in the 0-10 cm layer, but increased significantly from conventionally tilled to mulched soils. Coarser aggregates were generally wettable, while finer aggregates showed slight water repellency. Regardless of variations in the distribution of OC in different layers of aggregate from conventionally tilled soils, great or significant differences in the distribution of water repellency at the intra-aggregate level were not found. In case of mulched soils such differences were not significant. Finally, the intensity of water repellency was much more important than the concentration of OC in the stability to slaking of aggregates.

Microcalorimetric study of thermal unfolding of lysozyme in water/glycerol mixtures: An analysis by solvent exchange model

NASA Astrophysics Data System (ADS)

Spinozzi, Francesco; Ortore, Maria Grazia; Sinibaldi, Raffaele; Mariani, Paolo; Esposito, Alessandro; Cinelli, Stefania; Onori, Giuseppe

2008-07-01

Folded protein stabilization or destabilization induced by cosolvent in mixed aqueous solutions has been studied by differential scanning microcalorimetry and related to difference in preferential solvation of native and denatured states. In particular, the thermal denaturation of a model system formed by lysozyme dissolved in water in the presence of the stabilizing cosolvent glycerol has been considered. Transition temperatures and enthalpies, heat capacity, and standard free energy changes have been determined when applying a two-state denaturation model to microcalorimetric data. Thermodynamic parameters show an unexpected, not linear, trend as a function of solvent composition; in particular, the lysozyme thermodynamic stability shows a maximum centered at water molar fraction of about 0.6. Using a thermodynamic hydration model based on the exchange equilibrium between glycerol and water molecules from the protein solvation layer to the bulk, the contribution of protein-solvent interactions to the unfolding free energy and the changes of this contribution with solvent composition have been derived. The preferential solvation data indicate that lysozyme unfolding involves an increase in the solvation surface, with a small reduction of the protein-preferential hydration. Moreover, the derived changes in the excess solvation numbers at denaturation show that only few solvent molecules are responsible for the variation of lysozyme stability in relation to the solvent composition.

Covalent layer-by-layer grafting (LBLG) functionalized superhydrophobic stainless steel mesh for oil/water separation

NASA Astrophysics Data System (ADS)

Jiang, Bin; Zhang, Hongjie; Sun, Yongli; Zhang, Luhong; Xu, Lidong; Hao, Li; Yang, Huawei

2017-06-01

A superhydrophobic and superoleophilic stainless steel (SS) mesh for oil/water separation has been developed by using a novel, facile and inexpensive covalent layer-by-layer grafting (LBLG) method. Hierarchical micro/nanostructure surface was formed through grafting the (3-aminopropyl) triethoxysilane (SCA), polyethylenimine (PEI) and trimesoyl chloride (TMC) onto the mesh in sequence, accompanied with SiO2 nanoparticles subtly and firmly anchored in multilayers. Superhydrophobic characteristic was realized by self-assembly grafting of hydrophobic groups onto the surface. The as-prepared mesh exhibits excellent superhydrophobicity with a water contact angle of 159°. Moreover, with a low sliding angle of 4°, it shows the "lotus effect" for self-cleaning. As for application evaluation, the as-prepared mesh can be used for large-scale separation of oil/water mixtures with a relatively high separation efficiency after 30 times reuse (99.88% for n-octane/water mixture) and a high intrusion pressure (3.58 kPa). More importantly, the mesh exhibited excellent stability in the case of vibration situation, long-term storage as well as saline corrosion conditions, and the compatible pH range was determined to be 1-13. In summary, this work provides a brand new method of modifying SS mesh in a covalent LBLG way, and makes it possible to introduce various functionalized groups onto the surface.

Structural rearrangement of β-lactoglobulin at different oil-water interfaces and its effect on emulsion stability.

PubMed

Zhai, Jiali; Wooster, Tim J; Hoffmann, Søren V; Lee, Tzong-Hsien; Augustin, Mary Ann; Aguilar, Marie-Isabel

2011-08-02

Understanding the factors that control protein structure and stability at the oil-water interface continues to be a major focus to optimize the formulation of protein-stabilized emulsions. In this study, a combination of synchrotron radiation circular dichroism spectroscopy, front-face fluorescence spectroscopy, and dual polarization interferometry (DPI) was used to characterize the conformation and geometric structure of β-lactoglobulin (β-Lg) upon adsorption to two oil-water interfaces: a hexadecane-water interface and a tricaprylin-water interface. The results show that, upon adsorption to both oil-water interfaces, β-Lg went through a β-sheet to α-helix transition with a corresponding loss of its globular tertiary structure. The degree of conformational change was also a function of the oil phase polarity. The hexadecane oil induced a much higher degree of non-native α-helix compared to the tricaprylin oil. In contrast to the β-Lg conformation in solution, the non-native α-helical-rich conformation of β-Lg at the interface was resistant to further conformational change upon heating. DPI measurements suggest that β-Lg formed a thin dense layer at emulsion droplet surfaces. The effects of high temperature and the presence of salt on these β-Lg emulsions were then investigated by monitoring changes in the ζ-potential and particle size. In the absence of salt, high electrostatic repulsion meant β-Lg-stabilized emulsions were resistant to heating to 90 °C. Adding salt (120 mM NaCl) before or after heating led to emulsion flocculation due to the screening of the electrostatic repulsion between colloidal particles. This study has provided insight into the structural properties of proteins adsorbed at the oil-water interface and has implications in the formulation and production of emulsions stabilized by globular proteins.

Potentiometric sensors with carbon black supporting platinum nanoparticles.

PubMed

Paczosa-Bator, Beata; Cabaj, Leszek; Piech, Robert; Skupień, Krzysztof

2013-11-05

For the first time, a single-piece, all-solid-state ion-selective electrode was fabricated with carbon black supporting platinum nanoparticles (PtNPs-CB) and a polymeric membrane. The PtNPs-CB, as an intermediate layer, was drop-casted directly on the solid substrate, and then an ionophore-doped solvent polymeric membrane was added in order to form a sensor. The performance of the newly developed electrodes was evaluated on the basis of potassium and nitrate ions. The stability of the electrical potential for the electrodes was examined by performing current-reversal chronopotentiometry, and the influence of the interfacial water film was assessed by the potentiometric aqueous-layer test. Fabricated potassium- and nitrate-selective electrodes displayed a Nernstian slope and several outstanding properties such as high long-term potential stability, potential repeatability, and reproducibility.

Stability of Ruddlesden–Popper-structured oxides in humid conditions

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

Lehtimäki, M.; Yamauchi, H.; Karppinen, M., E-mail: maarit.karppinen@aalto.fi

2013-08-15

Some of layered transition-metal oxides are known to react with atmospheric humidity to form through topotactic intercalation reactions new water-containing layered structures. Here we investigate the influence of oxygen content (7−δ) of the Ruddlesden–Popper-structured Sr{sub 3}FeMO{sub 7−δ} (M=Ni, Mn, Ti) oxides on the water-intercalation reaction. It is found that their oxygen contents influence greatly the reactivity of the phases with water. Other factors possibly affecting the reactivity are discussed on the basis of the present data in combination with a comprehensive review of previous works on Ruddlesden–Popper and related layered oxide phases. - Graphical abstract: Many of the Ruddlesden–Popper-structured A{submore » 3}B{sub 2}O{sub 7−δ} oxides readily react with water via intercalation reactions. Three possible factors affecting the water intercalation are identified: oxygen content of the phase, ionic radius of cation A and valence state of cation B. The resultant layered water-derivative phases can be categorised into two groups, depending on the crystal symmetry of the phase. Highlights: • Ruddlesden–Popper oxides A{sub 3}B{sub 2}O{sub 7−δ} often accommodate water via intercalation reaction. • The lower the oxygen content 7−δ is the more readily the intercalation reaction occurs. • The second factor promoting the reaction is the large size of cation A. • The third possible factor is the high valence state of cation B. • Resultant water-derivatives can be categorised into two groups depending on symmetry.« less

Long-Term Stability of Residual Stress Improvement by Water Jet Peening Considering Working Processes.

PubMed

Hashimoto, Tadafumi; Osawa, Yusuke; Itoh, Shinsuke; Mochizuki, Masahito; Nishimoto, Kazutoshi

2013-06-01

To prevent primary water stress corrosion cracking (PWSCC), water jet peening (WJP) has been used on the welds of Ni-based alloys in pressurized water reactors (PWRs). Before WJP, the welds are machined and buffed in order to conduct a penetrant test (PT) to verify the weld qualities to access, and microstructure evolution takes place in the target area due to the severe plastic deformation. The compressive residual stresses induced by WJP might be unstable under elevated temperatures because of the high dislocation density in the compressive stress layer. Therefore, the stability of the compressive residual stresses caused by WJP was investigated during long-term operation by considering the microstructure evolution due to the working processes. The following conclusions were made: The compressive residual stresses were slightly relaxed in the surface layers of the thermally aged specimens. There were no differences in the magnitude of the relaxation based on temperature or time. The compressive residual stresses induced by WJP were confirmed to remain stable under elevated temperatures. The stress relaxation at the surface followed the Johnson-Mehl equation, which states that stress relaxation can occur due to the recovery of severe plastic strain, since the estimated activation energy agrees very well with the self-diffusion energy for Ni. By utilizing the additivity rule, it was indicated that stress relaxation due to recovery is completed during the startup process. It was proposed that the long-term stability of WJP under elevated temperatures must be assessed based on compressive stresses with respect to the yield stress. Thermal elastic-plastic creep analysis was performed to predict the effect of creep strain. After 100 yr of simulated continuous operation at 80% capacity, there was little change in the WJP compressive stresses under an actual operating temperature of 623 K. Therefore, the long-term stability of WJP during actual operation was analytically predicted.

Stability of perovskite solar cells on flexible substrates

NASA Astrophysics Data System (ADS)

Tam, Ho Won; Chen, Wei; Liu, Fangzhou; He, Yanling; Leung, Tik Lun; Wang, Yushu; Wong, Man Kwong; Djurišić, Aleksandra B.; Ng, Alan Man Ching; He, Zhubing; Chan, Wai Kin; Tang, Jinyao

2018-02-01

Perovskite solar cells are emerging photovoltaic technology with potential for low cost, high efficiency devices. Currently, flexible devices efficiencies over 15% have been achieved. Flexible devices are of significant interest for achieving very low production cost via roll-to-roll processing. However, the stability of perovskite devices remains a significant challenge. Unlike glass substrate which has negligible water vapor transmission rate (WVTR), polymeric flexible film substrates suffer from high moisture permeability. As PET and PEN flexible substrates exhibit higher water permeability then glass, transparent flexible backside encapsulation should be used to maximize light harvesting in perovskite layer while WVTR should be low enough. Wide band gap materials are transparent in the visible spectral range low temperature processable and can be a moisture barrier. For flexible substrates, approaches like atomic layer deposition (ALD) and low temperature solution processing could be used for metal oxide deposition. In this work, ALD SnO2, TiO2, Al2O3 and solution processed spin-on-glass was used as the barrier layer on the polymeric side of indium tin oxide (ITO) coated PEN substrates. The UV-Vis transmission spectra of the prepared substrates were investigated. Perovskite solar cells will be fabricated and stability of the devices were encapsulated with copolymer films on the top side and tested under standard ISOS-L-1 protocol and then compared to the commercial unmodified ITO/PET or ITO/PEN substrates. In addition, devices with copolymer films laminated on both sides successfully surviving more than 300 hours upon continuous AM1.5G illumination were demonstrated.

Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation

PubMed Central

Birkner, Nancy; Nayeri, Sara; Pashaei, Babak; Najafpour, Mohammad Mahdi; Casey, William H.; Navrotsky, Alexandra

2013-01-01

Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn3+/Mn4+ ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states. PMID:23667149

Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation.

PubMed

Birkner, Nancy; Nayeri, Sara; Pashaei, Babak; Najafpour, Mohammad Mahdi; Casey, William H; Navrotsky, Alexandra

2013-05-28

Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn(3+)/Mn(4+) ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states.

Single-layer group IV-V and group V-IV-III-VI semiconductors: Structural stability, electronic structures, optical properties, and photocatalysis

NASA Astrophysics Data System (ADS)

Lin, Jia-He; Zhang, Hong; Cheng, Xin-Lu; Miyamoto, Yoshiyuki

2017-07-01

Recently, single-layer group III monochalcogenides have attracted both theoretical and experimental interest at their potential applications in photonic devices, electronic devices, and solar energy conversion. Excited by this, we theoretically design two kinds of highly stable single-layer group IV-V (IV =Si ,Ge , and Sn; V =N and P) and group V-IV-III-VI (IV =Si ,Ge , and Sn; V =N and P; III =Al ,Ga , and In; VI =O and S) compounds with the same structures with single-layer group III monochalcogenides via first-principles simulations. By using accurate hybrid functional and quasiparticle methods, we show the single-layer group IV-V and group V-IV-III-VI are indirect bandgap semiconductors with their bandgaps and band edge positions conforming to the criteria of photocatalysts for water splitting. By applying a biaxial strain on single-layer group IV-V, single-layer group IV nitrides show a potential on mechanical sensors due to their bandgaps showing an almost linear response for strain. Furthermore, our calculations show that both single-layer group IV-V and group V-IV-III-VI have absorption from the visible light region to far-ultraviolet region, especially for single-layer SiN-AlO and SnN-InO, which have strong absorption in the visible light region, resulting in excellent potential for solar energy conversion and visible light photocatalytic water splitting. Our research provides valuable insight for finding more potential functional two-dimensional semiconductors applied in optoelectronics, solar energy conversion, and photocatalytic water splitting.

Silicon nitride protective coatings for silvered glass mirrors

DOEpatents

Tracy, C. Edwin; Benson, David K.

1988-01-01

A protective diffusion barrier for metalized mirror structures is provided by a layer or coating of silicon nitride which is a very dense, transparent, dielectric material that is impervious to water, alkali, and other impurities and corrosive substances that typically attack the metal layers of mirrors and cause degradation of the mirrors' reflectivity. The silicon nitride layer can be deposited on the substrate before metal deposition to stabilize the metal/substrate interface, and it can be deposited over the metal to encapsulate it and protect the metal from corrosion or other degradation. Mirrors coated with silicon nitride according to this invention can also be used as front surface mirrors.

Silicon nitride protective coatings for silvered glass mirrors

DOEpatents

Tracy, C.E.; Benson, D.K.

1984-07-20

A protective diffusion barrier for metalized mirror structures is provided by a layer or coating of silicon nitride which is a very dense, transparent, dielectric material that is impervious to water, alkali, and other impurities and corrosive substances that typically attack the metal layers of mirrors and cause degradation of the mirrors' reflectivity. The silicon nitride layer can be deposited on the substrate prior to metal deposition thereon to stabilize the metal/substrate interface, and it can be deposited over the metal to encapsulate it and protect the metal from corrosion or other degradation. Mirrors coated with silicon nitride according to this invention can also be used as front surface mirrors.

MoRu/Be multilayers for extreme ultraviolet applications

DOEpatents

Bajt, Sasa C.; Wall, Mark A.

2001-01-01

High reflectance, low intrinsic roughness and low stress multilayer systems for extreme ultraviolet (EUV) lithography comprise amorphous layers MoRu and crystalline Be layers. Reflectance greater than 70% has been demonstrated for MoRu/Be multilayers with 50 bilayer pairs. Optical throughput of MoRu/Be multilayers can be 30-40% higher than that of Mo/Be multilayer coatings. The throughput can be improved using a diffusion barrier to make sharper interfaces. A capping layer on the top surface of the multilayer improves the long-term reflectance and EUV radiation stability of the multilayer by forming a very thin native oxide that is water resistant.

Origin of the outer layer of martian low-aspect ratio layered ejecta craters

NASA Astrophysics Data System (ADS)

Boyce, Joseph M.; Wilson, Lionel; Barlow, Nadine G.

2015-01-01

Low-aspect ratio layered ejecta (LARLE) craters are one of the most enigmatic types of martian layered ejecta craters. We propose that the extensive outer layer of these craters is produced through the same base surge mechanism as that which produced the base surge deposits generated by near-surface, buried nuclear and high-explosive detonations. However, the LARLE layers have higher aspect ratios compared with base surge deposits from explosion craters, a result of differences in thicknesses of these layers. This characteristics is probably caused by the addition of large amounts of small particles of dust and ice derived from climate-related mantles of snow, ice and dust in the areas where LARLE craters form. These deposits are likely to be quickly stabilized (order of a few days to a few years) from eolian erosion by formation of duricrust produced by diffusion of water vapor out of the deposits.

Rheological and Magnetorheological Behaviour of Some Magnetic Fluids on Polar and Nonpolar Carrier Liquids

NASA Astrophysics Data System (ADS)

Bălău, Oana; Bica, Doina; Koneracka, Martina; Kopčansky, Peter; Susan-Resiga, Daniela; Vékás, Ladislau

Rheological and magnetorheological behaviour of monolayer and double layer sterically stabilized magnetic fluids, with transformer oil (UTR), diloctilsebacate (DOS), heptanol (Hept), pentanol (Pent) and water (W) as carrier liquids, were investigated. The data for volumic concentration dependence of dynamic viscosity of high colloidal stability UTR, DOS, Hept and Pent samples are particularly well fitted by the formulas given by Vand (1948) and Chow (1994). The Chow type dependence proved its universal character as the viscosity data for dilution series of various magnetic fluids are well fitted by the same curve, regardless the nonpolar or polar charcater of the sample. The magnetorheological effect measured for low and medium concentration water based magnetic fluids is much higher, due to agglomerate formation process, than the corresponding values obtained for the well stabilized UTR, DOS, Hept and Pent samples, even at very high volumic fraction of magnetic nanoparticles.

Quantitative Collection and Enzymatic Activity of Glucose Oxidase Nanotubes Fabricated by Templated Layer-by-Layer Assembly.

PubMed

Zhang, Shouwei; Demoustier-Champagne, Sophie; Jonas, Alain M

2015-08-10

We report on the fabrication of enzyme nanotubes in nanoporous polycarbonate membranes via the layer-by-layer (LbL) alternate assembly of polyethylenimine (PEI) and glucose oxidase (GOX), followed by dissolution of the sacrificial template in CH2Cl2, collection, and final dispersion in water. An adjuvant-assisted filtration methodology is exploited to extract quantitatively the nanotubes without loss of activity and morphology. Different water-soluble CH2Cl2-insoluble adjuvants are tested for maximal enzyme activity and nanotube stability; whereas NaCl disrupts the tubes by screening electrostatic interactions, the high osmotic pressure created by fructose also contributes to loosening the nanotubular structures. These issues are solved when using neutral, high molar mass dextran. The enzymatic activity of intact free nanotubes in water is then quantitatively compared to membrane-embedded nanotubes, showing that the liberated nanotubes have a higher catalytic activity in proportion to their larger exposed surface. Our study thus discloses a robust and general methodology for the fabrication and quantitative collection of enzymatic nanotubes and shows that LbL assembly provides access to efficient enzyme carriers for use as catalytic swarming agents.

Stabilization of model beverage cloud emulsions using protein-polysaccharide electrostatic complexes formed at the oil-water interface.

PubMed

Harnsilawat, Thepkunya; Pongsawatmanit, Rungnaphar; McClements, David J

2006-07-26

The potential of utilizing interfacial complexes, formed through the electrostatic interactions of proteins and polysaccharides at oil-water interfaces, to stabilize model beverage cloud emulsions has been examined. These interfacial complexes were formed by mixing charged polysaccharides with oil-in-water emulsions containing oppositely charged protein-coated oil droplets. Model beverage emulsions were prepared that consisted of 0.1 wt % corn oil droplets coated by beta-lactoglobulin (beta-Lg), beta-Lg/alginate, beta-Lg/iota-carrageenan, or beta-Lg/gum arabic interfacial layers (pH 3 or 4). Stable emulsions were formed when the polysaccharide concentration was sufficient to saturate the protein-coated droplets. The emulsions were subjected to variations in pH (from 3 to 7), ionic strength (from 0 to 250 mM NaCl), and thermal processing (from 30 or 90 degrees C), and the influence on their stability was determined. The emulsions containing alginate and carrageenan had the best stability to ionic strength and thermal processing. This study shows that the controlled formation of protein-polysaccharide complexes at droplet surfaces may be used to produce stable beverage emulsions, which may have important implications for industrial applications.

Influence of Inner Transducer Properties on EMF Response and Stability of Solid-Contact Anion Selective Membrane Electrodes Based on Metalloporphyrin Ionophores

PubMed Central

Górski, Łukasz; Matusevich, Alexey; Pietrzak, Mariusz; Wang, Lin; Meyerhoff, Mark E.; Malinowska, Elżbieta

2010-01-01

The performance of solid-contact/coated wire type electrodes with plasticized PVC membranes containing metalloporphyrins as anion selective ionophores is reported. The membranes are deposited on transducers based on graphite pastes and graphite rods. The hydrophobicity of the underlying conductive transducer surface is found to be a key factor that influences the formation of an aqueous layer beneath the polymer film. Elimination of this ill-defined water layer greatly improves the electrochemical properties of the ion-sensors, such as EMF stability and life-time. Only highly lipophilic electrode substrates, namely graphite paste with mineral oil, were shown to prevent the formation of aqueous layer underneath the ion-sensing membrane. The possibility of employing Co(III)-tetraphenylporphyrin both as NO2− selective ionophore and as electron/ion conducting species to ensure ion-to-electron translation was also discussed based on the results of preliminary experiments. PMID:20357903

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

Gu, Jing; Aguiar, Jeffery A.; Ferrere, Suzanne

Achieving solar-to-hydrogen efficiencies above 15% is key for the commercial success of photoelectrochemical water splitting devices. While tandem cells can reach those efficiencies, increasing the catalytic activity and long-term stability remains a significant challenge. We show that annealing a bilayer of amorphous titanium dioxide (TiO x) and molybdenum sulfide (MoS x) deposited onto GaInP 2 results in a photocathode with high catalytic activity (current density of 11 mA/cm -2 at 0 V vs. the reversible hydrogen electrode under 1 sun illumination) and stability (retention of 80% of initial photocurrent density over a 20 h durability test) for the hydrogen evolutionmore » reaction. Microscopy and spectroscopy reveal that annealing results in a graded MoS x/MoO x/TiO 2 layer that retains much of the high catalytic activity of amorphous MoS x but with stability similar to crystalline MoS 2. These findings demonstrate the potential of utilizing a hybridized, heterogeneous surface layer as a cost-effective catalytic and protective interface for solar hydrogen production.« less

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

Kim, Eun-Kyeong; Yeong Kim, Ji; Sub Kim, Sang, E-mail: sangsub@inha.ac.kr

We describe the preparation of superhydrophobic SiO{sub 2} layers through a combination of surface roughness and fluorination. Electrospraying SiO{sub 2} precursor solutions that were prepared by a sol-gel route and included trichloro(1H,1H,2H,2H-perfluorooctyl)silane as a fluorination source produced highly rough, fluorinated SiO{sub 2} layers. In sharp contrast to the fluorinated flat SiO{sub 2} layer, the fluorinated rough SiO{sub 2} layer showed much enhanced repellency toward liquid droplets of different surface tensions. The surface fraction and the work of adhesion of the superhydrophobic SiO{sub 2} layers were determined, respectively, based on Cassie-Baxter and Young-Dupre equations. The satisfactory long-term stability for 30 days,more » the ultraviolet resistance and the thermal stability up to 400 {sup o}C of the superhydrophobic SiO{sub 2} layers prepared in this work confirm a promising practical application. - Graphical abstract: A schematic illustration of the electrospray deposition used for preparing SiO{sub 2} layers. Shapes of liquid droplets of water, glycerol, coffee, juice and milk created on the fluorinated rough SiO{sub 2} layer deposited on a silicon wafer. Highlights: Black-Right-Pointing-Pointer Superhydrophobic SiO{sub 2} layers are realized by a combination of surface roughness and fluorination. Black-Right-Pointing-Pointer The fluorinated rough SiO{sub 2} layer shows enhanced repellency toward various liquid droplets. Black-Right-Pointing-Pointer The wetting behavior is explained based on Cassie-Baxter and Young-Dupre equations. Black-Right-Pointing-Pointer The superhydrophobic SiO{sub 2} layers confirm a promising practical application.« less

Use of CdS quantum dot-functionalized cellulose nanocrystal films for anti-counterfeiting applications

NASA Astrophysics Data System (ADS)

Chen, L.; Lai, C.; Marchewka, R.; Berry, R. M.; Tam, K. C.

2016-07-01

Structural colors and photoluminescence have been widely used for anti-counterfeiting and security applications. We report for the first time the use of CdS quantum dot (QD)-functionalized cellulose nanocrystals (CNCs) as building blocks to fabricate nanothin films via layer-by-layer (LBL) self-assembly for anti-counterfeiting applications. Both negatively- and positively-charged CNC/QD nanohybrids with a high colloidal stability and a narrow particle size distribution were prepared. The controllable LBL coating process was characterized by scanning electron microscopy and ellipsometry. The rigid structure of CNCs leads to nanoporous structured films on poly(ethylene terephthalate) (PET) substrates with high transmittance (above 70%) over the entire range of visible light and also resulted in increased hydrophilicity (contact angles of ~40 degrees). Nanothin films on PET substrates showed good flexibility and enhanced stability in both water and ethanol. The modified PET films with structural colors from thin-film interference and photoluminescence from QDs can be used in anti-counterfeiting applications.Structural colors and photoluminescence have been widely used for anti-counterfeiting and security applications. We report for the first time the use of CdS quantum dot (QD)-functionalized cellulose nanocrystals (CNCs) as building blocks to fabricate nanothin films via layer-by-layer (LBL) self-assembly for anti-counterfeiting applications. Both negatively- and positively-charged CNC/QD nanohybrids with a high colloidal stability and a narrow particle size distribution were prepared. The controllable LBL coating process was characterized by scanning electron microscopy and ellipsometry. The rigid structure of CNCs leads to nanoporous structured films on poly(ethylene terephthalate) (PET) substrates with high transmittance (above 70%) over the entire range of visible light and also resulted in increased hydrophilicity (contact angles of ~40 degrees). Nanothin films on PET substrates showed good flexibility and enhanced stability in both water and ethanol. The modified PET films with structural colors from thin-film interference and photoluminescence from QDs can be used in anti-counterfeiting applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr03039d

Layers of air in the water beneath the floating fern Salvinia are exposed to fluctuations in pressure.

PubMed

Mayser, Matthias J; Barthlott, Wilhelm

2014-12-01

Superhydrophobic, hierarchically structured, technical surfaces (Lotus-effect) are of high scientific and economic interest because of their remarkable properties. Recently, the immense potential of air-retaining superhydrophobic surfaces, for example, for low-friction transport of fluids and drag-reducing coatings of ships has begun to be explored. A major problem of superhydrophobic surfaces mimicking the Lotus-effect is the limited persistence of the air retained, especially under rough conditions of flow. However, there are a variety of floating or diving plant and animal species that possess air-retaining surfaces optimized for durable water-repellency (Salvinia-effect). Especially floating ferns of the genus Salvinia have evolved superhydrophobic surfaces capable of maintaining layers of air for months. Apart from maintaining stability under water, the layer of air has to withstand the stresses of water pressure (up to 2.5 bars). Both of these aspects have an application to create permanent air layers on ships' hulls. We investigated the effect of pressure on air layers in a pressure cell and exposed the air layer to pressures of up to 6 bars. We investigated the suppression of the air layer at increasing pressures as well as its restoration during decreases in pressure. Three of the four examined Salvinia species are capable of maintaining air layers at pressures relevant to the conditions applying to ships' hulls. High volumes of air per surface area are advantageous for retaining at least a partial Cassie-Baxter-state under pressure, which also helps in restoring the air layer after depressurization. Closed-loop structures such as the baskets at the top of the "egg-beater hairs" (see main text) also help return the air layer to its original level at the tip of the hairs by trapping air bubbles. © The Author 2014. Published by Oxford University Press on behalf of the Society for Integrative and Comparative Biology. All rights reserved. For permissions please email: journals.permissions@oup.com.

Diverse and tunable electronic structures of single-layer metal phosphorus trichalcogenides for photocatalytic water splitting

NASA Astrophysics Data System (ADS)

Liu, Jian; Li, Xi-Bo; Wang, Da; Lau, Woon-Ming; Peng, Ping; Liu, Li-Min

2014-02-01

The family of bulk metal phosphorus trichalcogenides (APX3, A = MII, M_{0.5}^IM_{0.5}^{III}; X = S, Se; MI, MII, and MIII represent Group-I, Group-II, and Group-III metals, respectively) has attracted great attentions because such materials not only own magnetic and ferroelectric properties, but also exhibit excellent properties in hydrogen storage and lithium battery because of the layered structures. Many layered materials have been exfoliated into two-dimensional (2D) materials, and they show distinct electronic properties compared with their bulks. Here we present a systematical study of single-layer metal phosphorus trichalcogenides by density functional theory calculations. The results show that the single layer metal phosphorus trichalcogenides have very low formation energies, which indicates that the exfoliation of single layer APX3 should not be difficult. The family of single layer metal phosphorus trichalcogenides exhibits a large range of band gaps from 1.77 to 3.94 eV, and the electronic structures are greatly affected by the metal or the chalcogenide atoms. The calculated band edges of metal phosphorus trichalcogenides further reveal that single-layer ZnPSe3, CdPSe3, Ag0.5Sc0.5PSe3, and Ag0.5In0.5PX3 (X = S and Se) have both suitable band gaps for visible-light driving and sufficient over-potentials for water splitting. More fascinatingly, single-layer Ag0.5Sc0.5PSe3 is a direct band gap semiconductor, and the calculated optical absorption further convinces that such materials own outstanding properties for light absorption. Such results demonstrate that the single layer metal phosphorus trichalcogenides own high stability, versatile electronic properties, and high optical absorption, thus such materials have great chances to be high efficient photocatalysts for water-splitting.

Correlation between mechanical behavior of protein films at the air/water interface and intrinsic stability of protein molecules.

PubMed

Martin, Anneke H; Cohen Stuart, Martien A; Bos, Martin A; van Vliet, Ton

2005-04-26

The relation between mechanical film properties of various adsorbed protein layers at the air/water interface and intrinsic stability of the corresponding proteins is discussed. Mechanical film properties were determined by surface deformation in shear and dilation. In shear, fracture stress, sigma(f), and fracture strain, gamma(f), were determined, as well as the relaxation behavior after macroscopic fracture. The dilatational measurements were performed in a Langmuir trough equipped with an infra-red reflection absorption spectroscopy (IRRAS) accessory. During compression and relaxation of the surface, the surface pressure, Pi, and adsorbed amount, Gamma (determined from the IRRAS spectra), were determined simultaneously. In addition, IRRAS spectra revealed information on conformational changes in terms of secondary structure. Possible correlations between macroscopic film properties and intrinsic stability of the proteins were determined and discussed in terms of molecular dimensions of single proteins and interfacial protein films. Molecular properties involved the area per protein molecule at Pi approximately 0 mN/m (A(0)), A(0)/M (M = molecular weight) and the maximum slope of the Pi-Gamma curves (dPi/dGamma). The differences observed in mechanical properties and relaxation behavior indicate that the behavior of a protein film subjected to large deformation may vary widely from predominantly viscous (yielding) to more elastic (fracture). This transition is also observed in gradual changes in A(0)/M. It appeared that in general protein layers with high A(0)/M have a high gamma(f) and behave more fluidlike, whereas solidlike behavior is characterized by low A(0)/M and low gamma(f). Additionally, proteins with a low A(0)/M value have a low adaptability in changing their conformation upon adsorption at the air/water interface. Both results support the conclusion that the hardness (internal cohesion) of protein molecules determines predominantly the mechanical behavior of adsorbed protein layers.

Earliest accumulation history of the north polar layered deposits, Mars from SHARAD

NASA Astrophysics Data System (ADS)

Nerozzi, Stefano; Holt, John W.

2018-07-01

The approximately 2 km thick north polar layered deposits (NPLD) are often considered to contain the most complete and detailed stratigraphic records of recent climate of Mars. Exposures of the dense layering within troughs and scarps allowed detailed reconstructions of the latest accumulation history of these water ice deposits, but we lack knowledge of their initial emplacement. The Shallow Radar (SHARAD) onboard Mars Reconnaissance Orbiter (MRO) penetrates the NPLD to their base and detects their internal layering, overcoming the limitation of scarce and scattered visible outcrops of the lowermost sequences. In this study, we map reflectors in SHARAD data that result from discrete stratigraphic horizons in order to delineate the three-dimensional stratigraphy of the lowermost ∼500 m NPLD sequence and reconstruct their accumulation history. We confirm the large-scale lateral continuity and thickness uniformity of the deposits previously detected within the lowermost NPLD. However, stratigraphic complexity-in the form of pinch-outs and significant thickness variations-arises when we examine single radar units. We find evidence of an initially limited geographic stability of water ice within two deposits that are centered at the North Pole and present-day Gemina Lingula. A period of lateral ice sheet growth followed, interrupted only once by a retreat episode. Lower net accumulation is observed on pre-existing slopes, suggesting a reduction of water ice stability due to increased solar radiation incidence and/or transport by katabatic winds. Lateral transport of water ice by wind is also suggested by thickness undulations toward the top of the sequence, resembling cyclic steps. Water ice accumulation models based on orbital forcing predict a sequence of deposition and retreat events that is generally compatible with our reconstructed accumulation history. Therefore, we interpret the stratigraphic complexity that we observe as regional and, possibly global, climate change induced by orbital forcing. We also find that at least two units are completely buried within the NPLD and do not outcrop, and that NPLD deposition in some places was contemporaneous with deposition of the stratigraphically underlying cavi unit in other places. Both of these findings show that radar reflector mapping is a necessary complement to any stratigraphic reconstruction based on visible exposures.

CuO-Functionalized Silicon Photoanodes for Photoelectrochemical Water Splitting Devices.

PubMed

Shi, Yuanyuan; Gimbert-Suriñach, Carolina; Han, Tingting; Berardi, Serena; Lanza, Mario; Llobet, Antoni

2016-01-13

One main difficulty for the technological development of photoelectrochemical (PEC) water splitting (WS) devices is the fabrication of active, stable and cost-effective photoelectrodes that ensure high performance. Here, we report the development of a CuO/Silicon based photoanode, which shows an onset potential for the water oxidation of 0.53 V vs SCE at pH 9, that is, an overpotential of 75 mV, and high stability above 10 h. These values account for a photovoltage of 420 mV due to the absorbed photons by silicon, as proven by comparing with analogous CuO/FTO electrodes that are not photoactive. The photoanodes have been fabricated by sputtering a thin film of Cu(0) on commercially available n-type Si wafers, followed by a photoelectrochemical treatment in basic pH conditions. The resulting CuO/Cu layer acts as (1) protective layer to avoid the corrosion of nSi, (2) p-type hole conducting layer for efficient charge separation and transportation, and (3) electrocatalyst to reduce the overpotential of the water oxidation reaction. The low cost, low toxicity, and good performance of CuO-based coatings can be an attractive solution to functionalize unstable materials for solar energy conversion.

Global instability in a laminar boundary layer perturbed by an isolated roughness element

NASA Astrophysics Data System (ADS)

Puckert, Dominik K.; Rist, Ulrich

2018-03-01

Roughness-induced boundary-layer instabilities are investigated by means of hot-film anemometry in a water channel to provide experimental evidence of a global instability. It is shown that the roughness wake dynamics depends on extrinsic disturbances (amplifier) at subcritical Reynolds numbers, whereas intrinsic, self-sustained oscillations (wavemaker) are suspected at supercritical Reynolds numbers. The critical Reynolds number, therefore, separates between two different instability mechanisms. Furthermore, the critical Reynolds number from recent theoretical results is successfully confirmed in this experiment, supporting the physical relevance of 3-d global stability theory.

Modulating in vitro gastric digestion of emulsions using composite whey protein-cellulose nanocrystal interfaces.

PubMed

Sarkar, Anwesha; Zhang, Shuning; Murray, Brent; Russell, Jessica A; Boxal, Sally

2017-10-01

In this study, we designed emulsions with an oil-water interface consisting of a composite layer of whey protein isolate (WPI, 1wt%) and cellulose nanocrystals (CNCs) (1-3wt%). The hypothesis was that a secondary layer of CNCs at the WPI-stabilized oil-water interface could protect the interfacial protein layer against in vitro gastric digestion by pepsin at 37°C. A combination of transmission electron microscopy, ζ-potential measurements, interfacial shear viscosity measurements and theoretical surface coverage considerations suggested the presence of CNCs and WPI together at the O/W interface, owing to the electrostatic attraction between complementarily charged WPI and CNCs at pH 3. Microstructural analysis and droplet sizing revealed that the presence of CNCs increased the resistance of the interfacial protein film to rupture by pepsin, thus inhibiting droplet coalescence in the gastric phase, which occurs rapidly in an emulsion stabilized by WPI alone. It appeared that there was an optimum concentration of CNCs at the interface for such barrier effects. Sodium dodecyl sulphate polyacrylamide gel electrophoresis (SDS-PAGE) results further confirmed that the presence of 3wt% of CNCs reduced the rate and extent of proteolysis of protein at the interface. Besides, evidence of adsorption of CNCs to the protein-coated droplets to form more rigid layers, there is also the possibility that network formation by the CNCs in the bulk (continuous) phase reduced the kinetics of proteolysis. Nevertheless, structuring emulsions with mixed protein-particle layers could be an effective strategy to tune and control interfacial barrier properties during gastric passage of emulsions. Copyright © 2017 Elsevier B.V. All rights reserved.

A new approach to triggering mechanism of volcano landslides based on zeta potential and surface free energy balance

NASA Astrophysics Data System (ADS)

Plaza, I.; Ontiveros-Ortega, A.; Calero, J.; Romero, C.

2018-01-01

The layers of Almagre (iron-rich deposits) from Tenerife Island are the result of thermal metamorphism of soils in contact with lava flow (1073-1273 K). These layers of small thickness relative to the basaltic wash, are interesting for geotechnical study, because the stability of the deposits is determined by the weakest element, in this case Almagre, which acts as a sliding plane. The flow of maritime air over the hillsides of the volcanic islands increases the content of cations in ashes deposits. This modifies the superficial properties of material that composes the substratum. This modification affects the retention of water and the cohesion of material making up the deposit. The results show that the presence of sodium and magnesium increased the hydrophobicity of the material, which had a weak water retention capacity and strong cohesion at basic pH. When there is iron in solution, repulsion between the particles is greater than one obtained with other studied electrolytes. Hence, the deposit is less stable, and Almagre under saturated water conditions constitutes an ideal layer for landslides.

Rheological behavior of oxide nanopowder suspensions

NASA Astrophysics Data System (ADS)

Cinar, Simge

Ceramic nanopowders offer great potential in advanced ceramic materials and many other technologically important applications. Because a material's rheological properties are crucial for most processing routes, control of the rheological behavior has drawn significant attention in the recent past. The control of rheological behavior relies on an understanding of how different parameters affect the suspension viscosities. Even though the suspension stabilization mechanisms are relatively well understood for sub-micron and micron size particle systems, this knowledge cannot be directly transferred to nanopowder suspensions. Nanopowder suspensions exhibit unexpectedly high viscosities that cannot be explained with conventional mechanisms and are still a topic of investigation. This dissertation aims to establish the critical parameters governing the rheological behavior of concentrated oxide nanopowder suspensions, and to elucidate the mechanisms by which these parameters control the rheology of these suspensions. Aqueous alumina nanopowders were chosen as a model system, and the findings were extrapolated to other oxide nanopowder systems such as zirconia, yttria stabilized zirconia, and titania. Processing additives such as fructose, NaCl, HCl, NaOH, and ascorbic acid were used in this study. The effect of solids content and addition of fructose on the viscosity of alumina nanopowder suspensions was investigated by low temperature differential scanning calorimetry (LT-DSC), rheological, and zeta potential measurements. The analysis of bound water events observed in LT-DSC revealed useful information regarding the rheological behavior of nanopowder suspensions. Because of the significance of interparticle interactions in nanopowder suspensions, the electrostatic stabilization was investigated using indifferent and potential determining ions. Different mechanisms, e.g., the effect of the change in effective volume fraction caused by fructose addition and electrostatic stabilization, were combined to optimize the viscosities and the ability to control the suspension viscosity. The intrinsic viscosities of nanopowder systems were estimated using the Krieger-Dougherty relation. Both the individual and the combined effects were evaluated using slip casting of green bodies. Also, ascorbic acid was used to disperse the alumina nanopowders (described here for the first time in the open literature). The mechanism of viscosity reduction was investigated by in situ Attenuated Total Reflectance Fourier Infrared Spectroscopy (ATR-FTIR), rheological, suspension pH, and zeta potential measurements. Lastly, the findings were extrapolated to several other oxide systems. The rheological behavior of zirconia, yttria stabilized zirconia, and titania nanopowder systems was investigated as a function of solids content, bound water, and intrinsic viscosity. The results indicated that nanopowder suspensions differ from sub-micron powder suspensions because of the higher bound water content and the short separation distances between particles causing increased interparticle interactions. The bound water event was associated with the powder surface. This layer differed from the electrostatic double layer in that it was modified by fructose molecules as well as by specifically adsorbed ions such as H+ and OH but not by indifferent electrolytes, such as NaCl. Because of the large surface area of nanopowders, this additional layer increased the effective solids content and led to higher viscosities. While the alumina suspensions were studied in detail, it was also shown that the bound water was not unique to the alumina nanopowder suspensions, but also present in other oxide systems. However, the bound water content was unique for each system and provided information about its origin. The presence of bound water resulted in lower the maximum achievable solids fractions for nanopowder systems. In order to achieve higher solids contents, the bound water layer had to be modified. Because of the limited separation distances and large surface areas of nanopowders, the electrostatic double layer has an amplified effect on the viscosity of the suspensions. The addition of NaCl decreased the viscosity of alumina nanopowder suspensions significantly by compressing the double layer hence limiting the repulsion length. We also discovered that ascorbic acid can be used to disperse the alumina nanopowder suspensions. By adding only 1 wt% of ascorbic acid, the viscosity of the suspensions decreased significantly. It was shown that ascorbic acid molecules adsorbed to the alumina surfaces and when the adsorption reached equilibrium, the lowest viscosities were observed. By lowering the viscosities, the maximum achievable solids content (where viscosity = 1 Pa at a shear rate of 100 s-1) could be increased up to about 0.35, which is the highest solids content achieved with readily available processing additives reported in the open literature. Even though it is almost impossible to isolate the individual effects, three dominant mechanisms were observed in nanopowder suspensions: (i) increase in effective volume fraction (bound water), (ii) interparticle interactions (electrostatic), and (iii) adsorption of organic molecules. It was shown that the understanding of the system's parameters enables the optimization of the rheological behavior of the suspensions and the prediction of the green body quality.

Passivation coating for flexible substrate mirrors

DOEpatents

Tracy, C. Edwin; Benson, David K.

1990-01-01

A protective diffusion barrier for metalized mirror structures is provided by a layer or coating of silicon nitride which is a very dense, transparent, dielectric material that is impervious to water, alkali, and other impurities and corrosive substances that typically attack the metal layers of mirrors and cause degradation of the mirrors' reflectivity. The silicon nitride layer can be deposited on the substrate before metal deposition thereon to stabilize the metal/substrate interface, and it can be deposited over the metal to encapsulate it and protect the metal from corrosion or other degradation. Mirrors coated with silicon nitride according to this invention can also be used as front surface mirrors. Also, the silver or other reflective metal layer on mirrors comprising thin, lightweight, flexible substrates of metal or polymer sheets coated with glassy layers can be protected with silicon nitride according to this invention.

Development of an improved model for runback water on aircraft surfaces

NASA Technical Reports Server (NTRS)

Al-Khalil, Kamel M.; Keith, Theo G., Jr.; De Witt, Kenneth J.

1992-01-01

A computer simulation for 'running wet' and evaporative aircraft anti-icing systems is developed. The model is based on the analysis of the liquid water film which forms in the regions of direct impingement and, then, breaks up near the impingement limits into rivulets. The wetness factor distribution resulting from the film breakup and the rivulet configuration on the surface are predicted using a stability analysis theory and the laws of mass energy conservation. The solid structure is modeled as a multiple layer wall. The anti-icing system modeled is of the thermal type utilizing hot air and/or electrical heating elements embedded within the wall layers. Experimental observations revealing some of the basic physics of the water flow on the surface are presented. Detailed qualitative documentation of the tests are given. Several numerical examples are considered, and the effect of some of the involved parameters on the system performance are investigated.

Out-of-water constitutional self-organization of chitosan-cinnamaldehyde dynagels.

PubMed

Marin, Luminita; Moraru, Simona; Popescu, Maria-Cristina; Nicolescu, Alina; Zgardan, Cristina; Simionescu, Bogdan C; Barboiu, Mihail

2014-04-14

An investigation of the constitutional adaptive gelation process of chitosan/cinnamaldehyde (C/Cy) dynagels is reported. These gels generate timely variant macroscopic organization across extended scales. In the first stage, imine-bond formation takes place "in-water" and generates low-ordered hydrogels. The progressive formation of imine bonds further induces "out-of-water" increased reactivity within interdigitated hydrophobic self-assembled layers of Cy, with a protecting environmental effect against hydrolysis and that leads to the stabilization of the imine bonds. The hydrophobic swelling due to Cy layers at the interfaces reaches a critical step when lamellar self-organized hybrids are generated (24 hours). This induces an important restructuration of the hydrogels on the micrometric scale, thus resulting in the formation of highly ordered microporous xerogel morphologies of high potential interest for chemical separations, drug delivery, and sensors. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydration states of AFm cement phases

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

Baquerizo, Luis G., E-mail: luis.baquerizoibarra@holcim.com; Matschei, Thomas; Scrivener, Karen L.

2015-07-15

The AFm phase, one of the main products formed during the hydration of Portland and calcium aluminate cement based systems, belongs to the layered double hydrate (LDH) family having positively charged layers and water plus charge-balancing anions in the interlayer. It is known that these phases present different hydration states (i.e. varying water content) depending on the relative humidity (RH), temperature and anion type, which might be linked to volume changes (swelling and shrinkage). Unfortunately the stability conditions of these phases are insufficiently reported. This paper presents novel experimental results on the different hydration states of the most important AFmmore » phases: monocarboaluminate, hemicarboaluminate, strätlingite, hydroxy-AFm and monosulfoaluminate, and the thermodynamic properties associated with changes in their water content during absorption/desorption. This data opens the possibility to model the response of cementitious systems during drying and wetting and to engineer systems more resistant to harsh external conditions.« less

Influence of Saharan dust outbreaks and atmospheric stability upon vertical profiles of size-segregated aerosols and water vapor

NASA Astrophysics Data System (ADS)

Giménez, Joaquín; Pastor, Carlos; Castañer, Ramón; Nicolás, José; Crespo, Javier; Carratalá, Adoración

2010-01-01

Vertical profiles of aerosols and meteorological parameters were obtained using a hot air balloon and motorized paraglider. They were studied under anticyclonic conditions in four different contexts. Three flights occurred near sunrise, and one took place in the central hours of the day. The effects of North African dust intrusions were analyzed, whose entrance to the study area took place above the Stable Boundary Layer (SBL) in flight 1 and below it in flight 2. These flights have been compared with a non-intrusion situation (flight 3). A fourth flight characterized the profiles in the central hours of the day with a well-formed Convective Boundary Layer (CBL). With respect to the particle number distribution, the results show that not all sizes increase within the presence of an intrusion; during the first flight the smallest particles were not affected. The particle sizes affected in the second flight fell within the 0.35-2.5 μm interval. Under situations of convective dynamics, the reduction percentage of the particle number concentration reduces with increasing altitude, independently of their size, with respect to stability conditions. The negative vertical gradient for aerosols and water vapor, characteristic of a highly stable SBL (flight 3) becomes a constant profile within a CBL (flight 4). There are two situations that seem to alter the negative vertical gradient of the water vapor mixing ratio within the SBL: the presence of an intrusion and the possible stratification of the SBL based on different degrees of stability.

Water Drainage from Unsaturated Soils in a Centrifuge Permeameter

NASA Astrophysics Data System (ADS)

Ornelas, G.; McCartney, J.; Zhang, M.

2013-12-01

This study involves an analysis of water drainage from an initially saturated silt layer in a centrifuge permeameter to evaluate the hydraulic properties of the soil layer in unsaturated conditions up to the point where the water phase becomes discontinuous. These properties include the soil water retention curve (SWRC) and the hydraulic conductivity function (HCF). The hydraulic properties of unsaturated silt are used in soil-atmosphere interaction models that take into account the role of infiltration and evaporation of water from soils due to atmospheric interaction. These models are often applied in slope stability analyses, landfill cover design, aquifer recharge analyses, and agricultural engineering. The hydraulic properties are also relevant to recent research concerning geothermal heating and cooling, as they can be used to assess the insulating effects of soil around underground heat exchangers. This study employs a high-speed geotechnical centrifuge to increase the self-weight of a compacted silt specimen atop a filter plate. Under a centrifuge acceleration of N times earth's gravity, the concept of geometric similitude indicates that the water flow process in a small-scale soil layer will be similar to those in a soil layer in the field that is N times thicker. The centrifuge acceleration also results in an increase in the hydraulic gradient across the silt specimen, which causes water to flow out of the pores following Darcy's law. The drainage test was performed until the rate of liquid water flow out of the soil layer slowed to a negligible level, which corresponds to the transition point at which further water flow can only occur due to water vapor diffusion following Fick's law. The data from the drainage test in the centrifuge were used to determine the SWRC and HCF at different depths in the silt specimen, which compared well with similar properties defined using other laboratory tests. The transition point at which liquid water flow stopped (and Darcy's law is no longer valid) was at a relatively high degree of saturation of 0.8. This finding is important as many water flow analyses in the literature assume that Darcy's law is valid over a much wider range of degrees of saturation, an error that potentially may lead to overestimates of water flow in unsaturated soil layers.

Carbon Papers and Aerogels Based on Graphene Layers and Chitosan: Direct Preparation from High Surface Area Graphite.

PubMed

Barbera, Vincenzina; Guerra, Silvia; Brambilla, Luigi; Maggio, Mario; Serafini, Andrea; Conzatti, Lucia; Vitale, Alessandra; Galimberti, Maurizio

2017-12-11

In this work, carbon papers and aerogels based on graphene layers and chitosan were prepared. They were obtained by mixing chitosan (CS) and a high surface area nanosized graphite (HSAG) in water in the presence of acetic acid. HSAG/CS water dispersions were stable for months. High resolution transmission electron microscopy revealed the presence of few graphene layers in water suspensions. Casting or lyophilization of such suspensions led to the preparation of carbon paper and aerogel, respectively. In X-ray spectra of both aerogels and carbon paper, peaks due to regular stacks of graphene layers were not detected: graphene with unaltered sp 2 structure was obtained directly from graphite without the use of any chemical reaction. The composites were demonstrated to be electrically conductive thanks to the graphene. Chitosan thus makes it possible to obtain monolithic carbon aerogels and flexible and free-standing graphene papers directly from a nanosized graphite by avoiding oxidation to graphite oxide and successive reduction. Strong interaction between polycationic chitosan and the aromatic substrate appears to be at the origin of the stability of HSAG/CS adducts. Cation-π interaction is hypothesized, also on the basis of X-ray photoelectron spectroscopy findings. This work paves the way for the easy large-scale preparation of carbon papers through a method that has a low environmental impact and is based on a biosourced polymer, graphene, and water.

The effect of hardness on the stability of citrate-stabilized gold nanoparticles and their uptake by Daphnia magna.

PubMed

Lee, Byung-Tae; Ranville, James F

2012-04-30

The stability and uptake by Daphnia magna of citrate-stabilized gold nanoparticles (AuNPs) in three different hardness-adjusted synthetic waters were investigated. Negatively charged AuNPs were found to aggregate and settle in synthetic waters within 24 h. Sedimentation rates depended on initial particle concentrations of 0.02, 0.04, and 0.08 nM AuNPs. Hardness of the synthetic waters affected the aggregation of AuNPs and is explained by the compression of diffuse double layer of AuNPs due to the increasing ionic strength. The fractal dimension of AuNPs in the reaction-limited regime of synthetic waters averaged 2.228±0.126 implying the rigid structures of aggregates driven by the collision of small particles with the growing aggregates. Four-day old D. magna accumulated more than 90% of AuNPs in 0.04 nM AuNP suspensions without any observed mortality. Exposure to pre-aggregated AuNP for 48 h in hard water did not show any significant difference in uptake, suggesting D. magna can also ingest settled AuNP aggregates. D. magna exposed to AuNPs shed their exoskeleton whereas the control did not generate any molts over 48 h. This implies that D. magna removed AuNPs on their exoskeleton by producing molts to decrease any adverse effects of adhered AuNPs. Copyright © 2012 Elsevier B.V. All rights reserved.

Nanoscale potentiometry.

PubMed

Bakker, Eric; Pretsch, Ernö

2008-01-01

Potentiometric sensors share unique characteristics that set them apart from other electrochemical sensors. Potentiometric nanoelectrodes have been reported and successfully used for many decades, and we review these developments. Current research chiefly focuses on nanoscale films at the outer or the inner side of the membrane, with outer layers for increasing biocompatibility, expanding the sensor response, or improving the limit of detection (LOD). Inner layers are mainly used for stabilizing the response and eliminating inner aqueous contacts or undesired nanoscale layers of water. We also discuss the ultimate detectability of ions with such sensors and the power of coupling the ultra-low LODs of ion-selective electrodes with nanoparticle labels to give attractive bioassays that can compete with state-of-the-art electrochemical detection.

Investigation of Thin Layered Cobalt Oxide Nano-Islands on Gold

NASA Astrophysics Data System (ADS)

Bajdich, Michal; Walton, Alex S.; Fester, Jakob; Arman, Mohammad A.; Osiecki, Jacek; Knudsen, Jan; Vojvodic, Aleksandra; Lauritsen, Jeppe V.

2015-03-01

Layered cobalt oxides have been shown to be highly active catalysts for the oxygen evolution reaction (OER), but the synergistic effect of contact with gold is yet to be fully understood. The synthesis of three distinct types of thin-layered cobalt oxide nano-islands supported on a single crystal gold (111) substrate is confirmed by combination of STM and XAS methods. In this work, we present DFT+U theoretical investigation of above nano-islands using several previously known structural models. Our calculations confirm stability of two low-oxygen pressure phases: (a) rock-salt Co-O bilayer and (b) wurtzite Co-O quadlayer and single high-oxygen pressure phase: (c) O-Co-O trilayer. The optimized geometries agree with STM structures and calculated oxidation states confirm the conversion from Co2+ to Co3+ found experimentally in XAS. The O-Co-O trilayer islands have the structure of a single layer of CoOOH proposed to be the true active phase for OER catalyst. For that reason, the effect of water on the Pourbaix stabilities of basal planes and edge sites is fully investigated. Lastly, we also present the corresponding OER theoretical overpotentials.

Grafting of alginates on UF/NF ceramic membranes for wastewater treatment.

PubMed

Athanasekou, C P; Romanos, G E; Kordatos, K; Kasselouri-Rigopoulou, V; Kakizis, N K; Sapalidis, A A

2010-10-15

The mechanism of heavy metal ion removal in processes involving multi-layered tubular ultrafiltration and nanofiltration (UF/NF) membranes was investigated by conducting retention experiments in both flow-through and cross-flow modes. The prospect of the regeneration of the membranes through an acidic process was also examined and discussed. The UF/NF membranes were functionalised with alginates to develop hybrid inorganic/organic materials for continuous, single pass, wastewater treatment applications. The challenge laid in the induction of additional metal adsorption and improved regeneration capacity. This was accomplished by stabilizing alginates either into the pores or on the top-separating layer of the membrane. The preservation of efficient water fluxes at moderate trans-membrane pressures introduced an additional parameter that was pursued in parallel to the membrane modification process. The deposition and stabilization of alginates was carried out via physical (filtration/cross-linking) and chemical (grafting) procedures. The materials developed by means of the filtration process exhibited a 25-60% enhancement of their Cd(2+) binding capacity, depending on the amount of the filtered alginate solution. The grafting process led to the development of alginate layers with adequate stability under acidic regeneration conditions and metal retention enhancement of 25-180%, depending on the silane involved as grafting agent and the solvent of silanisation. 2010 Elsevier B.V. All rights reserved.

Ultrathin platinum nanowires grown on single-layered nickel hydroxide with high hydrogen evolution activity.

PubMed

Yin, Huajie; Zhao, Shenlong; Zhao, Kun; Muqsit, Abdul; Tang, Hongjie; Chang, Lin; Zhao, Huijun; Gao, Yan; Tang, Zhiyong

2015-03-02

Design and synthesis of effective electrocatalysts for hydrogen evolution reaction in alkaline environments is critical to reduce energy losses in alkaline water electrolysis. Here we report a hybrid nanomaterial comprising of one-dimensional ultrathin platinum nanowires grown on two-dimensional single-layered nickel hydroxide. Judicious surface chemistry to generate the fully exfoliated nickel hydroxide single layers is explored to be the key for controllable growth of ultrathin platinum nanowires with diameters of about 1.8 nm. Impressively, this hybrid nanomaterial exhibits superior electrocatalytic activity for hydrogen evolution reaction in alkaline solution, which outperforms currently reported catalysts, and the obviously improved catalytic stability. We believe that this work may lead towards the development of single-layered metal hydroxide-based hybrid materials for applications in catalysis and energy conversion.

Double-Layer Structured CO2 Adsorbent Functionalized with Modified Polyethyleneimine for High Physical and Chemical Stability.

PubMed

Jeon, Sunbin; Jung, Hyunchul; Kim, Sung Hyun; Lee, Ki Bong

2018-06-18

CO 2 capture using polyethyleneimine (PEI)-impregnated silica adsorbents has been receiving a lot of attention. However, the absence of physical stability (evaporation and leaching of amine) and chemical stability (urea formation) of the PEI-impregnated silica adsorbent has been generally established. Therefore, in this study, a double-layer impregnated structure, developed using modified PEI, is newly proposed to enhance the physical and chemical stabilities of the adsorbent. Epoxy-modified PEI and diepoxide-cross-linked PEI were impregnated via a dry impregnation method in the first and second layers, respectively. The physical stability of the double-layer structured adsorbent was noticeably enhanced when compared to the conventional adsorbents with a single layer. In addition to the enhanced physical stability, the result of simulated temperature swing adsorption cycles revealed that the double-layer structured adsorbent presented a high potential working capacity (3.5 mmol/g) and less urea formation under CO 2 -rich regeneration conditions. The enhanced physical and chemical stabilities as well as the high CO 2 working capacity of the double-layer structured adsorbent were mainly attributed to the second layer consisting of diepoxide-cross-linked PEI.

A modified Bitter-type electromagnet and control system for cold atom experiments

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

Luan, Tian; Zhou, Tianwei; Chen, Xuzong, E-mail: xuzongchen@pku.edu.cn

2014-02-15

We present a modified Bitter-type electromagnet which features high magnetic field, fine electronic properties and efficient heat removal. The electromagnet is constructed from a stack of copper layers separated by mica layers that have the same shape. A distinctive design of cooling channels on the insulating layers and the parallel ducts between the layers ensures low resistance for cooling water to flow. A continuous current control system is also made to regulate the current through the electromagnet. In our experiment, versatile electromagnets are applied to generate magnetic field and gradient field. From our measurements, a peak magnetic field of 1000more » G and a peak gradient field of 80 G/cm are generated in the center of the apparatuses which are 7 cm and 5 cm away from the edge of each electromagnet with a current of 230 A and 120 A, respectively. With the effective feedback design in the current control system and cooling water flow of 3.8 l/min, the stability of the current through the electromagnets can reach 10{sup −5}.« less

In Situ Crystallization Synthesis of CsPbBr3 Perovskite Quantum Dot-Embedded Glasses with Improved Stability for Solid-State Lighting and Random Upconverted Lasing.

PubMed

Yuan, Shuo; Chen, Daqin; Li, Xinyue; Zhong, Jiasong; Xu, Xuhui

2018-06-06

All-inorganic cesium lead bromide CsPbBr 3 perovskite quantum dots (QDs) are emerging as potential candidates for their applications in optoelectronic devices but they suffer from poor long-term stability due to their high sensitivity to UV irradiation, heat, and especially to moisture. Although great advances in improving stability of perovskite QDs have been achieved by surface modification or encapsulation in polymer and silica, they are not sufficiently refrained from external environment due to nondense structures of these protective layers. In this work, in situ nanocrystallization strategy is developed to directly grow CsPbBr 3 QDs among a specially designed TeO 2 -based glass matrix. As a result, QD-embedded glass shows typical bright green emission assigned to exciton recombination radiation and significant improvement of photon/thermal stability and water resistance due to the effective protecting role of dense structural glass. Particularly, ∼90% of emission intensity is even remained after immersing QD-embedded glass in water up to 120 h, enabling them to find promising applications in white-light-emitting device with superior color stability and low-threshold random upconverted laser under ambient air condition.

The Weddell-Scotia Confluence in midwinter

NASA Astrophysics Data System (ADS)

Muench, Robin D.; Gunn, John T.; Husby, David M.

1990-10-01

The southern central Scotia Sea, site of the Weddell-Scotia Confluence where outflowing Weddell Sea waters converge with the eastward flowing waters of the Scotia Sea, was sampled during June-August (austral winter) 1988 with respect to temperature and salinity. Both drogued and ice-mounted drifters, tracked by Argos, were deployed in the region and yielded Lagrangian drift tracks of ice and water motion. The data substantiate past accounts of the region, based upon summer field research, as dominated by eastward flow upon which a complex array of mesoscale features is superimposed. Weddell-Scotia Confluence Water, documented by past summer work in the region and characterized by decreased static stability, was not detected, and the Scotia Front was not well defined. The region was one of intense mixing activity and primarily anticyclonic mesoscale features. Two such features, one an eddy and the other either an eddy or a meander in the Scotia Front, dominated the mesoscale field. With warm cores and containing Polar Front Water, they may have been advected eastward from Drake Passage or may have formed as detached eddies from a sharp northward bend in the Polar Front which typically lies just west of the study region. Several smaller eddies, primarily anticyclonic and some having warm cores, were also detected. There was no evidence of the deep convective mixing which has been hypothesized, on the basis of past summer data, to occur in winter, and vigorous vertical mixing was limited to a 100-m-thick upper mixed layer. Vertical stability in the upper layers was enhanced by low-salinity water derived from melting ice. Temperature-salinity analyses show that winter water in the study region can be derived through isopycnal mixing between waters from the Scotia Sea and waters from the northwestern Weddell Sea. This is in apparent contrast with summer conditions, wherein conditioning of water either through vertical mixing or via lateral mixing on continental margins has been invoked to arrive at the water mass characteristics which typify the Weddell-Scotia Confluence.

Atomic Layer Deposition of Metastable β-Fe 2 O 3 via Isomorphic Epitaxy for Photoassisted Water Oxidation

DOE PAGES

Emery, Jonathan D.; Schlepütz, Christian M.; Guo, Peijun; ...

2014-12-09

Here, we report the growth and photoelectrochemical (PEC) characterization of the uncommon bibyite phase of iron(III) oxide (β-Fe 2O 3) epitaxially stabilized via atomic layer deposition on an conductive, transparent, and isomorphic template (Sn-doped In 2O 3). Furthermore, as a photoanode, unoptimized β-Fe 2O 3 ultrathin films perform similarly to their ubiquitous α-phase (hematite) counterpart, but reveal a more ideal bandgap (1.8 eV), a ~0.1 V improved photocurrent onset potential, and longer wavelength (>600 nm) spectral response. Finally, stable operation under basic water oxidation justifies further exploration of this atypical phase and motivates the investigation of other unexplored metastable phasesmore » as new PEC materials.« less

Long-time aging in 3 mol.% yttria-stabilized tetragonal zirconia polycrystals at human body temperature.

PubMed

Keuper, Melanie; Berthold, Christoph; Nickel, Klaus Georg

2014-02-01

We present new findings on the low-temperature degradation of yttria-stabilized zirconia at 37°C over several years and at high and low partial pressures of water. With the aid of focused ion beam cross-section confirmation studies we are able to show an extensive linear, continuous degradation without retardation, even at low temperatures and low water pressures. The characteristic layer growth and its inferred rate constant imply a lifetime of tens of years under simple tension and open the possibility of studying the longevity of these ceramics more rigorously. In addition, we show reproducibility complications of accelerated aging tests by the use of different autoclaves and possible implications for standardized procedures. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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

Willow, Soohaeng Yoo; Xantheas, Sotiris S.

The effect of the Hofmeister anion series on the structure and stability of proteins is often discussed using simple systems such as a water-vapor interface with the assumption that the vapor region mimics the hydrophobic surface. Microscopic theories suggest that the Hofmeister anion series is highly correlated with the different contributions of the various ions to the surface tension of such a water-vapor interface. Proteins, however, have both hydrophobic and hydrophilic regions rather than just a pure hydrophobic one. Using a solvated parallel β -sheet layer consisting of both hydrophobic and positively charged hydrophilic surfaces as a more realistic modelmore » to represent a protein surface, we investigated the interaction of such a system with hydrophilic-like (SO42-) and hydrophobic-like (ClO4-) anions via Born-Oppenheimer Molecular Dynamics (BOMD) simulations. We found that both the SO42- and ClO4- anions prefer to reside on the hydrophilic rather than on the hydrophobic surface of the parallel β -sheet layer. In addition, our simulations suggest that the ClO4- ions not only penetrate towards the peptide groups through the hydrophilic residues, but also allow water molecules to penetrate as well to form water-peptide hydrogen bonds, while the SO42- ions stabilize the interface of the water-hydrophilic surface. Our results render a plausible explanation of why hydrophobic-like Hofmeister anions act as protein denaturants. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle.« less

Enhancing long-term photostability of BiVO4 photoanodes for solar water splitting by tuning electrolyte composition

NASA Astrophysics Data System (ADS)

Lee, Dong Ki; Choi, Kyoung-Shin

2018-01-01

As the performance of photoelectrodes used for solar water splitting continues to improve, enhancing the long-term stability of the photoelectrodes becomes an increasingly crucial issue. In this study, we report that tuning the composition of the electrolyte can be used as a strategy to suppress photocorrosion during solar water splitting. Anodic photocorrosion of BiVO4 photoanodes involves the loss of V5+ from the BiVO4 lattice by dissolution. We demonstrate that the use of a V5+-saturated electrolyte, which inhibits the photooxidation-coupled dissolution of BiVO4, can serve as a simple yet effective method to suppress anodic photocorrosion of BiVO4. The V5+ species in the solution can also incorporate into the FeOOH/NiOOH oxygen-evolution catalyst layer present on the BiVO4 surface during water oxidation, further enhancing water-oxidation kinetics. The effect of the V5+ species in the electrolyte on both the long-term photostability of BiVO4 and the performance of the FeOOH/NiOOH oxygen-evolution catalyst layer is systematically elucidated.

Coupled diffusion in lipid bilayers upon close approach

DOE PAGES

Pronk, Sander; Lindahl, Erik; Kasson, Peter M.

2014-12-23

Biomembrane interfaces create regions of slowed water dynamics in their vicinity. When two lipid bilayers come together, this effect is further accentuated, and the associated slowdown can affect the dynamics of larger-scale processes such as membrane fusion. We have used molecular dynamics simulations to examine how lipid and water dynamics are affected as two lipid bilayers approach each other. These two interacting fluid systems, lipid and water, both slow and become coupled when the lipid membranes are separated by a thin water layer. We show in particular that the water dynamics become glassy, and diffusion of lipids in the apposedmore » leaflets becomes coupled across the water layer, while the “outer” leaflets remain unaffected. This dynamic coupling between bilayers appears mediated by lipid–water–lipid hydrogen bonding, as it occurs at bilayer separations where water–lipid hydrogen bonds become more common than water–water hydrogen bonds. We further show that such coupling occurs in simulations of vesicle–vesicle fusion prior to the fusion event itself. As a result, such altered dynamics at membrane–membrane interfaces may both stabilize the interfacial contact and slow fusion stalk formation within the interface region.« less

Fabrication, characterization and antimicrobial activities of thymol-loaded zein nanoparticles stabilized by sodium caseinate-chitosan hydrochloride double layers.

PubMed

Zhang, Yaqiong; Niu, Yuge; Luo, Yangchao; Ge, Mei; Yang, Tian; Yu, Liangli Lucy; Wang, Qin

2014-01-01

Thymol-loaded zein nanoparticles stabilized with sodium caseinate (SC) and chitosan hydrochloride (CHC) were prepared and characterized. The SC stabilized nanoparticles had well-defined size range and negatively charged surface. Due to the presence of SC, the stabilized zein nanoparticles showed a shift of isoelectric point from 6.18 to 5.05, and had a desirable redispersibility in water at neutral pH after lyophilization. Coating with CHC onto the SC stabilized zein nanoparticles resulted in increased particle size, reversal of zeta potential value from negative to positive, and improved encapsulation efficiency. Both thymol-loaded zein nanoparticles and SC stabilized zein nanoparticles had a spherical shape and smooth surface, while the surfaces of CHC-SC stabilized zein nanoparticles seemed rough and had some clumps. Encapsulated thymol was more effective in suppressing gram-positive bacterium than un-encapsulated thymol for a longer time period. Copyright © 2013 Elsevier Ltd. All rights reserved.

Can Subglacial Meltwater Films Carve Into the till Beneath? Insights from a Coupled Till-Water Model

NASA Astrophysics Data System (ADS)

Kasmalkar, I.; Mantelli, E.; Suckale, J.

2017-12-01

Networks of water channels are known to exist beneath regions of the continental ice sheets such as Antarctica and Greenland. These channels are fed by meltwater and form along the interface between the ice and the underlying till layer. Their presence localizes basal strength by reducing pore pressure and hence alters the resistance to ice slip provided by the till. Subglacial channels thus play a major role in determining the rate of ice flow for glaciers and ice streams. It is unclear whether subglacial meltwater can evolve from a thin film into a network of distributed channels by erosion of the sediment bed. Models that involve hard-rock beds can only account for water channels that carve into the ice and not the till. Alternative approaches that include erodible sediment mostly assume viscous behavior in the till layer, which is not well supported by laboratory experiments of till failure. To better understand the physical processes that govern channelization, we couple water flow in a thin film with sediment transport to capture the dynamic interactions between water and till. We present a two-dimensional model which consists of a thin subglacial water film that is in the laminar regime and an erodible till layer that obeys the Shield's criterion. We use analytic techniques to study the long-term behavior of perturbations of the water-till interface. We discuss the stability of the system under such perturbations in the context of channel formation.

Factors that Influence the Formation and Stability of Thin, Cryo-EM Specimens

DOE PAGES

Glaeser, Robert M.; Han, Bong-Gyoon; Csencsits, Roseann; ...

2015-09-17

Poor consistency of the ice thickness from one area of a cryo-electron microscope (cryo-EM) specimen grid to another, from one grid to the next, and from one type of specimen to another, motivates a reconsideration of how to best prepare suitably thin specimens. We first review the three related topics of wetting, thinning, and stability against dewetting of aqueous films spread over a hydrophilic substrate. Furthermore, we then suggest that the importance of there being a surfactant monolayer at the air-water interface of thin, cryo-EM specimens has been largely underappreciated. In fact, a surfactant layer (of uncontrolled composition and surfacemore » pressure) can hardly be avoided during standard cryo-EM specimen preparation. Thus it is suggested that better control over the composition and properties of the surfactant layer may result in more reliable production of cryo-EM specimens with the desired thickness.« less

Suppressed decomposition of organometal halide perovskites by impermeable electron-extraction layers in inverted solar cells

PubMed Central

Brinkmann, K.O.; Zhao, J.; Pourdavoud, N.; Becker, T.; Hu, T.; Olthof, S.; Meerholz, K.; Hoffmann, L.; Gahlmann, T.; Heiderhoff, R.; Oszajca, M. F.; Luechinger, N. A.; Rogalla, D.; Chen, Y.; Cheng, B.; Riedl, T

2017-01-01

The area of thin-film photovoltaics has been overwhelmed by organometal halide perovskites. Unfortunately, serious stability concerns arise with perovskite solar cells. For example, methyl-ammonium lead iodide is known to decompose in the presence of water and, more severely, even under inert conditions at elevated temperatures. Here, we demonstrate inverted perovskite solar cells, in which the decomposition of the perovskite is significantly mitigated even at elevated temperatures. Specifically, we introduce a bilayered electron-extraction interlayer consisting of aluminium-doped zinc oxide and tin oxide. We evidence tin oxide grown by atomic layer deposition does form an outstandingly dense gas permeation barrier that effectively hinders the ingress of moisture towards the perovskite and—more importantly—it prevents the egress of decomposition products of the perovskite. Thereby, the overall decomposition of the perovskite is significantly suppressed, leading to an outstanding device stability. PMID:28067308

Factors that Influence the Formation and Stability of Thin, Cryo-EM Specimens

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

Glaeser, Robert M.; Han, Bong-Gyoon; Csencsits, Roseann

Poor consistency of the ice thickness from one area of a cryo-electron microscope (cryo-EM) specimen grid to another, from one grid to the next, and from one type of specimen to another, motivates a reconsideration of how to best prepare suitably thin specimens. We first review the three related topics of wetting, thinning, and stability against dewetting of aqueous films spread over a hydrophilic substrate. Furthermore, we then suggest that the importance of there being a surfactant monolayer at the air-water interface of thin, cryo-EM specimens has been largely underappreciated. In fact, a surfactant layer (of uncontrolled composition and surfacemore » pressure) can hardly be avoided during standard cryo-EM specimen preparation. Thus it is suggested that better control over the composition and properties of the surfactant layer may result in more reliable production of cryo-EM specimens with the desired thickness.« less

Detection of organic vapors on sputtered and annealed thin Au films

NASA Astrophysics Data System (ADS)

Kvitek, O.; Kopacek, V.; Reznickova, A.; Svorcik, V.

2018-03-01

Unique optical properties of metal nanostructures enable construction of new types of chemical sensors. Nanostructures composed of Au on glass substrate were prepared by annealing of 2-20 nm thick sputtered Au films at 300 °C for 1 h. The annealing leads to transformation of the as sputtered continuous Au layers to a nanoisland structure. The forming nanostructure shows a strong, well defined surface plasmon resonance absorption band in UV-Vis spectrum, which is useful for construction of a chemical sensor. The samples were used to detect vapors of acetone and water in an experimental testing apparatus. The achieved signal-to-noise ratio was 583 and 386 for acetone and water vapors, respectively on the nanostructure prepared from 4 nm thick Au layer. The nanostructured sensitive layers, however, showed poor signal stability; therefore a polymer overlayer was introduced to protect it. The employed polystyrene film prepared by spin-coating improved sensitivity and selectivity of the sensor, while the dynamic properties of the sensing influenced only slightly.

Application of functionalized nanofluid in thermosyphon

PubMed Central

2011-01-01

A water-based functionalized nanofluid was made by surface functionalizing the ordinary silica nanoparticles. The functionalized nanofluid can keep long-term stability. and no sedimentation was observed. The functionalized nanofluid as the working fluid is applied in a thermosyphon to understand the effect of this special nanofluid on the thermal performance of the thermosyphon. The experiment was carried out under steady operating pressures. The same work was also explored for traditional nanofluid (consisting of water and the same silica nanoparticles without functionalization) for comparison. Results indicate that a porous deposition layer exists on the heated surface of the evaporator during the operating process using traditional nanofluid; however, no coating layer exists for functionalized nanofluid. Functionalized nanofluid can enhance the evaporating heat transfer coefficient, while it has generally no effect on the maximum heat flux. Traditional nanofluid deteriorates the evaporating heat transfer coefficient but enhances the maximum heat flux. The existence of the deposition layer affects mainly the thermal performance, and no meaningful nanofluid effect is found in the present study. PMID:21846362

On-surface synthesis: a promising strategy toward the encapsulation of air unstable ultra-thin 2D materials.

PubMed

Li, Qiang; Zhao, Yinghe; Guo, Jiyuan; Zhou, Qionghua; Chen, Qian; Wang, Jinlan

2018-02-22

2D black phosphorus (BP) and transition metal chalcogenides (TMCs) have beneficial electronic, optical, and physical properties at the few-layer limit. However, irreversible degradation of exfoliated or chemical vapor deposition-grown ultrathin BP and TMCs like GaSe via oxidation under ambient conditions limits their applications. Herein, the on-surface growth of an oxidation-resistant 2D thin film of a metal coordination polymer is demonstrated by multiscale simulations. We show that the preparation of such heterostructures can be conducted in solution, in which pristine BP and GaSe present better stability than in an air environment. Our calculations reveal that the interaction between the polymer layer and 2D materials is dominated by van der Waals forces; thus, the electronic properties of pristine BP and GaSe are well preserved. Meanwhile, the isolation from oxygen and water can be achieved by monolayer polymers, due to the nature of their close-packed layers. Our facile strategy for enhancing the environmental stability of ultrathin materials is expected to accelerate efforts to implement 2D materials in electronic and optoelectronic applications.

Cathodic Electrodeposition of Ni-Mo on Semiconducting NiFe2 O4 for Photoelectrochemical Hydrogen Evolution in Alkaline Media.

PubMed

Wijten, Jochem H J; Jong, Ronald P H; Mul, Guido; Weckhuysen, Bert M

2018-04-25

Photocathodes for hydrogen evolution from water were made by electrodeposition of Ni-Mo layers on NiFe 2 O 4 substrates, deposited by spin coating on F:SnO 2 -glass. Analysis confirmed the formation of two separate layers, without significant reduction of NiFe 2 O 4 . Bare NiFe 2 O 4 was found to be unstable under alkaline conditions during (photo)electrochemistry. To improve the stability significantly, the deposition of a bifunctional Ni-Mo layer through a facile electrodeposition process was performed and the composite electrodes showed stable operation for at least 1 h. Moreover, photocurrents up to -2.1 mA cm -2 at -0.3 V vs. RHE were obtained for Ni-Mo/NiFe 2 O 4 under ambient conditions, showing that the new combination functions as both a stabilizing and catalytic layer for the photoelectrochemical evolution of hydrogen. The photoelectrochemical response of these composite electrodes decreased with increasing NiFe 2 O 4 layer thickness. Transient absorption spectroscopy showed that the lifetime of excited states is short and on the ns timescale. An increase in lifetime was observed for NiFe 2 O 4 of large layer thickness, likely explained by decreasing the defect density in the primary layer(s), as a result of repetitive annealing at elevated temperature. The photoelectrochemical and transient absorption spectroscopy results indicated that a short charge carrier lifetime limits the performance of Ni-Mo/NiFe 2 O 4 photocathodes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Aggregation and stability of anisotropic charged clay colloids in aqueous medium in the presence of salt.

PubMed

Ali, Samim; Bandyopadhyay, Ranjini

2016-01-01

Na-montmorillonite nanoclay is a colloid of layered mineral silicate. When dispersed in water, this mineral swells on absorption of water and exfoliates into platelets with electric double layers on their surfaces. Even at low particle concentration, the aqueous dispersion can exhibit a spontaneous ergodicity breaking phase transition from a free flowing liquid to nonequilibrium, kinetically arrested and disordered states such as gels and glasses. In an earlier publication [Applied Clay Science, 2015, 114, 8592], we showed that the stability of clay gels can be enhanced by adding a salt later to the clay dispersion prepared in deionized water, rather than by adding the clay mineral to a previously mixed salt solution. Here, we directly track the collapsing interface of sedimenting clay gels using an optical method and show that adding salt after dispersing the clay mineral does indeed result in more stable gels even in very dilute dispersions. These weak gels are seen to exhibit a transient collapse after a finite delay time, a phenomenon observed previously in depletion gels. The velocity of the collapse oscillates with the age of the sample. However, the average velocity of collapse increases with sample age up to a peak value before decreasing at higher ages. With increasing salt concentration, the delay time for transient collapse decreases, while the peak value of the collapsing velocity increases. Using ultrasound attenuation spectroscopy, rheometry and cryogenic scanning electron microscopy, we confirm that morphological changes of the gel network assembly, facilitated by thermal fluctuations, lead to the observed collapse phenomenon. Since clay minerals are used extensively in polymer nanocomposites, as rheological modifiers, stabilizers and gas absorbents, we believe that the results reported in this work are extremely useful for several practical applications and also for understanding geophysical phenomena such as the formation and stability of quicksand and river deltas.

Similarity scaling of turbulence in small temperate lake: implication for gas flux: implication for gas flux

NASA Astrophysics Data System (ADS)

Tedford, E. W.; MacIntyre, S.; Miller, S. D.; Czikowsky, M. J.

2013-12-01

The actively mixing layer, or surface layer, is the region of the upper mixed layer of lakes, oceans and the atmosphere directly influenced by wind, heating and cooling. Turbulence within the surface mixing layer has a direct impact on important ecological processes. The Monin-Obukhov length scale (LMO) is a critical length scale used in predicting and understanding turbulence in the actively mixed layer. On the water side of the air-water interface, LMO is defined as: LMO=-u*^3/(0.4 JB0) where u*, the shear velocity, is defined as (τ/rho)^0.5 where τ is the shear stress and rho is the density of water and JBO is the buoyancy flux at the surface. Above the depth equal to the absolute value of the Monin-Obukhov length scale (zMO), wind shear is assumed to dominate the production of turbulent kinetic energy (TKE). Below zMO, the turbulence is assumed to be suppressed when JB0 is stabilizing (warming surface waters) and enhanced when the buoyancy flux is destabilizing (cooling surface waters). Our observed dissipations were well represented using the canonical similarity scaling equations. The Monin-Obukhov length scale was generally effective in separating the surface-mixing layer into two regions: an upper region, dominated by wind shear; and a lower region, dominated by buoyancy flux. During both heating and cooling and above a depth equal to |LMO|, turbulence was dominated by wind shear and dissipation followed law of the wall scaling although was slightly augmented by buoyancy flux during both heating and cooling. Below a depth equal to |LMO| during cooling, dissipation was nearly uniform with depth. Although distinguishing between an upper region of the actively mixing layer dominated by wind stress and a lower portion dominated by buoyancy flux is typically accurate the most accurate estimates of dissipation include the effects of both wind stress and buoyancy flux throughout the actively mixed layer. We demonstrate and discuss the impact of neglecting the non-dominant forcing (buoyancy flux above zMO and wind stress below zMO) above and below zMO.

Aerogeophysical evidence for active volcanism beneath the West Antarctic Ice Sheet

NASA Technical Reports Server (NTRS)

Blankenship, Donald D.; Bell, Robin E.; Hodge, Steven M.; Brozena, John M.; Behrendt, John C.

1993-01-01

Although it is widely understood that the collapse of the West Antarctic Ice Sheet (WAIS) would cause a global sea-level rise of 6 m, there continues to be considerable debate about the response of this ice sheet to climate change. The stability of the WAIS, which is characterized by a bed grounded well below sea level, may depend on geologically controlled conditions at the base, which are independent of climate. Ice streams moving up to 750 m/yr disperse material from the interior through to the oceans. As these ice streams tend to buffer the reservoir of slow-moving inland ice from exposure to oceanic degradation, understanding the ice-streaming process is important for evaluating WAIS stability. There is strong evidence that ice streams slide on a lubricating layer of water-saturated till. Development of this basal layer requires both water and easily eroded sediments. Active lithospheric extension may elevate regional heat flux, increase basal melting, and trigger ice streaming. If a geologically defined boundary with a sharp contrast in geothermal flux exists beneath the WAIS, ice streams may only be capable of operating as a buffer over a restricted region. Should ocean waters penetrate beyond this boundary, the ice-stream buffer would disappear, possibly triggering a collapse of the inland ice reservoir. Aerogeophysical evidence for active volcanism and elevated heat flux beneath the WAIS near the critical region where ice streaming begins is presented.

Stability characteristics of compressible boundary layers over thermo-mechanically compliant walls

NASA Astrophysics Data System (ADS)

Dettenrieder, Fabian; Bodony, Daniel

2017-11-01

Transition prediction at hypersonic flight conditions continues to be a challenge and results in conservative safety factors that increase vehicle weight. The weight and thus cost reduction of the outer skin panels promises significant impact; however, fluid-structure interaction due to unsteady perturbations in the laminar boundary layer regime has not been systematically studied at conditions relevant for reusable, hypersonic flight. In this talk, we develop and apply convective and global stability analyses for compressible boundary layers over thermo-mechanically compliant panels. This compliance is shown to change the convective stability of the boundary layer modes, with both stabilization and destabilization observed. Finite panel lengths are shown to affect the global stability properties of the boundary layer.

Multilayer encapsulated mesoporous silica nanospheres as an oral sustained drug delivery system for the poorly water-soluble drug felodipine.

PubMed

Hu, Liang; Sun, Hongrui; Zhao, Qinfu; Han, Ning; Bai, Ling; Wang, Ying; Jiang, Tongying; Wang, Siling

2015-02-01

We used a combination of mesoporous silica nanospheres (MSN) and layer-by-layer (LBL) self-assembly technology to establish a new oral sustained drug delivery system for the poorly water-soluble drug felodipine. Firstly, the model drug was loaded into MSN, and then the loaded MSN were repeatedly encapsulated by chitosan (CHI) and acacia (ACA) via LBL self-assembly method. The structural features of the samples were studied using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and nitrogen adsorption. The encapsulating process was monitored by zeta-potential and surface tension measurements. The physical state of the drug in the samples was characterized by differential scanning calorimetry (DSC) and X-ray diffractometry (XRD). The influence of the multilayer with different number of layers on the drug release rate was studied using thermal gravimetric analysis (TGA) and surface tension measurement. The swelling effect and the structure changes of the multilayer were investigated to explore the relationship between the drug release behavior and the state of the multilayer under different pH conditions. The stability and mucosa adhesive ability of the prepared nanoparticles were also explored. After multilayer coating, the drug release rate was effectively controlled. The differences in drug release behavior under different pH conditions could be attributed to the different states of the multilayer. And the nanoparticles possessed good stability and strong mucosa adhesive ability. We believe that this combination offers a simple strategy for regulating the release rate of poorly water-soluble drugs and extends the pharmaceutical applications of inorganic materials and polymers. Copyright © 2014 Elsevier B.V. All rights reserved.

Influence of a uniform transverse magnetic field on the thermo-hydrodynamic stability in water-based nanofluids with metallic nanoparticles using the generalized Buongiorno's mathematical model

NASA Astrophysics Data System (ADS)

Wakif, Abderrahim; Boulahia, Zoubair; Mishra, S. R.; Mehdi Rashidi, Mohammad; Sehaqui, Rachid

2018-05-01

The onset of nanofluid convection in the presence of an externally applied magnetic field is investigated numerically based on the non-homogeneous Buongiorno's mathematical model. In this study, we use the latest experimental correlations and powerful analytical models for expressing the thermo-physical properties of some electrically conducting nanofluids, such as copper-water, sliver-water and gold-water nanofluids, in which the Brownian motion and thermophoresis effects on slip flow in nanofluids are taken into account in this model ( i.e., two-phase transport model). In this paper, we assume that the nanofluid has Newtonian behavior, confined horizontally between two infinite impermeable boundaries and heated from below, in such a way that the nanoparticles tend to concentrate near the upper wall. Considering the basic state of the nanofluidic system, the linear stability theory has been successfully applied to obtain the principal stability equations, which are solved numerically for an imposed volumetric fraction of nanoparticles and no-slip impermeable conditions at the isothermal walls bounding the nanofluid layer. The linear boundary-value problem obtained in this investigation is converted into a pure initial-value problem, so that we can solve it numerically by the fourth-fifth-order Runge-Kutta-Fehlberg method. The generalized Buongiorno's mathematical model proposed in this study allows performing a highly accurate computational analysis. In addition, the obtained results show that the stability of the studied nanofluidic system depends on several parameters, namely, the magnetic Chandrasekhar number Q , the reference value for the volumetric fraction of nanoparticles φ_0 and the size of nanoparticles d_p . In this analysis, the thermo-hydrodynamic stability of the studied nanofluid is controlled through the critical thermal Rayleigh number R_{ac} , which characterizes the onset of convection cells, whose size is L_c=2π/a_c . Furthermore, the effects of various pertinent parameters on the critical stability parameters R_{ac} and a_c are discussed in more detail through graphical and tabular illustrations, for three types of nanofluids including copper-water, sliver-water, and gold-water.

Numerical simulation of the free surface and water inflow of a slope, considering the nonlinear flow properties of gravel layers: a case study

NASA Astrophysics Data System (ADS)

Yang, Bin; Yang, Tianhong; Xu, Zenghe; Liu, Honglei; Shi, Wenhao; Yang, Xin

2018-02-01

Groundwater is an important factor of slope stability, and 90% of slope failures are related to the influence of groundwater. In the past, free surface calculations and the prediction of water inflow were based on Darcy's law. However, Darcy's law for steady fluid flow is a special case of non-Darcy flow, and many types of non-Darcy flows occur in practical engineering applications. In this paper, based on the experimental results of laboratory water seepage tests, the seepage state of each soil layer in the open-pit slope of the Yanshan Iron Mine, China, were determined, and the seepage parameters were obtained. The seepage behaviour in the silt layer, fine sand layer, silty clay layer and gravelly clay layer followed the traditional Darcy law, while the gravel layers showed clear nonlinear characteristics. The permeability increases exponentially and the non-Darcy coefficient decreases exponentially with an increase in porosity, and the relation among the permeability, the porosity and the non-Darcy coefficient is investigated. A coupled mathematical model is established for two flow fields, on the basis of Darcy flow in the low-permeability layers and Forchheimer flow in the high-permeability layers. In addition, the effect of the seepage in the slope on the transition from Darcy flow to Forchheimer flow was considered. Then, a numerical simulation was conducted by using finite-element software (FELAC 2.2). The results indicate that the free surface calculated by the Darcy-Forchheimer model is in good agreement with the in situ measurements; however, there is an evident deviation of the simulation results from the measured data when the Darcy model is used. Through a parameter sensitivity analysis of the gravel layers, it can be found that the height of the overflow point and the water inflow calculated by the Darcy-Forchheimer model are consistently less than those of the Darcy model, and the discrepancy between these two models increases as the permeability increases. The necessity of adopting the Darcy-Forchheimer model was explained. The Darcy-Forchheimer model would be applicable in slope engineering applications with highly permeable rock.

Numerical simulation of the free surface and water inflow of a slope, considering the nonlinear flow properties of gravel layers: a case study.

PubMed

Yang, Bin; Yang, Tianhong; Xu, Zenghe; Liu, Honglei; Shi, Wenhao; Yang, Xin

2018-02-01

Groundwater is an important factor of slope stability, and 90% of slope failures are related to the influence of groundwater. In the past, free surface calculations and the prediction of water inflow were based on Darcy's law. However, Darcy's law for steady fluid flow is a special case of non-Darcy flow, and many types of non-Darcy flows occur in practical engineering applications. In this paper, based on the experimental results of laboratory water seepage tests, the seepage state of each soil layer in the open-pit slope of the Yanshan Iron Mine, China, were determined, and the seepage parameters were obtained. The seepage behaviour in the silt layer, fine sand layer, silty clay layer and gravelly clay layer followed the traditional Darcy law, while the gravel layers showed clear nonlinear characteristics. The permeability increases exponentially and the non-Darcy coefficient decreases exponentially with an increase in porosity, and the relation among the permeability, the porosity and the non-Darcy coefficient is investigated. A coupled mathematical model is established for two flow fields, on the basis of Darcy flow in the low-permeability layers and Forchheimer flow in the high-permeability layers. In addition, the effect of the seepage in the slope on the transition from Darcy flow to Forchheimer flow was considered. Then, a numerical simulation was conducted by using finite-element software (FELAC 2.2). The results indicate that the free surface calculated by the Darcy-Forchheimer model is in good agreement with the in situ measurements; however, there is an evident deviation of the simulation results from the measured data when the Darcy model is used. Through a parameter sensitivity analysis of the gravel layers, it can be found that the height of the overflow point and the water inflow calculated by the Darcy-Forchheimer model are consistently less than those of the Darcy model, and the discrepancy between these two models increases as the permeability increases. The necessity of adopting the Darcy-Forchheimer model was explained. The Darcy-Forchheimer model would be applicable in slope engineering applications with highly permeable rock.

Numerical simulation of the free surface and water inflow of a slope, considering the nonlinear flow properties of gravel layers: a case study

PubMed Central

Yang, Bin; Xu, Zenghe; Liu, Honglei; Shi, Wenhao; Yang, Xin

2018-01-01

Groundwater is an important factor of slope stability, and 90% of slope failures are related to the influence of groundwater. In the past, free surface calculations and the prediction of water inflow were based on Darcy's law. However, Darcy's law for steady fluid flow is a special case of non-Darcy flow, and many types of non-Darcy flows occur in practical engineering applications. In this paper, based on the experimental results of laboratory water seepage tests, the seepage state of each soil layer in the open-pit slope of the Yanshan Iron Mine, China, were determined, and the seepage parameters were obtained. The seepage behaviour in the silt layer, fine sand layer, silty clay layer and gravelly clay layer followed the traditional Darcy law, while the gravel layers showed clear nonlinear characteristics. The permeability increases exponentially and the non-Darcy coefficient decreases exponentially with an increase in porosity, and the relation among the permeability, the porosity and the non-Darcy coefficient is investigated. A coupled mathematical model is established for two flow fields, on the basis of Darcy flow in the low-permeability layers and Forchheimer flow in the high-permeability layers. In addition, the effect of the seepage in the slope on the transition from Darcy flow to Forchheimer flow was considered. Then, a numerical simulation was conducted by using finite-element software (FELAC 2.2). The results indicate that the free surface calculated by the Darcy–Forchheimer model is in good agreement with the in situ measurements; however, there is an evident deviation of the simulation results from the measured data when the Darcy model is used. Through a parameter sensitivity analysis of the gravel layers, it can be found that the height of the overflow point and the water inflow calculated by the Darcy–Forchheimer model are consistently less than those of the Darcy model, and the discrepancy between these two models increases as the permeability increases. The necessity of adopting the Darcy–Forchheimer model was explained. The Darcy–Forchheimer model would be applicable in slope engineering applications with highly permeable rock. PMID:29515904

Influence of the Secondary Cell Wall Polymer on the Reassembly, Recrystallization, and Stability Properties of the S-Layer Protein from Bacillus stearothermophilus PV72/p2

PubMed Central

Sára, Margit; Dekitsch, Christine; Mayer, Harald F.; Egelseer, Eva M.; Sleytr, Uwe B.

1998-01-01

The high-molecular-weight secondary cell wall polymer (SCWP) from Bacillus stearothermophilus PV72/p2 is mainly composed of N-acetylglucosamine (GlcNAc) and N-acetylmannosamine (ManNAc) and is involved in anchoring the S-layer protein via its N-terminal region to the rigid cell wall layer. In addition to this binding function, the SCWP was found to inhibit the formation of self-assembly products during dialysis of the guanidine hydrochloride (GHCl)-extracted S-layer protein. The degree of assembly (DA; percent assembled from total S-layer protein) that could be achieved strongly depended on the amount of SCWP added to the GHCl-extracted S-layer protein and decreased from 90 to 10% when the concentration of the SCWP was increased from 10 to 120 μg/mg of S-layer protein. The SCWP kept the S-layer protein in the water-soluble state and favored its recrystallization on solid supports such as poly-l-lysine-coated electron microscopy grids. Derived from the orientation of the base vectors of the oblique S-layer lattice, the subunits had bound with their charge-neutral outer face, leaving the N-terminal region with the polymer binding domain exposed to the ambient environment. From cell wall fragments about half of the S-layer protein could be extracted with 1 M GlcNAc, indicating that the linkage type between the S-layer protein and the SCWP could be related to that of the lectin-polysaccharide type. Interestingly, GlcNAc had an effect on the in vitro self-assembly and recrystallization properties of the S-layer protein that was similar to that of the isolated SCWP. The SCWP generally enhanced the stability of the S-layer protein against endoproteinase Glu-C attack and specifically protected a potential cleavage site in position 138 of the mature S-layer protein. PMID:9696762

Role of specific cations and water entropy on the stability of branched DNA motif structures.

PubMed

Pascal, Tod A; Goddard, William A; Maiti, Prabal K; Vaidehi, Nagarajan

2012-10-11

DNA three-way junctions (TWJs) are important intermediates in various cellular processes and are the simplest of a family of branched nucleic acids being considered as scaffolds for biomolecular nanotechnology. Branched nucleic acids are stabilized by divalent cations such as Mg(2+), presumably due to condensation and neutralization of the negatively charged DNA backbone. However, electrostatic screening effects point to more complex solvation dynamics and a large role of interfacial waters in thermodynamic stability. Here, we report extensive computer simulations in explicit water and salt on a model TWJ and use free energy calculations to quantify the role of ionic character and strength on stability. We find that enthalpic stabilization of the first and second hydration shells by Mg(2+) accounts for 1/3 and all of the free energy gain in 50% and pure MgCl(2) solutions, respectively. The more distorted DNA molecule is actually destabilized in pure MgCl(2) compared to pure NaCl. Notably, the first shell, interfacial waters have very low translational and rotational entropy (i.e., mobility) compared to the bulk, an entropic loss that is overcompensated by increased enthalpy from additional electrostatic interactions with Mg(2+). In contrast, the second hydration shell has anomalously high entropy as it is trapped between an immobile and bulklike layer. The nonmonotonic entropic signature and long-range perturbations of the hydration shells to Mg(2+) may have implications in the molecular recognition of these motifs. For example, we find that low salt stabilizes the parallel configuration of the three-way junction, whereas at normal salt we find antiparallel configurations deduced from the NMR. We use the 2PT analysis to follow the thermodynamics of this transition and find that the free energy barrier is dominated by entropic effects that result from the decreased surface area of the antiparallel form which has a smaller number of low entropy waters in the first monolayer.

Some principles for formation of self-developing dichromate media

NASA Astrophysics Data System (ADS)

Sherstyuk, Valentin P.; Malov, Alexander N.; Maloletov, Sergei M.; Kalinkin, Vyacheslav V.

1991-02-01

The optical information recorded in dichromate gelatin (DCG) layers Induced the information of a latent. image Which rnder the action of water and alcohols transforms to a relief or Phase image. The action of water vapours ma appreciably increase diffraction efficiency. judging from the assumPtion that the introduction of multiatomic alcohols favours the retention of water'' moecu1es in a lager in the amount sufficient for deve1oment on its exposure and stabilization of chromium complexes1 a " self-development" regim has teen worked out. In this case the diffraction efficiency of recorded hc. 1ograms is c''ose to the theoretical limiting value for flatphase r''e c o rdI ng me (J i a. At present the occurence of a Primary latent holographic image (or structure) in dichromated gelatin (DCG) layers has been recognized The diffraction efficiency (DE) detected at a step of holographic recording is low (about 0. 1-IZ). It was shown earlier /j_ 2/ that the treatment bY water vaours or eXPOSUPC Of the layers under conditions of increased humidity results ma growth of DE up to the values enabling the use of DCG to record information in real time /3/j Latent image centres in exposed DC3 layers are predominantly chromium(V) compounds. It is particulary evidenced by the observed correlation between the rate of formation of Cr(V) compounds in a Photo process and the specific change in DE of a latent image /5/.

Ab initio simulation of changes in geometry, electronic structure, and Gibbs free energy caused by dehydration of hydrotalcites containing Cl⁻ and CO₃²⁻ counteranions.

PubMed

Costa, Deyse G; Rocha, Alexandre B; Souza, Wladmir F; Chiaro, Sandra Shirley X; Leitão, Alexandre A

2011-04-07

This ab initio study was performed to better understand the correlation between intercalated water molecules and layered double hydroxides (LDH), as well as the changes that occur by the dehydration process of Zn-Al hydrotalcite-like compounds containing Cl⁻ and CO₃²⁻ counterions. We have verified that the strong interaction among intercalated water molecules, cointercalated anions, and OH groups from hydroxyl layers is reflected in the thermal stability of these compounds. The Zn(2/3)Al(1/3)(OH)₂Cl(1/3)·2/3H₂O hydrotalcite loses all the intercalated water molecules around 125 °C, while the Zn(2/3)Al(1/3)(OH)₂(CO₃)(1/6)·4/6H₂O compound dehydrates at about 175 °C. These values are in good agreement with experimental data. The interlayer interactions were discussed on the basis of electron density difference analyses. Our calculation shows that the electron density in the interlayer region decreases during the dehydration process, inducing the migration of the Cl⁻ anion and the displacement of the hydroxyl layer from adjacent layers. Changes in these compound structures occur to recover part of the hydrogen bonds broken due to the removal of water molecules. It was observed that the chloride ion had initially a lower Löwdin charge (Cl(-0.43)), which has increased its absolute value (Cl(-0.58)) after the water molecules removal, while the charges on carbonate ions remain invariant, leading to the conclusion that the Cl⁻ anion can be more influenced by the amount of water molecules in the interlayer space than the CO₃²⁻ anion in hydrotalcite-like compounds.

Development of a stable cation modified graphene oxide membrane for water treatment

NASA Astrophysics Data System (ADS)

Yu, Wenzheng; (Yet Yu, Tong; Graham, Nigel

2017-12-01

Membranes prepared from layers of graphene oxide (GO) offer substantial advantages over conventional materials for water treatment (e.g. greater flux), but the stability of GO membranes in water has not been achieved until now. In this study the behavior of GO membranes prepared with different quantities and species of cations has been investigated to establish the feasibility of their application in water treatment. A range of cation-modified GO membranes were prepared and exposed to aqueous solutions containing specific chemical constituents. In pure water, unmodified and Na-modified GO membranes were highly unstable, while GO membranes modified with multivalent cations were stable provided there were sufficient quantities of cations present; their relative capability to achieve GO stability was as follows: Al3+  >  Ca2+  >  Mg2+  >  Na+. It is believed that the mechanism of cross-linking, and membrane stability, is via metal-carboxylate chelates and cation-graphite surface interactions (cation-π interaction), and that the latter appears to increase with increasing cation valency. The instability of cation (Ca or Al)-modified GO membranes by NaCl solutions during permeation occurred as Na+ exchanged with the incorporated multivalent cations, but a high content of Al3+ in the GO membrane impeded Al3+/Na+ exchange and thus retained membrane stability. In solutions containing biopolymers representative of surface waters or seawater (protein and polysaccharide solutions), Ca-GO membranes (even with high Ca2+ content) were not stable, while Al-GO membranes were stable if the Al3+ content was sufficiently high; Al-formed membranes also had a greater flux than Ca-GO membranes.

Stability of infinite slopes under transient partially saturated seepage conditions

NASA Astrophysics Data System (ADS)

Godt, Jonathan W.; ŞEner-Kaya, BaşAk; Lu, Ning; Baum, Rex L.

2012-05-01

Prediction of the location and timing of rainfall-induced shallow landslides is desired by organizations responsible for hazard management and warnings. However, hydrologic and mechanical processes in the vadose zone complicate such predictions. Infiltrating rainfall must typically pass through an unsaturated layer before reaching the irregular and usually discontinuous shallow water table. This process is dynamic and a function of precipitation intensity and duration, the initial moisture conditions and hydrologic properties of the hillside materials, and the geometry, stratigraphy, and vegetation of the hillslope. As a result, pore water pressures, volumetric water content, effective stress, and thus the propensity for landsliding vary over seasonal and shorter time scales. We apply a general framework for assessing the stability of infinite slopes under transient variably saturated conditions. The framework includes profiles of pressure head and volumetric water content combined with a general effective stress for slope stability analysis. The general effective stress, or suction stress, provides a means for rigorous quantification of stress changes due to rainfall and infiltration and thus the analysis of slope stability over the range of volumetric water contents and pressure heads relevant to shallow landslide initiation. We present results using an analytical solution for transient infiltration for a range of soil texture and hydrological properties typical of landslide-prone hillslopes and show the effect of these properties on the timing and depth of slope failure. We follow by analyzing field-monitoring data acquired prior to shallow landslide failure of a hillside near Seattle, Washington, and show that the timing of the slide was predictable using measured pressure head and volumetric water content and show how the approach can be used in a forward manner using a numerical model for transient infiltration.

On sharp vorticity gradients in elongating baroclinic eddies and their stabilization with a solid-body rotation

NASA Astrophysics Data System (ADS)

Sutyrin, Georgi G.

2016-06-01

Wide compensated vortices are not able to remain circular in idealized two-layer models unless the ocean depth is assumed to be unrealistically large. Small perturbations on both cyclonic and anticyclonic eddies grow slower if a middle layer with uniform potential vorticity (PV) is added, owing to a weakening of the vertical coupling between the upper and lower layers and a reduction of the PV gradient in the deep layer. Numerical simulations show that the nonlinear development of the most unstable elliptical mode causes self-elongation of the upper vortex core and splitting of the deep PV anomaly into two corotating parts. The emerging tripolar flow pattern in the lower layer results in self-intensification of the fluid rotation in the water column around the vortex center. Further vortex evolution depends on the model parameters and initial conditions, which limits predictability owing to multiple equilibrium attractors existing in the dynamical system. The vortex core strips thin filaments, which roll up into submesoscale vortices to result in substantial mixing at the vortex periphery. Stirring and damping of vorticity by bottom friction are found to be essential for subsequent vortex stabilization. The development of sharp PV gradients leads to nearly solid-body rotation inside the vortex core and formation of transport barriers at the vortex periphery. These processes have important implications for understanding the longevity of real-ocean eddies.

Influence of Near-Surface Severe Plastic Deformation of Mild Steel on the Inhibition Performance of Sodium Molybdate and 1H-Benzotriazole in Artificial Sea Water

NASA Astrophysics Data System (ADS)

Sabet Bokati, Kazem; Dehghanian, Changiz; Babaei, Mahdi

2018-02-01

The effects of near-surface severe plastic deformation (NS-SPD) on the inhibition performance of sodium molybdate (SM) and 1H-benzotriazole (BTA) for mild steel were investigated using weight loss, polarization and electrochemical impedance spectroscopy measurements. The crystal grain size of NS-SPD-processed surface was analyzed by x-ray diffractometry and field emission scanning electron microscopy. A deformed layer with thickness of 20 ± 5 µm was produced on mild steel surface after NS-SPD process due to accumulated strains. The NS-SPD process caused more effective adsorption of corrosion inhibitors due to the fabrication of a surface with a high density of preferential adsorption sites. However, the stability of protective layer was predominantly influenced by the effect of NS-SPD process on inhibition efficiency. The fairly good persistence of protective layer formed on the surface by SM-containing solution and also positive effect of NS-SPD process on adsorption of molybdate ions caused higher inhibition performance for sodium molybdate. However, NS-SPD process encouraged deterioration of protective layer formed on steel surface in the presence of BTA inhibitor. It was ascribed to partial coverage of surface, low stability of adsorbed layer and thus more adsorption of aggressive ions on unprotected area which was uncovered during immersion time.

Surface pressure and elasticity of hydrophobin HFBII layers on the air-water interface: rheology versus structure detected by AFM imaging.

PubMed

Stanimirova, Rumyana D; Gurkov, Theodor D; Kralchevsky, Peter A; Balashev, Konstantin T; Stoyanov, Simeon D; Pelan, Eddie G

2013-05-21

Here, we combine experiments with Langmuir trough and atomic force microscopy (AFM) to investigate the reasons for the special properties of layers from the protein HFBII hydrophobin spread on the air-water interface. The hydrophobin interfacial layers possess the highest surface dilatational and shear elastic moduli among all investigated proteins. The AFM images show that the spread HFBII layers are rather inhomogeneous, (i.e., they contain voids, monolayer and multilayer domains). A continuous compression of the layer leads to filling the voids and transformation of a part of the monolayer into a trilayer. The trilayer appears in the form of large surface domains, which can be formed by folding and subduction of parts from the initial monolayer. The trilayer appears also in the form of numerous submicrometer spots, which can be obtained by forcing protein molecules out of the monolayer and their self-assembly into adjacent pimples. Such structures are formed because not only the hydrophobic parts, but also the hydrophilic parts of the HFBII molecules can adhere to each other in the water medium. If a hydrophobin layer is subjected to oscillations, its elasticity considerably increases, up to 500 mN/m, which can be explained with compaction. The relaxation of the layer's tension after expansion or compression follows the same relatively simple law, which refers to two-dimensional diffusion of protein aggregates within the layer. The characteristic diffusion time after compression is longer than after expansion, which can be explained with the impedence of diffusion in the more compact interfacial layer. The results shed light on the relation between the mesoscopic structure of hydrophobin interfacial layers and their unique mechanical properties that find applications for the production of foams and emulsions of extraordinary stability; for the immobilization of functional molecules at surfaces, and as coating agents for surface modification.

Diverse and tunable electronic structures of single-layer metal phosphorus trichalcogenides for photocatalytic water splitting

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

Liu, Jian; Beijing Computational Science Research Center, Beijing 100084; College of Electrical and Information Engineering, Hunan Institute of Engineering, Xiangtan 411105, Hunan

2014-02-07

The family of bulk metal phosphorus trichalcogenides (APX{sub 3}, A = M{sup II}, M{sub 0.5}{sup I}M{sub 0.5}{sup III}; X = S, Se; M{sup I}, M{sup II}, and M{sup III} represent Group-I, Group-II, and Group-III metals, respectively) has attracted great attentions because such materials not only own magnetic and ferroelectric properties, but also exhibit excellent properties in hydrogen storage and lithium battery because of the layered structures. Many layered materials have been exfoliated into two-dimensional (2D) materials, and they show distinct electronic properties compared with their bulks. Here we present a systematical study of single-layer metal phosphorus trichalcogenides by density functionalmore » theory calculations. The results show that the single layer metal phosphorus trichalcogenides have very low formation energies, which indicates that the exfoliation of single layer APX{sub 3} should not be difficult. The family of single layer metal phosphorus trichalcogenides exhibits a large range of band gaps from 1.77 to 3.94 eV, and the electronic structures are greatly affected by the metal or the chalcogenide atoms. The calculated band edges of metal phosphorus trichalcogenides further reveal that single-layer ZnPSe{sub 3}, CdPSe{sub 3}, Ag{sub 0.5}Sc{sub 0.5}PSe{sub 3}, and Ag{sub 0.5}In{sub 0.5}PX{sub 3} (X = S and Se) have both suitable band gaps for visible-light driving and sufficient over-potentials for water splitting. More fascinatingly, single-layer Ag{sub 0.5}Sc{sub 0.5}PSe{sub 3} is a direct band gap semiconductor, and the calculated optical absorption further convinces that such materials own outstanding properties for light absorption. Such results demonstrate that the single layer metal phosphorus trichalcogenides own high stability, versatile electronic properties, and high optical absorption, thus such materials have great chances to be high efficient photocatalysts for water-splitting.« less

BELINDA: Broadband Emission Lidar with Narrowband Determination of Absorption. A new concept for measuring water vapor and temperature profiles

NASA Technical Reports Server (NTRS)

Theopold, F. A.; Weitkamp, C.; Michaelis, W.

1992-01-01

We present a new concept for differential absorption lidar measurements of water vapor and temperature profiles. The idea is to use one broadband emission laser and a narrowband filter system for separation of the 'online' and 'offline' return signals. It is shown that BELINDA offers improvements as to laser emission shape and stability requirements, background suppression, and last and most important a significant reduction of the influence of Rayleigh scattering. A suitably designed system based on this concept is presented, capable of measuring water vapor or temperature profiles throughout the planetary boundary layer.

Synthesis of robust water-soluble ZnS:Mn/SiO2 core/shell nanoparticles

NASA Astrophysics Data System (ADS)

Sun, Jing; Zhuang, Jiaqi; Guan, Shaowei; Yang, Wensheng

2008-04-01

Water-soluble Mn doped ZnS (ZnS:Mn) nanocrystals synthesized by using 3-mercaptopropionic acid (MPA) as stabilizer were homogeneously coated with a dense silica shell through a multi-step procedure. First, 3-mercaptopropyl triethoxy silane (MPS) was used to replace MPA on the particle surface to form a vitreophilic layer for further silica deposition under optimal experimental conditions. Then a two-step silica deposition was performed to form the final water-soluble ZnS:Mn/SiO2 core/shell nanoparticles. The as-prepared core/shell nanoparticles show little change in fluorescence intensity in a wide range of pH value.

Mechanics of Boundary Layer Transition. Part 5: Boundary Layer Stability theory in incompressible and compressible flow

NASA Technical Reports Server (NTRS)

Mack, L. M.

1967-01-01

The fundamentals of stability theory, its chief results, and the physical mechanisms at work are presented. The stability theory of the laminar boundary determines whether a small disturbance introduced into the boundary layer will amplify or damp. If the disturbance damps, the boundary layer remains laminar. If the disturbance amplifies, and by a sufficient amount, then transition to turbulence eventually takes place. The stability theory establishes those states of the boundary layer which are most likely to lead to transition, identifys those frequencies which are the most dangerous, and indicates how the external parameters can best be changed to avoid transition.

Erosion Performance of Gadolinium Zirconate-Based Thermal Barrier Coatings Processed by Suspension Plasma Spray

NASA Astrophysics Data System (ADS)

Mahade, Satyapal; Curry, Nicholas; Björklund, Stefan; Markocsan, Nicolaie; Nylén, Per; Vaßen, Robert

2017-01-01

7-8 wt.% Yttria-stabilized zirconia (YSZ) is the standard thermal barrier coating (TBC) material used by the gas turbines industry due to its excellent thermal and thermo-mechanical properties up to 1200 °C. The need for improvement in gas turbine efficiency has led to an increase in the turbine inlet gas temperature. However, above 1200 °C, YSZ has issues such as poor sintering resistance, poor phase stability and susceptibility to calcium magnesium alumino silicates (CMAS) degradation. Gadolinium zirconate (GZ) is considered as one of the promising top coat candidates for TBC applications at high temperatures (>1200 °C) due to its low thermal conductivity, good sintering resistance and CMAS attack resistance. Single-layer 8YSZ, double-layer GZ/YSZ and triple-layer GZdense/GZ/YSZ TBCs were deposited by suspension plasma spray (SPS) process. Microstructural analysis was carried out by scanning electron microscopy (SEM). A columnar microstructure was observed in the single-, double- and triple-layer TBCs. Phase analysis of the as-sprayed TBCs was carried out using XRD (x-ray diffraction) where a tetragonal prime phase of zirconia in the single-layer YSZ TBC and a cubic defect fluorite phase of GZ in the double and triple-layer TBCs was observed. Porosity measurements of the as-sprayed TBCs were made by water intrusion method and image analysis method. The as-sprayed GZ-based multi-layered TBCs were subjected to erosion test at room temperature, and their erosion resistance was compared with single-layer 8YSZ. It was shown that the erosion resistance of 8YSZ single-layer TBC was higher than GZ-based multi-layered TBCs. Among the multi-layered TBCs, triple-layer TBC was slightly better than double layer in terms of erosion resistance. The eroded TBCs were cold-mounted and analyzed by SEM.

Efficient defluoridation of water using reusable nanocrystalline layered double hydroxides impregnated polystyrene anion exchanger.

PubMed

Cai, Jianguo; Zhang, Yanyang; Pan, Bingcai; Zhang, Weiming; Lv, Lu; Zhang, Quanxing

2016-10-01

Water decontamination from fluoride is still a challenging task of global concern. Recently, Al-based layered double hydroxides (LDHs) have been extensively studied for specific fluoride adsorption from water. Unfortunately, they cannot be readily applied in scaled-up application due to their ultrafine particles as well as the regeneration issues caused by their poor stability at alkaline pHs. Here, we developed a novel (LDH)-based hybrid adsorbent, i.e., LALDH-201, by impregnating nanocrystalline Li/Al LDHs (LADLH) inside a commercial polystyrene anion exchanger D201. TEM image and XRD spectra of the resultant nanocomposite confirmed that the LDHs particles were nanosized inside the pores of D201 of highly crystalline nature and well-ordered layer structure. After impregnation, the chemical and mechanical stability of LALDH were significantly improved against pH variation, facilitating its application at a wide pH range (3.5-12). Fluoride adsorption onto LALDH-201 was compared to D201 and activated alumina, evidencing the preferable removal fluoride of LALDH-201. Fluoride adsorption onto LALDH-201 followed pseudo-second-order model, with the maximum capacity (62.5 mg/g from the Sips model) much higher than the other two adsorbents. Fixed-bed adsorption run indicated the qualified treatable volume of the fluoride contaminated groundwater (4.1 mg/L initially) with LALDH-201 was about 11 times as much as with the anion exchanger D201 when the breakthrough point was set as 1.5 mg/L. The capacity of LALDH-201 could be effectively refreshed for continuous column operation without observable loss by using the mixed solution of 0.01 M NaOH + 1 M NaCl. The above results suggested that the hybrid adsorbent LALDH-201 is very promising for water defluoridation in scaled-up application. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of hydrogen on the device performance and stability characteristics of amorphous InGaZnO thin-film transistors with a SiO2/SiNx/SiO2 buffer

NASA Astrophysics Data System (ADS)

Han, Ki-Lim; Ok, Kyung-Chul; Cho, Hyeon-Su; Oh, Saeroonter; Park, Jin-Seong

2017-08-01

We investigate the influence of the multi-layered buffer consisting of SiO2/SiNx/SiO2 on amorphous InGaZnO (a-IGZO) thin-film transistors (TFTs). The multi-layered buffer inhibits permeation of water from flexible plastic substrates and prevents degradation of overlying organic layers. The a-IGZO TFTs with a multi-layered buffer suffer less positive bias temperature stress instability compared to the device with a single SiO2 buffer layer after annealing at 250 °C. Hydrogen from the SiNx layer diffuses into the active layer and reduces electron trapping at loosely bound oxygen defects near the SiO2/a-IGZO interface. Quantitative analysis shows that a hydrogen density of 1.85 × 1021 cm-3 is beneficial to reliability. However, the multi-layered buffer device annealed at 350 °C resulted in conductive characteristics due to the excess carrier concentration from the higher hydrogen density of 2.12 × 1021 cm-3.

Structural properties of hydration shell around various conformations of simple polypeptides.

PubMed

Czapiewski, Dariusz; Zielkiewicz, Jan

2010-04-08

In this paper we investigate structural properties of water within the solvation shell around the peptide core created by a well-defined conformation of polypeptide chain. The following secondary structures are investigated: linear (straight chain), and three helices PII (polyproline-like), 3(10), and alpha. We propose using the two-particle contribution to entropy as a rational measure of the water structural ordering within the solvation layer. This contribution divides into two terms, depending on the peptide-water and water-water interactions, respectively, and in this paper both terms are investigated. The structure of "solvation" water is described by the second term, and therefore it mainly attracts our attention. Determination of this term, however, is not an easy task, requiring some controversial approximations. Therefore, we have transformed this term to the form of some rational parameter which measures the local structural ordering of water within the solvation shell. Moreover, the results of several independent investigations are reported: we adopt the harmonic approximation for an independent estimation of the water entropy within the solvation shell, and we also study structure of the water-water hydrogen bond network, mean geometry of a single hydrogen bond, the self-diffusion coefficients (both translational and rotational) of water, and the mean lifetimes of water-water and water-peptide hydrogen bonds. All the obtained results lead to the conclusion that the local structure of water within the solvation shell changes only slightly in comparison to the bulk one. If so, the measure of local water ordering proposed by us is exploited with the aim to gain the deeper insight on the structural properties of "solvation" water. It has been shown that this parameter can be factored into three terms, which measure translational, configurational, and orientational ordering, respectively. Using this factoring, the ordering map for a precise description of the water local ordering has been built. An interesting correlation is observed: the points on this map lie approximately on the straight line, while the linear conformations clearly deviate from the general tendency. Further analysis of the obtained results allows us to express the supposition that an increasing local ordering of water around given secondary structure corresponds to an increasing relative stability of this structure in aqueous solution. Analyzing the geometry of the water-water hydrogen bond network within the solvation layer, we find some systematic deviations of this geometry from the bulk water properties. We also observe that the alanine peptides (excluding the linear form) disturb the hydrogen bond network in the less range, and in another way than the various conformations of polyglycine, while the linear form of polyalanine behaves very similarly to the glycine ones. Next, investigating the dynamic properties, we also conclude that water near the peptide surface creates a pseudorigid structure, a "halo" around the peptide core. This "halo" is stabilized by slightly higher energy of the hydrogen bonds network: we have found that within this region the hydrogen bonds network is slightly less distorted, the water-water hydrogen bonds are a little more stable and their mean lifetime is clearly longer that that of bulk water. Significant differences between the alanine- and glycine-based polypeptides are also visible. It has also been found that this solvation layer interacts with the polyalanine in another way than with polyglycine. Although in the case of the glycine-based polypeptide this layer slides relatively freely over the peptide surface, for the alanine-based polypeptide this sliding is strongly hindered by the presence of the methyl groups, and this effect is additionally enhanced by a rise in the solvation layer rigidity. Thus, the survey of various dynamic properties allows us to perceive and to explain distinct differences in behavior of water within the solvation shell around both glycine and alanine peptides.

Surfactant-free carnauba wax dispersion and its use for layer-by-layer assembled protective surface coatings on wood

NASA Astrophysics Data System (ADS)

Lozhechnikova, Alina; Bellanger, Hervé; Michen, Benjamin; Burgert, Ingo; Österberg, Monika

2017-02-01

Protection from liquid water and UV radiation are equally important, and a sophisticated approach is needed when developing surface coatings that preserve the natural and well-appreciated aesthetic appearance of wood. In order to prevent degradation and prolong the service life of timber, a protective coating was assembled using carnauba wax particles and zinc oxide nanoparticles via layer-by-layer deposition in water. For this purpose, a facile sonication route was developed to produce aqueous wax dispersion without any surfactants or stabilizers. The suspension was stable above pH 4 due to the electrostatic repulsion between the negatively charged wax particles. The particle size could be controlled by the initial wax concentration with average particle sizes ranging from 260 to 360 nm for 1 and 10 g/L, respectively. The deposition of wax particles onto the surface of spruce wood introduced additional roughness to the wood surface at micron level, while zinc oxide provided nano roughness and UV-absorbing properties. In addition to making wood superhydrophobic, this novel multilayer coating enhanced the natural moisture buffering capability of spruce. Moreover, wood surfaces prepared in this fashion showed a significant reduction in color change after exposure to UV light. A degradation of the wax through photocatalytic activity of the ZnO particles was measured by FTIR, indicating that further studies are required to achieve long-term stability. Nevertheless, the developed coating showed a unique combination of superhydrophobicity and excellent moisture buffering ability and some UV protection, all achieved using an environmentally friendly coating process, which is beneficial to retain the natural appearance of wood and improve indoor air quality and comfort.

Computational and Experimental Study of the Transient Transport Phenomena in a Full-Scale Twin-Roll Continuous Casting Machine

NASA Astrophysics Data System (ADS)

Xu, Mianguang; Li, Zhongyang; Wang, Zhaohui; Zhu, Miaoyong

2017-02-01

To gain a fundamental understanding of the transient fluid flow in twin-roll continuous casting, the current paper applies both large eddy simulation (LES) and full-scale water modeling experiments to investigate the characteristics of the top free surface, stirring effect of the roll rotation, boundary layer fluctuations, and backflow stability. The results show that, the characteristics of the top free surface and the flow field in the wedge-shaped pool region are quite different with/without the consideration of the roll rotation. The roll rotation decreases the instantaneous fluctuation range of the top free surface, but increases its horizontal velocity. The stirring effect of the roll rotating makes the flow field more homogenous and there exists clear shear flow on the rotating roll surface. The vortex shedding induced by the Kármán Vortex Street from the submerged entry nozzle (SEN) causes the "velocity magnitude wave" and strongly influences the boundary layer stability and the backflow stability. The boundary layer fluctuations or the "velocity magnitude wave" induced by the vortex shedding could give rise to the internal porosity. In strip continuous casting process, the vortex shedding phenomenon indicates that the laminar flow can give rise to instability and that it should be made important in the design of the feeding system and the setting of the operating parameters.

Simultaneous protection of organic p- and n-channels in complementary inverter from aging and bias-stress by DNA-base guanine/Al2O3 double layer.

PubMed

Lee, Junyeong; Hwang, Hyuncheol; Min, Sung-Wook; Shin, Jae Min; Kim, Jin Sung; Jeon, Pyo Jin; Lee, Hee Sung; Im, Seongil

2015-01-28

Although organic field-effect transistors (OFETs) have various advantages of lightweight, low-cost, mechanical flexibility, and nowadays even higher mobility than amorphous Si-based FET, stability issue under bias and ambient condition critically hinder its practical application. One of the most detrimental effects on organic layer comes from penetrated atmospheric species such as oxygen and water. To solve such degradation problems, several molecular engineering tactics are introduced: forming a kinetic barrier, lowering the level of molecule orbitals, and increasing the band gap. However, direct passivation of organic channels, the most promising strategy, has not been reported as often as other methods. Here, we resolved the ambient stability issues of p-type (heptazole)/or n-type (PTCDI-C13) OFETs and their bias-stability issues at once, using DNA-base small molecule guanine (C5H5N5O)/Al2O3 bilayer. The guanine protects the organic channels as buffer/and H getter layer between the channels and capping Al2O3, whereas the oxide capping resists ambient molecules. As a result, both p-type and n-type OFETs are simultaneously protected from gate-bias stress and 30 days-long ambient aging, finally demonstrating a highly stable, high-gain complementary-type logic inverter.

Photoelectrolysis at the oxide-electrolyte interface as interpreted through the 'transition' layer model

NASA Astrophysics Data System (ADS)

Kalia, R. K.; Weber, Michael F.; Schumacher, L.; Dignam, M. J.

1980-12-01

A transition layer model of the oxide-electrolyte interface, proposed earlier by one of us, is outlined and then examined in the light of experimental data relating primarily to photoelectrolysis of water at semiconducting oxide electrodes. The model provides useful insight into the behaviour of the system and allows a calculation of thc minimum bias potential needed for photoelectrolysis, thus illuminating the origin of the requirement for such an external bias. In order to electrolyse water without a bias, the model requires an n-type oxide to be sufficiently reduced so that it is thermodynamically capable of chemically reducing water to produce hydrogen at 1 atm pressure. Similarly, for bias-free operation, a p-type metal oxide must be thermodynamically unstable with respect to the release of oxygen at 1 atm pressure. In the face of these requirements it is apparent that oxide stability is bound to be in general a serious problem for nonstoichiometric single metal oxides.

Interfacial engineering of metal-insulator-semiconductor junctions for efficient and stable photoelectrochemical water oxidation

PubMed Central

Digdaya, Ibadillah A.; Adhyaksa, Gede W. P.; Trześniewski, Bartek J.; Garnett, Erik C.; Smith, Wilson A.

2017-01-01

Solar-assisted water splitting can potentially provide an efficient route for large-scale renewable energy conversion and storage. It is essential for such a system to provide a sufficiently high photocurrent and photovoltage to drive the water oxidation reaction. Here we demonstrate a photoanode that is capable of achieving a high photovoltage by engineering the interfacial energetics of metal–insulator–semiconductor junctions. We evaluate the importance of using two metals to decouple the functionalities for a Schottky contact and a highly efficient catalyst. We also illustrate the improvement of the photovoltage upon incidental oxidation of the metallic surface layer in KOH solution. Additionally, we analyse the role of the thin insulating layer to the pinning and depinning of Fermi level that is responsible to the resulting photovoltage. Finally, we report the advantage of using dual metal overlayers as a simple protection route for highly efficient metal–insulator–semiconductor photoanodes by showing over 200 h of operational stability. PMID:28660883

Water-Gated n-Type Organic Field-Effect Transistors for Complementary Integrated Circuits Operating in an Aqueous Environment.

PubMed

Porrazzo, Rossella; Luzio, Alessandro; Bellani, Sebastiano; Bonacchini, Giorgio Ernesto; Noh, Yong-Young; Kim, Yun-Hi; Lanzani, Guglielmo; Antognazza, Maria Rosa; Caironi, Mario

2017-01-31

The first demonstration of an n-type water-gated organic field-effect transistor (WGOFET) is here reported, along with simple water-gated complementary integrated circuits, in the form of inverting logic gates. For the n-type WGOFET active layer, high-electron-affinity organic semiconductors, including naphthalene diimide co-polymers and a soluble fullerene derivative, have been compared, with the latter enabling a high electric double layer capacitance in the range of 1 μF cm -2 in full accumulation and a mobility-capacitance product of 7 × 10 -3 μF/V s. Short-term stability measurements indicate promising cycling robustness, despite operating the device in an environment typically considered harsh, especially for electron-transporting organic molecules. This work paves the way toward advanced circuitry design for signal conditioning and actuation in an aqueous environment and opens new perspectives in the implementation of active bio-organic interfaces for biosensing and neuromodulation.

Water-Gated n-Type Organic Field-Effect Transistors for Complementary Integrated Circuits Operating in an Aqueous Environment

PubMed Central

2017-01-01

The first demonstration of an n-type water-gated organic field-effect transistor (WGOFET) is here reported, along with simple water-gated complementary integrated circuits, in the form of inverting logic gates. For the n-type WGOFET active layer, high-electron-affinity organic semiconductors, including naphthalene diimide co-polymers and a soluble fullerene derivative, have been compared, with the latter enabling a high electric double layer capacitance in the range of 1 μF cm–2 in full accumulation and a mobility–capacitance product of 7 × 10–3 μF/V s. Short-term stability measurements indicate promising cycling robustness, despite operating the device in an environment typically considered harsh, especially for electron-transporting organic molecules. This work paves the way toward advanced circuitry design for signal conditioning and actuation in an aqueous environment and opens new perspectives in the implementation of active bio-organic interfaces for biosensing and neuromodulation. PMID:28180187

Enhanced electrical stability of flexible indium tin oxide films prepared on stripe SiO 2 buffer layer-coated polymer substrates by magnetron sputtering

NASA Astrophysics Data System (ADS)

Yu, Zhi-nong; Zhao, Jian-jian; Xia, Fan; Lin, Ze-jiang; Zhang, Dong-pu; Leng, Jian; Xue, Wei

2011-03-01

The electrical stability of flexible indium tin oxide (ITO) films fabricated on stripe SiO 2 buffer layer-coated polyethylene terephthalate (PET) substrates by magnetron sputtering was investigated by the bending test. The ITO thin films with stripe SiO 2 buffer layer under bending have better electrical stability than those with flat SiO 2 buffer layer and without buffer layer. Especially in inward bending text, the ITO thin films with stripe SiO 2 buffer layer only have a slight resistance change when the bending radius r is not less than 8 mm, while the resistances of the films with flat SiO 2 buffer layer and without buffer layer increase significantly at r = 16 mm with decreasing bending radius. This improvement of electrical stability in bending test is due to the small mismatch factor α in ITO-SiO 2, the enhanced interface adhesion and the balance of residual stress. These results indicate that the stripe SiO 2 buffer layer is suited to enhance the electrical stability of flexible ITO film under bending.

Evaluation of thermal stability in spectrally selective few-layer metallo-dielectric structures for solar thermophotovoltaics

NASA Astrophysics Data System (ADS)

Shimizu, Makoto; Kohiyama, Asaka; Yugami, Hiroo

2018-06-01

The thermal stability of spectrally selective few-layer metallo-dielectric structures is evaluated to analyze their potential as absorber and emitter materials in solar thermophotovoltaic (STPV) systems. High-efficiency (e.g., STPV) systems require materials with spectrally selective properties, especially at high temperatures (>1273 K). Aiming to develop such materials for high-temperature applications, we propose a few-layer structure composed of a refractory metal (i.e., Mo) nanometric film sandwiched between the layers of a dielectric material (i.e., hafnium oxide, HfO2) deposited on a Mo bulk substrate. In vacuum conditions (<5 × 10-2 Pa), the few-layer structure shows thermal stability at 1423 K for at least 1 h. At 1473 K, the spectral selectivity was degraded. This could have been caused by the oxidation of the Mo thin film by the residual oxygen through the grain boundaries of the upper HfO2 layer. This experiment showed the potential stability of few-layer structures for applications working at temperatures greater than 1273 K as well as the degradation mechanism of the few-layer structure. This characteristic is expected to help improve the thermal stability in few-layer structures further.

Characterization of the Marine Boundary Layer and the Trade-Wind Inversion over the Sub-tropical North Atlantic

NASA Astrophysics Data System (ADS)

Carrillo, J.; Guerra, J. C.; Cuevas, E.; Barrancos, J.

2016-02-01

The stability of the lower troposphere along the east side of the sub-tropical North Atlantic is analyzed and characterized using upper air meteorological long-term records at the Canary Islands (Tenerife), Madeira (Madeira) and Azores (Terceira) archipelagos. The most remarkable characteristic is the strong stratification observed in the lower troposphere, with a strengthening of stability centred at levels near 900 and 800 hPa in a significant percentage of soundings (ranging from 17 % in Azores to 33 % in Güimar, Canary Islands). We show that this double structure is associated with the top of the marine boundary layer (MBL) and the trade-wind inversion (TWI) respectively. The top of the MBL coincides with the base of the first temperature inversion (≈ 900 hPa) where a sharp change in water vapour mixing ratio is observed. A second temperature inversion is found near 800 hPa, which is characterized by a large directional wind shear just above the inversion layer, tied to the TWI. We find that seasonal and latitudinal variations of the height and strength of both temperature inversions are driven by large-scale subsiding air from the upper troposphere associated with the descent branch of the Hadley cell. Increased general subsidence in summertime enhances stability in the lower troposphere, more markedly in the southern stations, where the inversion-layer heights are found at lower levels enhancing the main features of these two temperature inversions. A simple conceptual model that explains the lower tropospheric inversion enhancement by subsidence is proposed.

Effect of guar gum and salt concentrations on drag reduction and shear degradation properties of turbulent flow of water in a pipe.

PubMed

Sokhal, Kamaljit Singh; Gangacharyulu, Dasaroju; Bulasara, Vijaya Kumar

2018-02-01

Concentrated solutions of guar gum in water (1000-3000ppm) with and without KCl salt (1000-4000ppm) were injected near the wall for a short period (2.5min) to investigate their effect on drag reduction in turbulent flow of water through a pipe (Re≈17000-45000). Relative to bulk solution, the concentrations of polymer and salt were 50-150ppm and 50-200ppm, respectively. A drag reduction of 71.45% was observed for 3000ppm of biopolymer without salt. Guar gum experienced mechanical degradation under high shear conditions and addition of KCl improved shear stability up to 47% (for Re≈45000). A polymer concentration of 3000ppm and salt concentration of 2000ppm in the injection fluid were found to be optimum for achieving the highest drag reduction with better shear stability. Results indicated that boundary layer injection shows better drag reduction ability than pre-mixed solutions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Boundary Layer Height and Buoyancy Determine the Horizontal Scale of Convective Self-Aggregation

DOE PAGES

Yang, Da

2018-01-24

Organized rainstorms and their associated overturning circulations can self-emerge over an ocean surface with uniform temperature in cloud-resolving simulations. This phenomenon is referred to as convective self-aggregation. Convective self-aggregation is argued to be an important building block for tropical weather systems and may help regulate tropical atmospheric humidity and thereby tropical climate stability. Here the author presents a boundary layer theory for the horizontal scale λ of 2D (x, z) convective self-aggregation by considering both the momentum and energy constraints for steady circulations. This theory suggests that λ scales with the product of the boundary layer height h and themore » square root of the amplitude of density variation between aggregated moist and dry regions in the boundary layer, and that this density variation mainly arises from the moisture variation due to the virtual effect of water vapor. Furthermore, this theory predicts the following: 1) the order of magnitude of λ is ~2000 km, 2) the aspect ratio of the boundary layer λ/h increases with surface warming, and 3) λ decreases when the virtual effect of water vapor is disabled. These predictions are confirmed using a sui te of cloud-resolving simulations spanning a wide range of climates.« less

Boundary Layer Height and Buoyancy Determine the Horizontal Scale of Convective Self-Aggregation

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

Yang, Da

Organized rainstorms and their associated overturning circulations can self-emerge over an ocean surface with uniform temperature in cloud-resolving simulations. This phenomenon is referred to as convective self-aggregation. Convective self-aggregation is argued to be an important building block for tropical weather systems and may help regulate tropical atmospheric humidity and thereby tropical climate stability. Here the author presents a boundary layer theory for the horizontal scale λ of 2D (x, z) convective self-aggregation by considering both the momentum and energy constraints for steady circulations. This theory suggests that λ scales with the product of the boundary layer height h and themore » square root of the amplitude of density variation between aggregated moist and dry regions in the boundary layer, and that this density variation mainly arises from the moisture variation due to the virtual effect of water vapor. Furthermore, this theory predicts the following: 1) the order of magnitude of λ is ~2000 km, 2) the aspect ratio of the boundary layer λ/h increases with surface warming, and 3) λ decreases when the virtual effect of water vapor is disabled. These predictions are confirmed using a sui te of cloud-resolving simulations spanning a wide range of climates.« less

Fabrication and improved photoelectrochemical properties of a transferred GaN-based thin film with InGaN/GaN layers.

PubMed

Cao, Dezhong; Xiao, Hongdi; Gao, Qingxue; Yang, Xiaokun; Luan, Caina; Mao, Hongzhi; Liu, Jianqiang; Liu, Xiangdong

2017-08-17

Herein, a lift-off mesoporous GaN-based thin film, which consisted of a strong phase-separated InGaN/GaN layer and an n-GaN layer, was fabricated via an electrochemical etching method in a hydrofluoric acid (HF) solution for the first time and then transferred onto quartz or n-Si substrates, acting as photoanodes during photoelectrochemical (PEC) water splitting in a 1 M NaCl aqueous solution. Compared to the as-grown GaN-based film, the transferred GaN-based thin films possess higher and blue-shifted light emission, presumably resulting from an increase in the surface area and stress relaxation in the InGaN/GaN layer embedded on the mesoporous n-GaN. The properties such as (i) high photoconversion efficiency, (ii) low turn-on voltage (-0.79 V versus Ag/AgCl), and (iii) outstanding stability enable the transferred films to have excellent PEC water splitting ability. Furthermore, as compared to the film transferred onto the quartz substrate, the film transferred onto the n-Si substrate exhibits higher photoconversion efficiency (2.99% at -0.10 V) due to holes (h + ) in the mesoporous n-GaN layer that originate from the n-Si substrate.

Onset and localisation of convection during transient growth of mushy sea ice

NASA Astrophysics Data System (ADS)

Wells, Andrew; Hitchen, Joe

2017-11-01

More than 20 million square kilometres of the polar oceans freeze over each year to form sea ice. Sea ice is a mushy layer: a reactive, porous, multiphase material consisting of ice crystals bathed in liquid brine. Atmospheric cooling generates a density gradient in the interstitial brine, which can drive convection and rejection of brine from the sea ice to force ocean circulation and mixing. We use linear stability analysis and nonlinear numerical simulations to consider the convection in a transiently growing mushy layer. An initial salt water layer is cooled from above via a linearised thermal exchange with the atmosphere, and generates a growing mushy layer with the porosity varying in space and time. We determine how the critical porous-medium Rayleigh number for the onset of convection varies with the surface cooling rate, and the initial temperature and salinity of the solidifying salt water. Differences in the cooling conditions modify the structure of the ice and the resulting convection cells. Weak cooling leads to full-depth convection through ice with slowly varying porosity, whilst stronger cooling leads to localised convection confined to a highly permeable basal layer. These results provide insight into the onset of convective brine drainage from growing sea ice.

Ternary liquid mixtures control the multiplicity, shape and internal structure of emulsion droplets

NASA Astrophysics Data System (ADS)

Haase, Martin F.; Brujic, Jasna

2014-03-01

It is important to control the shape, internal structure and stability of emulsion droplets for drug delivery, biochemical assays, and the design of materials with novel physical properties. Successful methods involve the mechanical manipulation of the flow of oil in water using complex microfluidic devices to make multiple emulsions with a sequential introduction of specific reactants. Instead, here we show how the thermodynamics of immiscible liquid mixtures tailor emulsions using a single dripping instability. For example, the initial composition and choice of surfactant govern the multiplicity of concentric alternating oil and water layers inside the droplets. Stabilizing ternary droplets using nanoparticles gives rise to a plethora of shapes whose geometry is defined by the deformability of the shell and the flow rate. Another option is to incorporate lipids to the multiple emulsion droplet, which form vesicles upon expulsion of the inner water droplets. Depending on the number of initial water droplets, these vesicles eventually form complex hollow topologies, which can be used as junctions or scaffolds for the self-assembly of colloidal particles in the future.

Effect of dielectric layers on device stability of pentacene-based field-effect transistors.

PubMed

Di, Chong-an; Yu, Gui; Liu, Yunqi; Guo, Yunlong; Sun, Xiangnan; Zheng, Jian; Wen, Yugeng; Wang, Ying; Wu, Weiping; Zhu, Daoben

2009-09-07

We report stable organic field-effect transistors (OFETs) based on pentacene. It was found that device stability strongly depends on the dielectric layer. Pentacene thin-film transistors based on the bare or polystyrene-modified SiO(2) gate dielectrics exhibit excellent electrical stabilities. In contrast, the devices with the octadecyltrichlorosilane (OTS)-treated SiO(2) dielectric layer showed the worst stabilities. The effects of the different dielectrics on the device stabilities were investigated. We found that the surface energy of the gate dielectric plays a crucial role in determining the stability of the pentacene thin film, device performance and degradation of electrical properties. Pentacene aggregation, phase transfer and film morphology are also important factors that influence the device stability of pentacene devices. As a result of the surface energy mismatch between the dielectric layer and organic semiconductor, the electronic performance was degraded. Moreover, when pentacene was deposited on the OTS-treated SiO(2) dielectric layer with very low surface energy, pentacene aggregation occurred and resulted in a dramatic decrease of device performance. These results demonstrated that the stable OFETs could be obtained by using pentacene as a semiconductor layer.

Antibody adsorption on the surface of water studied by neutron reflection

PubMed Central

Li, Zongyi; Holman, Robert; Pan, Fang; Campbell, Richard A.; Campana, Mario; Li, Peixun; Webster, John R. P.; Bishop, Steven; Narwal, Rojaramani; Uddin, Shahid

2017-01-01

ABSTRACT Surface and interfacial adsorption of antibody molecules could cause structural unfolding and desorbed molecules could trigger solution aggregation, resulting in the compromise of physical stability. Although antibody adsorption is important and its relevance to many mechanistic processes has been proposed, few techniques can offer direct structural information about antibody adsorption under different conditions. The main aim of this study was to demonstrate the power of neutron reflection to unravel the amount and structural conformation of the adsorbed antibody layers at the air/water interface with and without surfactant, using a monoclonal antibody ‘COE-3′ as the model. By selecting isotopic contrasts from different ratios of H2O and D2O, the adsorbed amount, thickness and extent of the immersion of the antibody layer could be determined unambiguously. Upon mixing with the commonly-used non-ionic surfactant Polysorbate 80 (Tween 80), the surfactant in the mixed layer could be distinguished from antibody by using both hydrogenated and deuterated surfactants. Neutron reflection measurements from the co-adsorbed layers in null reflecting water revealed that, although the surfactant started to remove antibody from the surface at 1/100 critical micelle concentration (CMC) of the surfactant, complete removal was not achieved until above 1/10 CMC. The neutron study also revealed that antibody molecules retained their globular structure when either adsorbed by themselves or co-adsorbed with the surfactant under the conditions studied. PMID:28353420

Organization of Lipids in the Tear Film: A Molecular-Level View

PubMed Central

Wizert, Alicja; Iskander, D. Robert; Cwiklik, Lukasz

2014-01-01

Biophysical properties of the tear film lipid layer are studied at the molecular level employing coarse grain molecular dynamics (MD) simulations with a realistic model of the human tear film. In this model, polar lipids are chosen to reflect the current knowledge on the lipidome of the tear film whereas typical Meibomian-origin lipids are included in the thick non-polar lipids subphase. Simulation conditions mimic those experienced by the real human tear film during blinks. Namely, thermodynamic equilibrium simulations at different lateral compressions are performed to model varying surface pressure, and the dynamics of the system during a blink is studied by non-equilibrium MD simulations. Polar lipids separate their non-polar counterparts from water by forming a monomolecular layer whereas the non-polar molecules establish a thick outermost lipid layer. Under lateral compression, the polar layer undulates and a sorting of polar lipids occurs. Moreover, formation of three-dimensional aggregates of polar lipids in both non-polar and water subphases is observed. We suggest that these three-dimensional structures are abundant under dynamic conditions caused by the action of eye lids and that they act as reservoirs of polar lipids, thus increasing stability of the tear film. PMID:24651175

Distribution of an Acoustic Scattering Layer, Petermann Fjord, Northwest Greenland

NASA Astrophysics Data System (ADS)

Heffron, E.; Mayer, L. A.; Jakobsson, M.; Hogan, K.; Jerram, K.

2017-12-01

The Petermann 2015 Expedition was a comprehensive paleoceanographic and paleoclimatological study of the marine-terminating Petermann Glacier and its outlet system in Northwest Greenland carried out July-August 2015. The purpose was the reconstruction of glacial history and current glacial processes in Petermann Fjord to better understand the fate of the Petermann Glacier and its floating ice tongue that acts as a critical buttressing force to the outlet glacier draining about 4% of the Greenland Ice Sheet. Seafloor mapping was a critical component of the study and an EM122 multibeam sonar was utilized for this purpose; additionally, water column data were acquired with this sonar and an EK80 split-beam echosounder. During the expedition, the mapping team noted an acoustic scattering layer in the EK80 and EM122 water column data which was observed to change depth in a spatially consistent manner that appeared to be related to location. Initial onboard processing revealed what appears to be a strong spatial coherence in the layer distribution that corresponds to our understanding of the complex circulation pattern in the study area, including inflow of warmer Atlantic waters and outflow of subglacial waters. This initial processing was limited to observations at 46 discrete locations that corresponded to CTD stations, a very small subset of the 4800 line kilometers of data collected by each sonar. Both sonars were run 24 hours per day over the 30-day expedition, providing continuous time-varying acoustic coverage of the study area. Post-cruise additional data has been processed to extract the acoustic returns from the scattering layer using a combination of commercial sonar processing software and specialized MATLAB and Python routines. 3-D surfaces have been generated from the extracted points in order to visualize the continuous spatial and temporal distribution of the scattering layer across the entire study area. Multiple crossings of the same location at different times of day address the question of the temporal stability of the scattering layer while the detailed map of the spatial distribution demonstrates the relationship of the scattering layer to the water masses and implies that continuous acoustic coverage may be a powerful proxy for oceanography.

Region-specific role of water in collagen unwinding and assembly.

PubMed

Ravikumar, Krishnakumar M; Hwang, Wonmuk

2008-09-01

Conformational stability of the collagen triple helix affects its turnover and determines tissue homeostasis. Although it is known that the presence of imino acids (prolines or hydroxyprolines) confer stability to the molecule, little is known regarding the stability of the imino-poor region lacking imino acids, which plays a key role in collagen cleavage. In particular, there have been continuing debates about the role of water in collagen stability. We addressed these issues using molecular dynamics simulations on 30-residue long collagen triple helices, including a structure that has a biologically relevant 9-residue imino-poor region from type III collagen (PDB ID: 1BKV). A torsional map approach was used to characterize the conformational motion of the molecule that differ between imino-rich and imino-poor regions. At temperatures 300 K and above, unwinding initiates at a common cleavage site, the glycine-isoleucine bond in the imino-poor region. This provides a linkage between previous observations that unwinding of the imino-poor region is a requirement for collagenase cleavage, and that isolated collagen molecules are unstable at body temperature. We found that unwinding of the imino-poor region is controlled by dynamic water bridges between backbone atoms with average lifetimes on the order of a few picoseconds, as the degree of unwinding strongly correlated with the loss of water bridges, and unwinding could be either prevented or enhanced, respectively by enforcing or forbidding water bridge formation. While individual water bridges were short-lived in the imino-poor region, the hydration shell surrounding the entire molecule was stable even at 330 K. The diameter of the hydrated collagen including the first hydration shell was about 14 A, in good agreement with the experimentally measured inter-collagen distances. These results elucidate the general role of water in collagen turnover: water not only affects collagen cleavage by controlling its torsional motion, but it also forms a larger-scale lubrication layer mediating collagen self-assembly. 2008 Wiley-Liss, Inc.

Inhibition of ordinary and diffusive convection in the water condensation zone of the ice giants and implications for their thermal evolution

NASA Astrophysics Data System (ADS)

Friedson, A. James; Gonzales, Erica J.

2017-11-01

We explore the conditions under which ordinary and double-diffusive thermal convection may be inhibited by water condensation in the hydrogen atmospheres of the ice giants and examine the consequences. The saturation of vapor in the condensation layer induces a vertical gradient in the mean molecular weight that stabilizes the layer against convective instability when the abundance of vapor exceeds a critical value. In this instance, the layer temperature gradient can become superadiabatic and heat must be transported vertically by another mechanism. On Uranus and Neptune, water is inferred to be sufficiently abundant for inhibition of ordinary convection to take place in their respective condensation zones. We find that suppression of double-diffusive convection is sensitive to the ratio of the sedimentation time scale of the condensates to the buoyancy period in the condensation layer. In the limit of rapid sedimentation, the layer is found to be stable to diffusive convection. In the opposite limit, diffusive convection can occur. However, if the fluid remains saturated, then layered convection is generally suppressed and the motion is restricted in form to weak, homogeneous, oscillatory turbulence. This form of diffusive convection is a relatively inefficient mechanism for transporting heat, characterized by low Nusselt numbers. When both ordinary and layered convection are suppressed, the condensation zone acts effectively as a thermal insulator, with the heat flux transported across it only slightly greater than the small value that can be supported by radiative diffusion. This may allow a large superadiabatic temperature gradient to develop in the layer over time. Once the layer has formed, however, it is vulnerable to persistent erosion by entrainment of fluid into the overlying convective envelope of the cooling planet, potentially leading to its collapse. We discuss the implications of our results for thermal evolution models of the ice giants, for understanding Uranus' anomalously low intrinsic luminosity, and for inducing episodes of intense convection in the atmospheres of Saturn, Uranus, and Neptune.

Stable annual pattern of water use by Acacia tortilis in Sahelian Africa.

PubMed

Do, Frederic C; Rocheteau, Alain; Diagne, Amadou L; Goudiaby, Venceslas; Granier, André; Lhomme, Jean-Paul

2008-01-01

Water use by mature trees of Acacia tortilis (Forsk.) Hayne ssp. raddiana (Savi) Brenan var. raddiana growing in the northern Sahel was continuously recorded over 4 years. Water use was estimated from xylem sap flow measured by transient heat dissipation. Concurrently, cambial growth, canopy phenology, leaf water potential, climatic conditions and soil water availability (SWA) were monitored. In addition to the variation attributable to interannual variation in rainfall, SWA was increased by irrigation during one wet season. The wet season lasted from July to September, and annual rainfall ranged between 146 and 367 mm. The annual amount and pattern of tree water use were stable from year-to-year despite interannual and seasonal variations in SWA in the upper soil layers. Acacia tortilis transpired readily throughout the year, except for one month during the dry season when defoliation was at a maximum. Maximum water use of about 23 l (dm sapwood area)(-2) day(-1) was recorded at the end of the wet season. While trees retained foliage in the dry season, the decline in water use was modest at around 30%. Variation in predawn leaf water potential indicated that the trees were subject to soil water constraint. The rapid depletion of water in the uppermost soil layers after the wet season implies that there was extensive use of water from deep soil layers. The deep soil profile revealed (1) the existence of living roots at 25 m and (2) that the availability of soil water was low (-1.6 MPa) down to the water table at a depth of 31 m. However, transpiration was recorded at a predawn leaf water potential of -2.0 MPa, indicating that the trees used water from both intermediary soil layers and the water table. During the full canopy stage, mean values of whole-tree hydraulic conductance were similar in the wet and dry seasons. We propose that the stability of water use at the seasonal and annual scales resulted from a combination of features, including an extensive rooting habit related to deep water availability and an effective regulation of canopy conductance. Despite a limited effect on tree water use, irrigation during the wet season sharply increased predawn leaf water potential and cambial growth of trunks and branches.

Solid oxide fuel cell operable over wide temperature range

DOEpatents

Baozhen, Li; Ruka, Roswell J.; Singhal, Subhash C.

2001-01-01

Solid oxide fuel cells having improved low-temperature operation are disclosed. In one embodiment, an interfacial layer of terbia-stabilized zirconia is located between the air electrode and electrolyte of the solid oxide fuel cell. The interfacial layer provides a barrier which controls interaction between the air electrode and electrolyte. The interfacial layer also reduces polarization loss through the reduction of the air electrode/electrolyte interfacial electrical resistance. In another embodiment, the solid oxide fuel cell comprises a scandia-stabilized zirconia electrolyte having high electrical conductivity. The scandia-stabilized zirconia electrolyte may be provided as a very thin layer in order to reduce resistance. The scandia-stabilized electrolyte is preferably used in combination with the terbia-stabilized interfacial layer. The solid oxide fuel cells are operable over wider temperature ranges and wider temperature gradients in comparison with conventional fuel cells.

Interfacial material for solid oxide fuel cell

DOEpatents

Baozhen, Li; Ruka, Roswell J.; Singhal, Subhash C.

1999-01-01

Solid oxide fuel cells having improved low-temperature operation are disclosed. In one embodiment, an interfacial layer of terbia-stabilized zirconia is located between the air electrode and electrolyte of the solid oxide fuel cell. The interfacial layer provides a barrier which controls interaction between the air electrode and electrolyte. The interfacial layer also reduces polarization loss through the reduction of the air electrode/electrolyte interfacial electrical resistance. In another embodiment, the solid oxide fuel cell comprises a scandia-stabilized zirconia electrolyte having high electrical conductivity. The scandia-stabilized zirconia electrolyte may be provided as a very thin layer in order to reduce resistance. The scandia-stabilized electrolyte is preferably used in combination with the terbia-stabilized interfacial layer. The solid oxide fuel cells are operable over wider temperature ranges and wider temperature gradients in comparison with conventional fuel cells.

The ocean mixed layer under Southern Ocean sea-ice: Seasonal cycle and forcing

NASA Astrophysics Data System (ADS)

Pellichero, Violaine; Sallée, Jean-Baptiste; Schmidtko, Sunke; Roquet, Fabien; Charrassin, Jean-Benoît

2017-02-01

The oceanic mixed layer is the gateway for the exchanges between the atmosphere and the ocean; in this layer, all hydrographic ocean properties are set for months to millennia. A vast area of the Southern Ocean is seasonally capped by sea-ice, which alters the characteristics of the ocean mixed layer. The interaction between the ocean mixed layer and sea-ice plays a key role for water mass transformation, the carbon cycle, sea-ice dynamics, and ultimately for the climate as a whole. However, the structure and characteristics of the under-ice mixed layer are poorly understood due to the sparseness of in situ observations and measurements. In this study, we combine distinct sources of observations to overcome this lack in our understanding of the polar regions. Working with elephant seal-derived, ship-based, and Argo float observations, we describe the seasonal cycle of the ocean mixed-layer characteristics and stability of the ocean mixed layer over the Southern Ocean and specifically under sea-ice. Mixed-layer heat and freshwater budgets are used to investigate the main forcing mechanisms of the mixed-layer seasonal cycle. The seasonal variability of sea surface salinity and temperature are primarily driven by surface processes, dominated by sea-ice freshwater flux for the salt budget and by air-sea flux for the heat budget. Ekman advection, vertical diffusivity, and vertical entrainment play only secondary roles. Our results suggest that changes in regional sea-ice distribution and annual duration, as currently observed, widely affect the buoyancy budget of the underlying mixed layer, and impact large-scale water mass formation and transformation with far reaching consequences for ocean ventilation.

Study on lithium/air secondary batteries-Stability of NASICON-type lithium ion conducting glass-ceramics with water

NASA Astrophysics Data System (ADS)

Hasegawa, Satoshi; Imanishi, Nobuyuki; Zhang, Tao; Xie, Jian; Hirano, Atsushi; Takeda, Yasuo; Yamamoto, Osamu

The water stability of the fast lithium ion conducting glass-ceramic electrolyte, Li 1+ x+ yAl xTi 2- xSi yP 3- yO 12 (LATP), has been examined in distilled water, and aqueous solutions of LiNO 3, LiCl, LiOH, and HCl. This glass-ceramics are stable in aqueous LiNO 3 and aqueous LiCl, and unstable in aqueous 0.1 M HCl and 1 M LiOH. In distilled water, the electrical conductivity slightly increases as a function of immersion time in water. The Li-Al/Li 3- xPO 4- yN y/LATP/aqueous 1 M LiCl/Pt cell, where lithium phosphors oxynitrides Li 3- xPO 4- yN y (LiPON) are used to protect the direct reaction of Li and LATP, shows a stable open circuit voltage (OCV) of 3.64 V at 25 °C, and no cell resistance change for 1 week. Lithium phosphors oxynitride is effectively used as a protective layer to suppress the reaction between the LATP and Li metal. The water-stable Li/LiPON/LATP system can be used in Li/air secondary batteries with the air electrode containing water.

Recent variability of the tropical tropopause inversion layer

NASA Astrophysics Data System (ADS)

Wang, Wuke; Matthes, Katja; Schmidt, Torsten; Neef, Lisa

2013-12-01

The recent variability of the tropopause temperature and the tropopause inversion layer (TIL) are investigated with Global Positioning System Radio Occultation data and simulations with the National Center for Atmospheric Research's Whole Atmosphere Community Climate Model (WACCM). Over the past decade (2001-2011) the data show an increase of 0.8 K in the tropopause temperature and a decrease of 0.4 K in the strength of the tropopause inversion layer in the tropics, meaning that the vertical temperature gradient has declined, and therefore that the stability above the tropopause has weakened. WACCM simulations with finer vertical resolution show a more realistic TIL structure and variability. Model simulations show that the increased tropopause temperature and the weaker tropopause inversion layer are related to weakened upwelling in the tropics. Such changes in the thermal structure of the upper troposphere and lower stratosphere may have important implications for climate, such as a possible rise in water vapor in the lower stratosphere.

Biosensor properties of SOI nanowire transistors with a PEALD Al{sub 2}O{sub 3} dielectric protective layer

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

Popov, V. P., E-mail: popov@isp.nsc.ru; Ilnitskii, M. A.; Zhanaev, E. D.

2016-05-15

The properties of protective dielectric layers of aluminum oxide Al{sub 2}O{sub 3} applied to prefabricated silicon-nanowire transistor biochips by the plasma enhanced atomic layer deposition (PEALD) method before being housed are studied depending on the deposition and annealing modes. Coating the natural silicon oxide with a nanometer Al{sub 2}O{sub 3} layer insignificantly decreases the femtomole sensitivity of biosensors, but provides their stability in bioliquids. In deionized water, transistors with annealed aluminum oxide are closed due to the trapping of negative charges of <(1–10) × 10{sup 11} cm{sup −2} at surface states. The application of a positive potential to the substratemore » (V{sub sub} > 25 V) makes it possible to eliminate the negative charge and to perform multiple measurements in liquid at least for half a year.« less

An Inexpensive Co-Intercalated Layered Double Hydroxide Composite with Electron Donor-Acceptor Character for Photoelectrochemical Water Splitting

PubMed Central

Zheng, Shufang; Lu, Jun; Yan, Dongpeng; Qin, Yumei; Li, Hailong; Evans, David G.; Duan, Xue

2015-01-01

In this paper, the inexpensive 4,4-diaminostilbene-2,2-disulfonate (DAS) and 4,4-dinitro-stilbene-2,2- disulfonate (DNS) anions with arbitrary molar ratios were successfully co-intercalated into Zn2Al-layered double hydroxides (LDHs). The DAS(50%)-DNS/LDHs composite exhibited the broad UV-visible light absorption and fluorescence quenching, which was a direct indication of photo-induced electron transfer (PET) process between the intercalated DAS (donor) and DNS (acceptor) anions. This was confirmed by the matched HOMO/LUMO energy levels alignment of the intercalated DAS and DNS anions, which was also compatible for water splitting. The DAS(50%)-DNS/LDHs composite was fabricated as the photoanode and Pt as the cathode. Under the UV-visible light illumination, the enhanced photo-generated current (4.67 mA/cm2 at 0.8 V vs. SCE) was generated in the external circuit, and the photoelectrochemical water split was realized. Furthermore, this photoelectrochemical water splitting performance had excellent crystalline, electrochemical and optical stability. Therefore, this novel inorganic/organic hybrid photoanode exhibited potential application prospect in photoelectrochemical water splitting. PMID:26174201

A balanced water layer concept for subglacial hydrology in large scale ice sheet models

NASA Astrophysics Data System (ADS)

Goeller, S.; Thoma, M.; Grosfeld, K.; Miller, H.

2012-12-01

There is currently no doubt about the existence of a wide-spread hydrological network under the Antarctic ice sheet, which lubricates the ice base and thus leads to increased ice velocities. Consequently, ice models should incorporate basal hydrology to obtain meaningful results for future ice dynamics and their contribution to global sea level rise. Here, we introduce the balanced water layer concept, covering two prominent subglacial hydrological features for ice sheet modeling on a continental scale: the evolution of subglacial lakes and balance water fluxes. We couple it to the thermomechanical ice-flow model RIMBAY and apply it to a synthetic model domain inspired by the Gamburtsev Mountains, Antarctica. In our experiments we demonstrate the dynamic generation of subglacial lakes and their impact on the velocity field of the overlaying ice sheet, resulting in a negative ice mass balance. Furthermore, we introduce an elementary parametrization of the water flux-basal sliding coupling and reveal the predominance of the ice loss through the resulting ice streams against the stabilizing influence of less hydrologically active areas. We point out, that established balance flux schemes quantify these effects only partially as their ability to store subglacial water is lacking.

Nanosized thin SnO₂ layers doped with Te and TeO₂ as room temperature humidity sensors.

PubMed

Georgieva, Biliana; Podolesheva, Irena; Spasov, Georgy; Pirov, Jordan

2014-05-21

In this paper the humidity sensing properties of layers prepared by a new method for obtaining doped tin oxide are studied. Different techniques-SEM, EDS in SEM, TEM, SAED, AES and electrical measurements-are used for detailed characterization of the thin layers. The as-deposited layers are amorphous with great specific area and low density. They are built up of a fine grained matrix, consisting of Sn- and Te-oxides, and a nanosized dispersed phase of Te, Sn and/or SnTe. The chemical composition of both the matrix and the nanosized particles depends on the ratio R(Sn/Te) and the evaporation conditions. It is shown that as-deposited layers with R(Sn/Te) ranging from 0.4 to 0.9 exhibit excellent characteristics as humidity sensors operating at room temperature-very high sensitivity, good selectivity, fast response and short recovery period. Ageing tests have shown that the layers possess good long-term stability. Results obtained regarding the type of the water adsorption on the layers' surface help better understand the relation between preparation conditions, structure, composition and humidity sensing properties.

Density functional theory study of bulk and single-layer magnetic semiconductor CrPS4

NASA Astrophysics Data System (ADS)

Zhuang, Houlong L.; Zhou, Jia

2016-11-01

Searching for two-dimensional (2D) materials with multifunctionality is one of the main goals of current research in 2D materials. Magnetism and semiconducting are certainly two desirable functional properties for a single 2D material. In line with this goal, here we report a density functional theory (DFT) study of bulk and single-layer magnetic semiconductor CrPS4. We find that the ground-state magnetic structure of bulk CrPS4 exhibits the A-type antiferromagnetic ordering, which transforms to ferromagnetic (FM) ordering in single-layer CrPS4. The calculated formation energy and phonon spectrum confirm the stability of single-layer CrPS4. The band gaps of FM single-layer CrPS4 calculated with a hybrid density functional are within the visible-light range. We also study the effects of FM ordering on the optical absorption spectra and band alignments for water splitting, indicating that single-layer CrPS4 could be a potential photocatalyst. Our work opens up ample opportunities of energy-related applications of single-layer CrPS4.

Convection induced by selective absorption of radiation: A laboratory model of conditional instability

NASA Astrophysics Data System (ADS)

Krishnamurti, Ruby

1998-01-01

When there is internal heating in a fluid layer, convection can occur even if the static state is one of stable stratification. We have been investigating through laboratory experiments such a stably stratified layer of water which is heated above and cooled below. The water contains in dilute solution thymol blue (a pH indicator), which normally colors the water orange. It turns yellow if the pH is low, blue if the pH is high. A small DC voltage is applied across the layer, by using the bottom boundary as the positive electrode, the top boundary as the negative electrode. The hydroxyl ions formed near the bottom boundary cause the orange fluid to turn blue. The fluid layer is uniformly and steadily illuminated from above with light from a sodium vapor lamp. This radiation travels with negligible absorption through the orange fluid but is strongly absorbed by the blue fluid. The resultant warming of the blue fluid can lead to convective instability, with the blue fluid rising into warm upper layers, which it would continue to penetrate as long as it remains blue and as long as the radiative heating is sufficient to exceed the higher ambient temperatures above. This radiative heating occurs only in the blue rising flow; the sinking fluid is orange and is not heated. We have found that with a strongly stably stratified layer, convective plumes are unable to penetrate far and they remain shallow. However, for a weakly stratified layer, plumes grow tall and furthermore collect into a large convective cluster which persists as a steady coherent structure. The present paper deals also with the formulation of the governing equations to include the fluid-state-dependent heat source. A linear stability analysis shows that the critical Rayleigh number for onset of motion is drastically reduced. Furthermore, the cell size at onset is larger by a factor of √ 3/2 than in the classical Rayleigh-Benard convection problem. However, the laboratory fluid cells were much further broadened (by a factor of 8 or 10) when they penetrated into the stably stratified fluid above. In this case, the rising region is narrow and the sinking region is broad, so that downward vertical velocities are correspondingly small. In this way, the downwards-forced warm fluid has time to cool by conduction to the cold boundary. Steady finite amplitude solutions and their stability are analyzed and it is shown that there is a parameter range in which finite amplitude hexagonal cells are stable.

Atomic Layer Deposition Al2O3 Coatings Significantly Improve Thermal, Chemical, and Mechanical Stability of Anodic TiO2 Nanotube Layers

PubMed Central

2017-01-01

We report on a very significant enhancement of the thermal, chemical, and mechanical stability of self-organized TiO2 nanotubes layers, provided by thin Al2O3 coatings of different thicknesses prepared by atomic layer deposition (ALD). TiO2 nanotube layers coated with Al2O3 coatings exhibit significantly improved thermal stability as illustrated by the preservation of the nanotubular structure upon annealing treatment at high temperatures (870 °C). In addition, a high anatase content is preserved in the nanotube layers against expectation of the total rutile conversion at such a high temperature. Hardness of the resulting nanotube layers is investigated by nanoindentation measurements and shows strongly improved values compared to uncoated counterparts. Finally, it is demonstrated that Al2O3 coatings guarantee unprecedented chemical stability of TiO2 nanotube layers in harsh environments of concentrated H3PO4 solutions. PMID:28291942

Boundary-layer stability and airfoil design

NASA Technical Reports Server (NTRS)

Viken, Jeffrey K.

1986-01-01

Several different natural laminar flow (NLF) airfoils have been analyzed for stability of the laminar boundary layer using linear stability codes. The NLF airfoils analyzed come from three different design conditions: incompressible; compressible with no sweep; and compressible with sweep. Some of the design problems are discussed, concentrating on those problems associated with keeping the boundary layer laminar. Also, there is a discussion on how a linear stability analysis was effectively used to improve the design for some of the airfoils.

[Soil organic carbon mineralization of Black Locust forest in the deep soil layer of the hilly region of the Loess Plateau, China].

PubMed

Ma, Xin-Xin; Xu, Ming-Xiang; Yang, Kai

2012-11-01

The deep soil layer (below 100 cm) stores considerable soil organic carbon (SOC). We can reveal its stability and provide the basis for certification of the deep soil carbon sinks by studying the SOC mineralization in the deep soil layer. With the shallow soil layer (0-100 cm) as control, the SOC mineralization under the condition (temperature 15 degrees C, the soil water content 8%) of Black Locust forest in the deep soil layer (100-400 cm) of the hilly region of the Loess Plateau was studied. The results showed that: (1) There was a downward trend in the total SOC mineralization with the increase of soil depth. The total SOC mineralization in the sub-deep soil (100-200 cm) and deep soil (200-400 cm) were equivalent to approximately 88.1% and 67.8% of that in the shallow layer (0-100 cm). (2) Throughout the carbon mineralization process, the same as the shallow soil, the sub-deep and deep soil can be divided into 3 stages. In the rapid decomposition phase, the ratio of the mineralization or organic carbon to the total mineralization in the sub-deep and deep layer (0-10 d) was approximately 50% of that in the shallow layer (0-17 d). In the slow decomposition phase, the ratio of organic carbon mineralization to total mineralization in the sub-deep, deep layer (11-45 d) was 150% of that in the shallow layer (18-45 d). There was no significant difference in this ratio among these three layers (46-62 d) in the relatively stable stage. (3) There was no significant difference (P > 0.05) in the mineralization rate of SOC among the shallow, sub-deep, deep layers. The stability of SOC in the deep soil layer (100-400 cm) was similar to that in the shallow soil layer and the SOC in the deep soil layer was also involved in the global carbon cycle. The change of SOC in the deep soil layer should be taken into account when estimating the effects of soil carbon sequestration in the Hilly Region of the Loess Plateau, China.

EnviroAtlas - Metrics for Austin, TX

EPA Pesticide Factsheets

This EnviroAtlas web service supports research and online mapping activities related to EnviroAtlas (https://enviroatlas.epa.gov/EnviroAtlas). The layers in this web service depict ecosystem services at the census block group level for the community of Austin, Texas. These layers illustrate the ecosystems and natural resources that are associated with clean air (https://enviroatlas.epa.gov/arcgis/rest/services/Communities/ESC_ATX_CleanAir/MapServer); clean and plentiful water (https://enviroatlas.epa.gov/arcgis/rest/services/Communities/ESC_ATX_CleanPlentifulWater/MapServer); natural hazard mitigation (https://enviroatlas.epa.gov/arcgis/rest/services/Communities/ESC_ATX_NaturalHazardMitigation/MapServer); climate stabilization (https://enviroatlas.epa.gov/arcgis/rest/services/Communities/ESC_ATX_ClimateStabilization/MapServer); food, fuel, and materials (https://enviroatlas.epa.gov/arcgis/rest/services/Communities/ESC_ATX_FoodFuelMaterials/MapServer); recreation, culture, and aesthetics (https://enviroatlas.epa.gov/arcgis/rest/services/Communities/ESC_ATX_RecreationCultureAesthetics/MapServer); and biodiversity conservation (https://enviroatlas.epa.gov/arcgis/rest/services/Communities/ESC_ATX_BiodiversityConservation/MapServer), and factors that place stress on those resources. EnviroAtlas allows the user to interact with a web-based, easy-to-use, mapping application to view and analyze multiple ecosystem services for the conterminous United States as well as de

Effects of bulk colloidal stability on adsorption layers of poly(diallyldimethylammonium chloride)/sodium dodecyl sulfate at the air-water interface studied by neutron reflectometry.

PubMed

Campbell, Richard A; Yanez Arteta, Marianna; Angus-Smyth, Anna; Nylander, Tommy; Varga, Imre

2011-12-29

We show for the oppositely charged system poly(diallyldimethylammonium chloride)/sodium dodecyl sulfate that the cliff edge peak in its surface tension isotherm results from the comprehensive precipitation of bulk complexes into sediment, leaving a supernatant that is virtually transparent and a depleted adsorption layer at the air/water interface. The aggregation and settling processes take about 3 days to reach completion and occur at bulk compositions around charge neutrality of the complexes which lack long-term colloidal stability. We demonstrate excellent quantitative agreement between the measured surface tension values and a peak calculated from the surface excess of surfactant in the precipitation region measured by neutron reflectometry, using the approximation that there is no polymer left in the liquid phase. The nonequilibrium nature of the system is emphasized by the production of very different interfacial properties from equivalent aged samples that are handled differently. We go on to outline our perspective on the "true equilibrium" state of this intriguing system and conclude with a comment on its practical relevance given that the interfacial properties can be so readily influenced by the handling of kinetically trapped bulk aggregates. © 2011 American Chemical Society

Fast electrosynthesis of Fe-containing layered double hydroxide arrays toward highly efficient electrocatalytic oxidation reactions† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5sc02417j

PubMed Central

Li, Zhenhua; An, Hongli; Wang, Zixuan; Xu, Simin; Evans, David G.; Duan, Xue

2015-01-01

A new electrochemical synthesis route was developed for the fabrication of Fe-containing layered double hydroxide (MFe-LDHs, M = Ni, Co and Li) hierarchical nanoarrays, which exhibit highly-efficient electrocatalytic performances for the oxidation reactions of several small molecules (water, hydrazine, methanol and ethanol). Ultrathin MFe-LDH nanoplatelets (200–300 nm in lateral length; 8–12 nm in thickness) perpendicular to the substrate surface are directly prepared within hundreds of seconds (<300 s) under cathodic potential. The as-obtained NiFe-LDH nanoplatelet arrays display promising behavior in the oxygen evolution reaction (OER), giving rise to a rather low overpotential (0.224 V) at 10.0 mA cm–2 with largely enhanced stability, much superior to previously reported electro-oxidation catalysts as well as the state-of-the-art Ir/C catalyst. Furthermore, the MFe-LDH nanoplatelet arrays can also efficiently catalyze several other fuel molecules’ oxidation (e.g., hydrazine, methanol and ethanol), delivering a satisfactory electrocatalytic activity and a high operation stability. In particular, this preparation method of Fe-containing LDHs is amenable to fast, effective and large-scale production, and shows promising applications in water splitting, fuel cells and other clean energy devices. PMID:29435211

[State of Fungal Lipases of Rhizopus microsporus, Penicillium sp. and Oospora lactis in Border Layers Water-Solid Phase and Factors Affecting Catalytic Properties of Enzymes].

PubMed

Khasanov, Kh T; Davranov, K; Rakhimov, M M

2015-01-01

We demonstrated that a change in the catalytic activity of fungal lipases synthesized by Rhizopus microsporus, Penicillium sp. and Oospora lactis and their ability to absorb on different sorbents depended on the nature of groups on the solid phase surface in the model systems water: lipid and water: solid phase. Thus, the stability of Penicillium sp. lipases increased 85% in the presence ofsorsilen or DEAE-cellulose, and 55% of their initial activity respectively was preserved. In the presence of silica gel and CM-cellulose, a decreased rate of lipid hydrolysis by Pseudomonas sp. enzymes was observed in water medium, and the hydrolysis rate increased by 2.4 and 1.5 times respectively in the presence of aminoaerosil and polykefamid. In an aqueous-alcohol medium, aminoaerosil and polykefamid decreased the rate of substrate hydrolysis by more than 30 times. The addition of aerosil to aqueous and aqueous-alcohol media resulted in an increase in the hydrolysis rate by 1.2-1.3 times. Sorsilen stabilized Penicillium sp. lipase activity at 40, 45, 50 and 55 degrees C. Either stabilization or inactivation of lipases was observed depending on the pH of the medium and the nature of chemical groups localized on the surface of solid phase. The synthetizing activity of lipases also changed depending on the conditions.

Stabilization of water in oil in water (W/O/W) emulsion using whey protein isolate-conjugated durian seed gum: enhancement of interfacial activity through conjugation process.

PubMed

Tabatabaee Amid, Bahareh; Mirhosseini, Hamed

2014-01-01

The present work was conducted to investigate the effect of purification and conjugation processes on functional properties of durian seed gum (DSG) used for stabilization of water in oil in water (W/O/W) emulsion. Whey protein isolate (WPI) was conjugated to durian seed gum through the covalent linkage. In order to prepare WPI-DSG conjugate, covalent linkage of whey protein isolate to durian seed gum was obtained by Maillard reaction induced by heating at 60 °C and 80% (±1%) relative humidity. SDS-polyacrylamide gel electrophoresis was used to test the formation of the covalent linkage between whey protein isolate and durian seed gum after conjugation process. In this study, W/O/W stabilized by WPI-conjugated DSG A showed the highest interface activity and lowest creaming layer among all prepared emulsions. This indicated that the partial conjugation of WPI to DSG significantly improved its functional characteristics in W/O/W emulsion. The addition of WPI-conjugated DSG to W/O/W emulsion increased the viscosity more than non-conjugated durian seed gum (or control). This might be due to possible increment of the molecular weight after linking the protein fraction to the structure of durian seed gum through the conjugation process. Copyright © 2013 Elsevier B.V. All rights reserved.

Tropopause inversion layer and water vapour

NASA Astrophysics Data System (ADS)

Peinke, Isabel; Reutter, Philipp; Hoor, Peter; Spichtinger, Peter

2013-04-01

The tropopause inversion layer (TIL) is a phenomenon located close to the tropopause, characterized by an enhanced static stability (N2) right above the temperature inversion of the tropopause and by its adjacent minima. There is low understanding of formation and maintenance of the TIL, but different hypotheses exist. On one hand, the balanced dynamic in this region has an important impact on the evolution and sustainment of the TIL. On the other hand, the radiative effects of ozone and water vapor near the tropopause might play an important role for the formation and maintenance of the TIL. We use high resolution radiosonde data over the Meteorological Observatory Lindenberg, Germany for the period February 2000 to April 2001 to investigate the impact of water vapor on the TIL. Starting from the mean profiles, we analyze the main features of the tropopause and the TIL. As it is known from the literature, we find a stronger TIL in summer compared to winter. However, our results show a complementary behavior in the seasonal cycle of the tropopause height and the TIL strength. The influence of the relative humidity over ice (RHi) on the TIL was also investigated. We show that high values of RHi lead to a cooler tropopause temperature and an enhanced strength of the TIL. This means that the maximum of the static stability is higher for high values of RHi and the adjacent minima are smaller than for low values of RHi.

The impact of N,N-dimethyldodecylamine N-oxide (DDAO) concentration on the crystallisation of sodium dodecyl sulfate (SDS) systems and the resulting changes to crystal structure, shape and the kinetics of crystal growth.

PubMed

Summerton, Emily; Hollamby, Martin J; Zimbitas, Georgina; Snow, Tim; Smith, Andrew J; Sommertune, Jens; Bettiol, Jeanluc; Jones, Christopher; Britton, Melanie M; Bakalis, Serafim

2018-05-19

At low temperatures stability issues arise in commercial detergent products when surfactant crystallisation occurs, a process which is not currently well-understood. An understanding of the phase transition can be obtained using a simple binary SDS (sodium dodecyl sulfate) + DDAO (N,N-dimethyldodecylamine N-oxide) aqueous system. It expected that the crystallisation temperature of an SDS system can be lowered with addition of DDAO, thus providing a route to improve detergent stability. Detergent systems are typically comprised of anionic surfactants, non-ionic surfactants and water. This study explores the crystallisation of a three component system consisting of sodium dodecyl sulfate (SDS), N,N-dimethyldodecylamine N-oxide (DDAO), and water using wide-angle X-ray scattering (WAXS), differential scanning calorimetry (DSC) and confocal Raman microscopy. The presence of DDAO lowered the crystallisation temperature of a 20 wt% SDS system. For all aqueous mixtures of SDS + DDAO at low temperatures, SDS hydrated crystals, SDS.1/2H 2 O or SDS·H 2 O, formed. SDS hydrates comprising of layers of SDS separated by water layers. DDAO tended to reside in the vicinity of these SDS crystals. In the absence of DDAO an additional intermediary hydrate structure, SDS.1/8H 2 O, formed whereas for mixed SDS + DDAO systems no such structure was detected during crystallisation. Copyright © 2018. Published by Elsevier Inc.

Low-temperature fabrication of an HfO2 passivation layer for amorphous indium-gallium-zinc oxide thin film transistors using a solution process.

PubMed

Hong, Seonghwan; Park, Sung Pyo; Kim, Yeong-Gyu; Kang, Byung Ha; Na, Jae Won; Kim, Hyun Jae

2017-11-24

We report low-temperature solution processing of hafnium oxide (HfO 2 ) passivation layers for amorphous indium-gallium-zinc oxide (a-IGZO) thin-film transistors (TFTs). At 150 °C, the hafnium chloride (HfCl 4 ) precursor readily hydrolyzed in deionized (DI) water and transformed into an HfO 2 film. The fabricated HfO 2 passivation layer prevented any interaction between the back surface of an a-IGZO TFT and ambient gas. Moreover, diffused Hf 4+ in the back-channel layer of the a-IGZO TFT reduced the oxygen vacancy, which is the origin of the electrical instability in a-IGZO TFTs. Consequently, the a-IGZO TFT with the HfO 2 passivation layer exhibited improved stability, showing a decrease in the threshold voltage shift from 4.83 to 1.68 V under a positive bias stress test conducted over 10,000 s.

Role of humidity in reducing the friction of graphene layers on textured surfaces

NASA Astrophysics Data System (ADS)

Li, Zheng-yang; Yang, Wen-jing; Wu, Yan-ping; Wu, Song-bo; Cai, Zhen-bing

2017-05-01

A multiple-layer graphene was prepared on steel surface to reduce friction and wear. A graphene-containing ethanol solution was dripped on the steel surface, and several layers of graphene flakes were deposited on the surface after ethanol evaporated. Tribological performance of graphene-contained surface (GCS) was induced by reciprocating ball against plate contact in different RH (0% (dry nitrogen), 30%, 60%, and 90%). Morphology and wear scar were analyzed by OM, 2D profile, SEM, Raman spectroscopy, and XPS. Results show that GCS can substantially reduce the wear and coefficient of friction (COF) in 60% relative humidity (RH). Low COF occurs due to graphene layer providing a small shear stress on the friction interface. Meanwhile, conditions of high RH and textured surface could make the low COF persist for a longer time. High moisture content can stabilize and protect the graphene C-network from damage due to water dissociative chemisorption with carbon dangling bonds, and the textured surface was attributed to release graphene layer stored in the dimple.

Hydrated states of MgSO4 at equatorial latiudes on Mars

USGS Publications Warehouse

Feldman, W.C.; Mellon, M.T.; Maurice, S.; Prettyman, T.H.; Carey, J.W.; Vaniman, D.T.; Bish, D.L.; Fialips, C.I.; Chipera, S.J.; Kargel, J.S.; Elphic, R.C.; Funsten, H.O.; Lawrence, D.J.; Tokar, R.L.

2004-01-01

The stability of water ice, epsomite, and hexahydrite to loss of H 2O molecules to the atmosphere at equatorial latitudes of Mars was studied to determine their potential contributions to the measured abundance of water-equivalent hydrogen (WEH). Calculation of the relative humidity based on estimates of yearly averages of water-vapor pressures and temperatures at the Martian surface was used for this purpose. Water ice was found to be sufficiently unstable everywhere within 45?? of the equator that if the observed WEH is due to water ice, it requires a low-permeability cover layer near the surface to isolate the water ice below from the atmosphere above. In contrast, epsomite or hexahydrite may be stable in many near-equatorial locations where significant amounts of WEH are observed. Copyright 2004 by the American Geophysical Union.

Stable aqueous based Cu nanoparticle ink for printing well-defined highly conductive features on a plastic substrate.

PubMed

Jeong, Sunho; Song, Hae Chun; Lee, Won Woo; Lee, Sun Sook; Choi, Youngmin; Son, Wonil; Kim, Eui Duk; Paik, Choon Hoon; Oh, Seok Heon; Ryu, Beyong-Hwan

2011-03-15

With the aim of inkjet printing highly conductive and well-defined Cu features on plastic substrates, aqueous based Cu ink is prepared for the first time using water-soluble Cu nanoparticles with a very thin surface oxide layer. Owing to the specific properties, high surface tension and low boiling point, of water, the aqueous based Cu ink endows a variety of advantages over conventional Cu inks based on organic solvents in printing narrow conductive patterns without irregular morphologies. It is demonstrated how the design of aqueous based ink affects the basic properties of printed conductive features such as surface morphology, microstructure, conductivity, and line width. The long-term stability of aqueous based Cu ink against oxidation is analyzed through an X-ray photoelectron spectroscopy (XPS) based investigation on the evolution of the surface oxide layer in the aqueous based ink.

Unsteady viscous effects in the flow over an oscillating surface. [mathematical model

NASA Technical Reports Server (NTRS)

Lerner, J. I.

1972-01-01

A theoretical model for the interaction of a turbulent boundary layer with an oscillating wavy surface over which a fluid is flowing is developed, with an application to wind-driven water waves and to panel flutter in low supersonic flow. A systematic methodology is developed to obtain the surface pressure distribution by considering separately the effects on the perturbed flow of a mean shear velocity profile, viscous stresses, the turbulent Reynolds stresses, compressibility, and three-dimensionality. The inviscid theory is applied to the wind-water wave problem by specializing to traveling-wave disturbances, and the pressure magnitude and phase shift as a function of the wave phase speed are computed for a logarithmic mean velocity profile and compared with inviscid theory and experiment. The results agree with experimental evidence for the stabilization of the panel motion due to the influence of the unsteady boundary layer.

Theoretical Insights into a CO Dimerization Mechanism in CO2 Electroreduction.

PubMed

Montoya, Joseph H; Shi, Chuan; Chan, Karen; Nørskov, Jens K

2015-06-04

In this work, we present DFT simulations that demonstrate the ability of Cu to catalyze CO dimerization in CO2 and CO electroreduction. We describe a previously unreported CO dimer configuration that is uniquely stabilized by a charged water layer on both Cu(111) and Cu(100). Without this charged water layer at the metal surface, the formation of the CO dimer is prohibitively endergonic. Our calculations also demonstrate that dimerization should have a lower activation barrier on Cu(100) than Cu(111), which, along with a more exergonic adsorption energy and a corresponding higher coverage of *CO, is consistent with experimental observations that Cu(100) has a high activity for C-C coupling at low overpotentials. We also demonstrate that this effect is present with cations other than H(+), a finding that is consistent with the experimentally observed pH independence of C2 formation on Cu.

Super-hydrophobic graphene coated polyurethane (GN@PU) sponge with great oil-water separation performance

NASA Astrophysics Data System (ADS)

Zhang, Xiaotan; Liu, Dongyan; Ma, Yuling; Nie, Jing; Sui, Guoxin

2017-11-01

The graphene/polyurethane (GN@PU) sponge was prepared via simple dip-coating PU sponges in graphene aqueous suspension containing cellulose nanowhiskers (CNWs), where CNWs played a vital role to facilitate the uniform graphene sheets coated on the skeletons of polyurethane sponge (PU). The super-hydrophobic GN@PU sponge was obtained by optimizing the ratio of GN and CNWs to choose the final coating suspensions of GN/CNWs mixture or pure graphene. The GN@PU sponge showed densely packed graphene sheets, contributing super-hydrophobicity to the sponge with water contact angle of 152° and a large lubricating oil absorption value of 31 g g-1. The elasticity, mechanical durability, thermal and chemical stability were all found to be improved after coating with the thin GN layers. Moreover, the GN@PU sponges possess outstanding recyclability and stability since no decline in absorption efficiency was observed after more than 100 cycles.

Chitosan/silica coated carbon nanotubes composite proton exchange membranes for fuel cell applications.

PubMed

Liu, Hai; Gong, Chunli; Wang, Jie; Liu, Xiaoyan; Liu, Huanli; Cheng, Fan; Wang, Guangjin; Zheng, Genwen; Qin, Caiqin; Wen, Sheng

2016-01-20

Silica-coated carbon nanotubes (SCNTs), which were obtained by a simple sol-gel method, were utilized in preparation of chitosan/SCNTs (CS/SCNTs) composite membranes. The thermal and oxidative stability, morphology, mechanical properties, water uptake and proton conductivity of CS/SCNTs composite membranes were investigated. The insulated and hydrophilic silica layer coated on CNTs eliminates the risk of electronic short-circuiting and enhances the interaction between SCNTs and chitosan to ensure the homogenous dispersion of SCNTs, although the water uptake of CS/SCNTs membranes is reduced owing to the decrease of the effective number of the amino functional groups of chitosan. The CS/SCNTs composite membranes are superior to the pure CS membrane in thermal and oxidative stability, mechanical properties and proton conductivity. The results of this study suggest that CS/SCNTs composite membranes exhibit promising potential for practical application in proton exchange membranes. Copyright © 2015 Elsevier Ltd. All rights reserved.

Disintegration and cancer immunotherapy efficacy of a squalane-in-water delivery system emulsified by bioresorbable poly(ethylene glycol)-block-polylactide.

PubMed

Chen, Wei-Lin; Liu, Shih-Jen; Leng, Chih-Hsiang; Chen, Hsin-Wei; Chong, Pele; Huang, Ming-Hsi

2014-02-01

Vaccine adjuvant is conferred on the substance that helps to enhance antigen-specific immune response. Here we investigated the disintegration characteristics and immunotherapy potency of an emulsified delivery system comprising bioresorbable polymer poly(ethylene glycol)-polylactide (PEG-PLA), phosphate buffer saline (PBS), and metabolizable oil squalane. PEG-PLA-stabilized oil-in-water emulsions show good stability at 4 °C and at room temperature. At 37 °C, squalane/PEG-PLA/PBS emulsion with oil/aqueous weight ratio of 7/3 (denominated PELA73) was stable for 6 weeks without phase separation. As PEG-PLA being degraded, 30% of free oil at the surface layer and 10% of water at the bottom disassociated from the PELA73 emulsion were found after 3 months. A MALDI-TOF MS study directly on the DIOS plate enables us to identify low molecular weight components released during degradation. Our results confirm the loss of PLA moiety of the emulsifier PEG-PLA directly affected the stability of PEG-PLA-stabilized emulsion, leading to emulsion disintegration and squalane/water phase separation. As adjuvant for cancer immunotherapeutic use, an HPV16 E7 peptide antigen formulated with PELA73 plus immunostimulatory CpG molecules could strongly enhance antigen-specific T-cell responses as well as anti-tumor ability with respected to non-formulated or Alum-formulated peptide. Accordingly, these advances may be a potential immunoregulatory strategy in manipulating the immune responses induced by tumor-associated antigens. Copyright © 2013 The Authors. Published by Elsevier Ltd.. All rights reserved.

Origins of the Non-DLVO Force between Glass Surfaces in Aqueous Solution.

PubMed

Adler, Joshua J.; Rabinovich, Yakov I.; Moudgil, Brij M.

2001-05-15

Direct measurement of surface forces has revealed that silica surfaces seem to have a short-range repulsion that is not accounted for in classical DLVO theory. The two leading hypotheses for the origin of the non-DLVO force are (i) structuring of water at the silica interface or (ii) water penetration into the surface resulting in a gel layer. In this article, the interaction of silica surfaces will be reviewed from the perspective of the non-DLVO force origin. In an attempt to more accurately describe the behavior of silica and glass surfaces, alternative models of how surfaces with gel layers should interact are proposed. It is suggested that a lessened van der Waals attraction originating from a thin gel layer may explain both the additional stability and the coagulation behavior of silica. It is important to understand the mechanisms underlying the existence of the non-DLVO force which is likely to have a major influence on the adsorption of polymers and surfactants used to modify the silica surface for practical applications in the ceramic, mineral, and microelectronic industries. Copyright 2001 Academic Press.

Membrane formation in liquids by adding an antagonistic salt

NASA Astrophysics Data System (ADS)

Sadakane, Koichiro; Seto, Hideki

2018-03-01

Antagonistic salts are composed of hydrophilic and hydrophobic ions. In a binary mixture, such as water and organic solvent, these ion pairs preferentially dissolve to those phases, respectively, and there is a coupling between the charge density and the composition. The heterogeneous distribution of ions forms a large electric double layer at the interface between these solvents. This reduces the interfacial tension between water and organic solvent, and stabilizes an ordered structure, such as a membrane. These phenomena have been extensively studied from both theoretical and experimental point of view. In addition, the numerical simulations can reproduce such ordered structures.

Stable solar-driven oxidation of water by semiconducting photoanodes protected by transparent catalytic nickel oxide films.

PubMed

Sun, Ke; Saadi, Fadl H; Lichterman, Michael F; Hale, William G; Wang, Hsin-Ping; Zhou, Xinghao; Plymale, Noah T; Omelchenko, Stefan T; He, Jr-Hau; Papadantonakis, Kimberly M; Brunschwig, Bruce S; Lewis, Nathan S

2015-03-24

Reactively sputtered nickel oxide (NiOx) films provide transparent, antireflective, electrically conductive, chemically stable coatings that also are highly active electrocatalysts for the oxidation of water to O2(g). These NiOx coatings provide protective layers on a variety of technologically important semiconducting photoanodes, including textured crystalline Si passivated by amorphous silicon, crystalline n-type cadmium telluride, and hydrogenated amorphous silicon. Under anodic operation in 1.0 M aqueous potassium hydroxide (pH 14) in the presence of simulated sunlight, the NiOx films stabilized all of these self-passivating, high-efficiency semiconducting photoelectrodes for >100 h of sustained, quantitative solar-driven oxidation of water to O2(g).

Effect of surfactant on temperature stability of solid lipid nanoparticles studied by dynamic light scattering

NASA Astrophysics Data System (ADS)

Kumar, Sacheen; Kaur, Jaspreet

2013-06-01

Solid lipid nanoparticles are new paradigm of drug delivery system of water insoluble active pharmaceutical ingredient. Paliperidone, an antipsychotic used in treatment of schizophrenia is a water insoluble molecule with low bioavailability was studied. Macrogol glyceride surfactant, bile salt based surfactant and sodium dodecyl sulphate were used to stabilize the solid lipid as dispersed nanoparticles form by adsorbing on the surface of the nanoparticles. Anionic surfactants bile salt and sodium dodecyl sulphate were found to stabilize forming a monomolecular layer of surfactants on the surface of nanoparticles; whereas macrogol glyceride based surfactant have intrusion in the matrix of lipid nanoparticles. So intrusion of macrogol glyceride in matrix was observed by studying the change in size of nanoparticles with respect to temperature with the help of dynamic light scattering. In case of macrogol glyceride size decrease start form 50°C, for bile salt and sodium dodecyl sulphate size deacrease start at 60°C. So that structural disturbance of nanoparticles by the macrogol glyceride on the surface was found maximum as compared to anionic surfactant.

The influence of wildfire severity on soil char composition and nitrogen dynamics

NASA Astrophysics Data System (ADS)

Rhoades, Charles; Fegel, Timothy; Chow, Alex; Tsai, Kuo-Pei; Norman, John, III; Kelly, Eugene

2017-04-01

Forest fires cause lasting ecological changes and alter the biogeochemical processes that control stream water quality. Decreased plant nutrient uptake is the mechanism often held responsible for lasting post-fire shifts in nutrient supply and demand, though other upland and in-stream factors also likely contribute to elevated stream nutrient losses. Soil heating, for example, creates pyrogenic carbon (C) and char layers that influence C and nitrogen (N) cycling. Char layer composition and persistence vary across burned landscapes and are influenced first by fire behavior through the temperature and duration of combustion and then by post-fire erosion. To evaluate the link between soil char and stream C and N export we studied areas burned by the 2002 Hayman Fire, the largest wildfire in Colorado, USA history. We compared soil C and N pools and processes across ecotones that included 1) unburned forests, 2) areas with moderate and 3) high wildfire severity. We analyzed 1-2 cm thick charred organic layers that remain visible 15 years after the fire, underlying mineral soils, and soluble leachate from both layers. Unburned soils released more dissolved organic C and N (DOC and DON) from organic and mineral soil layers than burned soils. The composition of DOC leachate characterized by UV-fluorescence, emission-excitation matrices (EEMs) and Fluorescence Regional Integration (FRI) found similarity between burned and unburned soils, underscoring a common organic matter source. Humic and fulvic acid-like fractions, contained in regions V and III of the FRI model, comprised the majority of the fluorescing DOM in both unburned and char layers. Similarity between two EEMs indices (Fluorescence and Freshness), further denote that unburned soils and char layers originate from the same source and are consistent with visual evidence char layers contain significant amounts of unaltered OM. However, the EEMs humification index (HIX) and compositional analysis with pyrolysis GCMS both indicate that C contained or leached from severely-burned char layers has higher aromaticity and thus chemical stability compared to C in unburned soils. Mineral soil (0-5 cm depth) beneath char layers in high severity portions of the Hayman Fire had significantly more soil N and C and lower pH. Potential net mineralization - an index of the supply of plant-available nitrogen - differed between the severely-burned areas and both unburned and moderately-burn areas. Negative net mineralization in unburned and moderately burned soils indicates immobilization or retention of inorganic N by soil microbes. In contrast, soils burned at high severity produced inorganic N sources available to plants, leaching and gas losses. Water soluble nitrate comprised a larger proportion of inorganic N leached from the char layer of high severity burns. Mineral soil in those areas had both higher water soluble nitrate and total inorganic N in leachate. Char layers that have persisted for fifteen years influence soil N turnover within the Hayman Fire affected area and may contribute to elevated N losses in streams burned at high severity. The chemical stability of soil char layers perpetuates their importance for C sequestration and N dynamics in burned landscapes.

Mechanics of graded glass composites and zinc oxide thin films grown at 90 degrees Celsius in water

NASA Astrophysics Data System (ADS)

Fillery, Scott Pierson

2007-06-01

The purpose of this research was to study the mechanical stability of two different material systems. The glass laminate system, exhibiting a threshold strength when placed under an applied load and ZnO thin films grown on GaN buffered Al2O3 substrates, exhibiting variations in film stability with changes to the Lateral Epitaxial Overgrowth architecture. The glass laminates were fabricated to contain periodic thin layers containing biaxial compressive stresses using ion exchange treatments to create residual compressive stresses at the surface of soda lime silicate glass sheets. Wafer direct bonding of the ion exchanged glass sheets resulted in the fabrication of glass laminates with thin layers of compressive stress adjacent to the glass interfaces. The threshold flexural strength of the ion exchanged glass laminates was determined to be 112 MPa after the introduction of indentation cracks with indent loads ranging from 1kg to 5kg and the laminates were found to exhibit a threshold strength, i.e., a stress below which failure will not occur. Contrary to similar ceramic laminates where cracks either propagate across the compressive layer or bifurcate within the compressive layer, the cracks in the glass laminates were deflected along the interface between the bonded sheets. ZnO films were grown on (0001) GaN buffered Al2O3 substrates by aqueous solution routes at 90°C. The films were found to buckle under compressive residual stresses at film thicknesses greater than 4mum. Lateral epitaxial overgrowth techniques using hexagonal hole arrays showed an increasing film stability with larger array spacing, resulting in film thicknesses up to 92mum. Stress determinations using Raman spectroscopy indicated that stress relaxation at the free surface during film growth played a major role in film stability. Investigations using Finite Element Analysis and Raman spectroscopy demonstrated that the strain energy within the film/substrate system decreased with increasing array spacing. ZnO films grown on III-nitride LED devices for use as transparent conducting layers showed intrinsic n-type doping, high transparency and adequate electrical contact resistance, resulting in linear light output with forward bias current and improved light extraction.

Utilize Cementitious High Carbon Fly Ash (CHCFA) to Stabilize Cold In-Place Recycled (CIR) Asphalt Pavement as Base Coarse

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

Wen, Haifang; Li, Xiaojun; Edil, Tuncer

The purpose of this study was to evaluate the performance of cementitious high carbon fly ash (CHCFA) stabilized recycled asphalt pavement as a base course material in a real world setting. Three test road cells were built at MnROAD facility in Minnesota. These cells have the same asphalt surface layers, subbases, and subgrades, but three different base courses: conventional crushed aggregates, untreated recycled pavement materials (RPM), and CHCFA stabilized RPM materials. During and after the construction of the three cells, laboratory and field tests were carried out to characterize the material properties. The test results were used in the mechanistic-empiricalmore » pavement design guide (MEPDG) to predict the pavement performance. Based on the performance prediction, the life cycle analyses of cost, energy consumption, and greenhouse gasses were performed. The leaching impacts of these three types of base materials were compared. The laboratory and field tests showed that fly ash stabilized RPM had higher modulus than crushed aggregate and RPM did. Based on the MEPDG performance prediction, the service life of the Cell 79 containing fly ash stabilized RPM, is 23.5 years, which is about twice the service life (11 years) of the Cell 77 with RPM base, and about three times the service life (7.5 years) of the Cell 78 with crushed aggregate base. The life cycle analysis indicated that the usage of the fly ash stabilized RPM as the base of the flexible pavement can significantly reduce the life cycle cost, the energy consumption, the greenhouse gases emission. Concentrations of many trace elements, particularly those with relatively low water quality standards, diminish over time as water flows through the pavement profile. For many elements, concentrations below US water drinking water quality standards are attained at the bottom of the pavement profile within 2-4 pore volumes of flow.« less

Fe-Al interface intermixing and the role of Ti, V, and Zr as a stabilizing interlayer at the interface

NASA Astrophysics Data System (ADS)

Priyantha, W.; Smith, R. J.; Chen, H.; Kopczyk, M.; Lerch, M.; Key, C.; Nachimuthu, P.; Jiang, W.

2009-03-01

Fe-Al bilayer interfaces with and without interface stabilizing layers (Ti, V, Zr) were fabricated using dc magnetron sputtering. Intermixing layer thickness and the effectiveness of the stabilizing layer (Ti, V, Zr) at the interface were studied using Rutherford backscattering spectrometry (RBS) and x-ray reflectometry (XRR). The result for the intermixing thickness of the AlFe layer is always higher when Fe is deposited on Al as compared to when Al is deposited on Fe. By comparing measurements with computer simulations, the thicknesses of the AlFe layers were determined to be 20.6 Å and 41.1 Å for Al/Fe and Fe/Al bilayer systems, respectively. The introduction of Ti and V stabilizing layers at the Fe-Al interface reduced the amount of intermixing between Al and Fe, consistent with the predictions of model calculations. The Zr interlayer, however, was ineffective in stabilizing the Fe-Al interface in spite of the chemical similarities between Ti and Zr. In addition, analysis suggests that the Ti interlayer is not effective in stabilizing the Fe-Al interface when the Ti interlayer is extremely thin (˜3 Å) for these sputtered metallic films.

Physicochemical Properties and Chemical Stability of β-Carotene Bilayer Emulsion Coated with Bovine Serum Albumin and Arabic Gum Compared to Monolayer Emulsions.

PubMed

Sheng, Bulei; Li, Lin; Zhang, Xia; Jiao, Wenjuan; Zhao, Di; Wang, Xue; Wan, Liting; Li, Bing; Rong, Hui

2018-02-23

β-carotene is a lipophilic micronutrient that is considered beneficial to human health. However, there are some limitations in utilizing β-carotene in functional foods or dietary supplements currently because of its poor water dispersibility and chemical stability. A new type of β-carotene bilayer emulsion delivery system was prepared by a layer-by-layer electrostatic deposition technique, for which were chosen bovine serum albumin (BSA) as the inner emulsifier and Arabic gum (GA) as the outer emulsifier. The physicochemical properties of bilayer emulsions were mainly characterized by droplet size distribution, zeta potential, rheological behavior, Creaming Index (CI), and encapsulation ratio of β-carotene. Besides this, the effects of processing conditions (pH, thermal treatment, UV radiation, strong oxidant) and storage time on the chemical stability of bilayer emulsions were also evaluated. The bilayer emulsion had a small droplet size (221.27 ± 5.17 nm) and distribution (PDI = 0.23 ± 0.02), strong zeta potential (-30.37 ± 0.71 mV), good rheological behavior (with the highest viscosity that could reduce the possibility of flocculation) and physical stability (CI = 0), high β-carotene encapsulation ratio (94.35 ± 0.71%), and low interfacial tension (40.81 ± 0.86 mN/m). It also obtained better chemical stability under different environmental stresses when compared with monolayer emulsions studied, because it had a dense and thick bilayer structure.

Localized in situ polymerization on graphene surfaces for stabilized graphene dispersions.

PubMed

Das, Sriya; Wajid, Ahmed S; Shelburne, John L; Liao, Yen-Chih; Green, Micah J

2011-06-01

We demonstrate a novel in situ polymerization technique to develop localized polymer coatings on the surface of dispersed pristine graphene sheets. Graphene sheets show great promise as strong, conductive fillers in polymer nanocomposites; however, difficulties in dispersion quality and interfacial strength between filler and matrix have been a persistent problem for graphene-based nanocomposites, particularly for pristine graphene. With this in mind, a physisorbed polymer layer is used to stabilize graphene sheets in solution. To create this protective layer, we formed an organic microenvironment around dispersed graphene sheets in surfactant solutions, and created a nylon 6, 10 or nylon 6, 6 coating via interfacial polymerization. Technique lies at the intersection of emulsion and admicellar polymerization; a similar technique was originally developed to protect luminescent properties of carbon nanotubes in solution. These coated graphene dispersions are aggregation-resistant and may be reversibly redispersed in water even after freeze-drying. The coated graphene holds promise for a number of applications, including multifunctional graphene-polymer nanocomposites. © 2011 American Chemical Society

Use of CdS quantum dot-functionalized cellulose nanocrystal films for anti-counterfeiting applications.

PubMed

Chen, L; Lai, C; Marchewka, R; Berry, R M; Tam, K C

2016-07-21

Structural colors and photoluminescence have been widely used for anti-counterfeiting and security applications. We report for the first time the use of CdS quantum dot (QD)-functionalized cellulose nanocrystals (CNCs) as building blocks to fabricate nanothin films via layer-by-layer (LBL) self-assembly for anti-counterfeiting applications. Both negatively- and positively-charged CNC/QD nanohybrids with a high colloidal stability and a narrow particle size distribution were prepared. The controllable LBL coating process was characterized by scanning electron microscopy and ellipsometry. The rigid structure of CNCs leads to nanoporous structured films on poly(ethylene terephthalate) (PET) substrates with high transmittance (above 70%) over the entire range of visible light and also resulted in increased hydrophilicity (contact angles of ∼40 degrees). Nanothin films on PET substrates showed good flexibility and enhanced stability in both water and ethanol. The modified PET films with structural colors from thin-film interference and photoluminescence from QDs can be used in anti-counterfeiting applications.

Protein adsorption at the electrified air-water interface: implications on foam stability.

PubMed

Engelhardt, Kathrin; Rumpel, Armin; Walter, Johannes; Dombrowski, Jannika; Kulozik, Ulrich; Braunschweig, Björn; Peukert, Wolfgang

2012-05-22

The surface chemistry of ions, water molecules, and proteins as well as their ability to form stable networks in foams can influence and control macroscopic properties such as taste and texture of dairy products considerably. Despite the significant relevance of protein adsorption at liquid interfaces, a molecular level understanding on the arrangement of proteins at interfaces and their interactions has been elusive. Therefore, we have addressed the adsorption of the model protein bovine serum albumin (BSA) at the air-water interface with vibrational sum-frequency generation (SFG) and ellipsometry. SFG provides specific information on the composition and average orientation of molecules at interfaces, while complementary information on the thickness of the adsorbed layer can be obtained with ellipsometry. Adsorption of charged BSA proteins at the water surface leads to an electrified interface, pH dependent charging, and electric field-induced polar ordering of interfacial H(2)O and BSA. Varying the bulk pH of protein solutions changes the intensities of the protein related vibrational bands substantially, while dramatic changes in vibrational bands of interfacial H(2)O are simultaneously observed. These observations have allowed us to determine the isoelectric point of BSA directly at the electrolyte-air interface for the first time. BSA covered air-water interfaces with a pH near the isoelectric point form an amorphous network of possibly agglomerated BSA proteins. Finally, we provide a direct correlation of the molecular structure of BSA interfaces with foam stability and new information on the link between microscopic properties of BSA at water surfaces and macroscopic properties such as the stability of protein foams.

Nucleation processes of nanobubbles at a solid/water interface

NASA Astrophysics Data System (ADS)

Fang, Chung-Kai; Ko, Hsien-Chen; Yang, Chih-Wen; Lu, Yi-Hsien; Hwang, Ing-Shouh

2016-04-01

Experimental investigations of hydrophobic/water interfaces often return controversial results, possibly due to the unknown role of gas accumulation at the interfaces. Here, during advanced atomic force microscopy of the initial evolution of gas-containing structures at a highly ordered pyrolytic graphite/water interface, a fluid phase first appeared as a circular wetting layer ~0.3 nm in thickness and was later transformed into a cap-shaped nanostructure (an interfacial nanobubble). Two-dimensional ordered domains were nucleated and grew over time outside or at the perimeter of the fluid regions, eventually confining growth of the fluid regions to the vertical direction. We determined that interfacial nanobubbles and fluid layers have very similar mechanical properties, suggesting low interfacial tension with water and a liquid-like nature, explaining their high stability and their roles in boundary slip and bubble nucleation. These ordered domains may be the interfacial hydrophilic gas hydrates and/or the long-sought chemical surface heterogeneities responsible for contact line pinning and contact angle hysteresis. The gradual nucleation and growth of hydrophilic ordered domains renders the original homogeneous hydrophobic/water interface more heterogeneous over time, which would have great consequence for interfacial properties that affect diverse phenomena, including interactions in water, chemical reactions, and the self-assembly and function of biological molecules.

A flexible, robust and antifouling asymmetric membrane based on ultra-long ceramic/polymeric fibers for high-efficiency separation of oil/water emulsions.

PubMed

Wang, Kui; Yiming, Wubulikasimu; Saththasivam, Jayaprakash; Liu, Zhaoyang

2017-07-06

Polymeric and ceramic asymmetric membranes have dominated commercial membranes for water treatment. However, polymeric membranes are prone to becoming fouled, while ceramic membranes are mechanically fragile. Here, we report a novel concept to develop asymmetric membranes based on ultra-long ceramic/polymeric fibers, with the combined merits of good mechanical stability, excellent fouling resistance and high oil/water selectivity, in order to meet the stringent requirements for practical oil/water separation. The ultra-long dimensions of ceramic nanofibers/polymeric microfibers endow this novel membrane with mechanical flexibility and robustness, due to the integrated and intertwined structure. This membrane is capable of separating oil/water emulsions with high oil-separation efficiency (99.9%), thanks to its nanoporous selective layer made of ceramic nanofibers. Further, this membrane also displays superior antifouling properties due to its underwater superoleophobicity and ultra-low oil adhesion of the ceramic-based selective layer. This membrane exhibits high water permeation flux (6.8 × 10 4 L m -2 h -1 bar -1 ) at low operation pressures, which is attributed to its 3-dimensional (3D) interconnected fiber-based structure throughout the membrane. In addition, the facile fabrication process and inexpensive materials required for this membrane suggest its significant potential for industrial applications.

Spray dried microparticles of chia oil using emulsion stabilized by whey protein concentrate and pectin by electrostatic deposition.

PubMed

Noello, C; Carvalho, A G S; Silva, V M; Hubinger, M D

2016-11-01

Chia seed oil has a high content of α-linolenic acid (60%) and linoleic acid (20%). Use of this oil in different products is limited due to its liquid state, and the presence of insaturation is a trigger for oxidation. In this context, to facilitate the incorporation of chia oil in food products and increase its protection against oxidation, the aim of this work was to produce chia oil microparticles by spray drying using emulsions stabilized by whey protein concentrate (ζ-potential +13.4 at pH3.8) and pectin (ζ-potential -40.4 at pH3.8) through the electrostatic layer-by-layer deposition technique and emulsions prepared with only whey protein concentrate. Emulsions stabilized by whey protein concentrate and stabilized by whey protein concentrate-pectin were prepared using maltodextrin (10 DE) and modified starch (Hi-Cap® 100). They were characterized in relation to stability, droplet size, ζ-Potential and optical microscopy. The microparticles were characterized in relation to moisture content, water activity, particle size, microstructure and oxidative stability by the Rancimat method. Emulsions stabilized by whey protein concentrate-pectin with added maltodextrin 10 DE and emulsions stabilized by whey protein concentrate with added modified starch (Hi-Cap® 100) were stable after 24h. Emulsions stabilized by whey protein concentrate and by whey protein concentrate-pectin showed droplets with mean diameter ranging from 0.80 to 1.31μm, respectively and ζ-potential varying from -6.9 to -27.43mV, respectively. After spray drying, the microparticles showed an mean diameter ranging from 7.00 to 9.00μm. All samples presented high encapsulation efficiency values, above 99%. Microparticles produced with modified starch showed a smoother spherical surface than particles with maltodextrin 10 DE, which presented a wrinkled surface. All microparticles exhibited higher oxidative stability than chia oil in pure form. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ultrasonication assisted Layer-by-Layer technology for the preparation of multi-functional anticancer drugs paclitaxel and lapatinib

NASA Astrophysics Data System (ADS)

Zhang, Xingcai

In this dissertation, ultrasonication assisted Layer-by-Layer (LbL) technology for the preparation of multifunctional poorly water-soluble anticancer drug nanoparticles, paclitaxel and lapatinib, has been developed. Many FDA approved drugs are very low soluble in water; therefore, it is very difficult to load and control their release and targeting efficiently, which greatly confines their application. The development of this method will pave the way for the development and application of those low soluble anticancer drugs. In the first part of this dissertation, the first approach for powerful ultrasonication, the top-down approach (sonicating bulk drug crystals in polyelectrolyte solution), was successfully applied for the preparation of the nanoparticles of paclitaxel. For this approach, a 200 nm diameter was a kind of "magic" barrier for colloidal particles prepared. This diameter barrier may be related to the nucleation size of the solvent vapor microbubbles. Consequently, agents enhancing bubbling formation (such as NH4HCO3) were applied to decrease paclitaxel colloid particles to 100-120 nm. Those paclitaxel nanoparticles were Layer-by-Layer coated with a 10-20 nm polycation/polyanion shell to provide aqueous colloidal stability and slower particle dissolution. However, a large obstacle of these powerful ultrasonication methods was a necessity of long ca 45 minutes high power ultrasonication which resulted in TiO2 contamination from titanium electrode. The small amount of TiO2 contamination from ultrasonication did negatively affect the in vivo testing of this system in mice, and had to be removed before low toxicity of the Layer-by-Layer coated paclitaxel nanoparticles were observed. In the second part of the dissertation, the second approach for sonication, the bottom-up approach (sonicating drug in a water-miscible organic solvent followed by slow water add-in) was successfully applied for the preparation of the nanoparticles of lapatinib and paclitaxel with less powerful sonication. By using polymeric excipients combined with non-ionic and anionic surfactants along with regular sonication, the prepared particle sizes was uniform at around 140-150 nm. Less sonication time (ca 15 minutes) and lower sonication power avoided TiO2 contamination. The amphiphiles attached to the hydrophobic nanoparticles and served as anchors for LbL shell. The inner LbL layers and surfactants minimized the surface free energy, thereby preventing crystal form changes and nanoparticles coalescence, while the outermost layers enhanced colloidal stability. In the third part of the dissertation, LbL shells with PEGylation (using a block copolymer of poly-L-lysine (PLL) and PEG) for lapatinib were developed for enhanced colloidal stability in high molarity PBS buffer. In the above proposed paclitaxel and lapatinib formulation, we obtained 150-200 nm with high drug content of 80-90% due to very thin capsule walls (ca 10 nm). The drug release time from the LbL capsules was found to be between 10 and 20 hours depending on the shell thickness. Washless Layer-by-Layer assembly was used: 1) addition of polycation in the amount that is enough to reverse surface charge of the dispersion to a high positive (+30 mV) value; 2) addition of polyanion in the amount that is enough to reverse surface charge of the dispersion to a high negative (-30 mV) value. No intermediate washing of nanoparticles was done until the shell was complete. The washless method had the advantage of time and energy saving, preservation of the sample structure and no losses of sample. In the last part of the dissertation, we elaborated nanoformulation of two drugs in one nanocapsule locating paclitaxel in the core and lapatinib on the shell periphery. With this formulation, combining in one nanoparticle dual drugs, we reached the drugs' efficiency synergy. In a multidrug-resistant (MDR) ovarian cancer cell line, OVCAR-3, LbL lapatinib/paclitaxel nanocolloids mediated an enhanced cell growth inhibition in comparison with the LbL paclitaxel-only and LbL lapatinib-only treatment, not to say the free one drug treatment.

Atomically thin transition metal layers: Atomic layer stabilization and metal-semiconductor transition

NASA Astrophysics Data System (ADS)

Hwang, Jeongwoon; Oh, Young Jun; Kim, Jiyoung; Sung, Myung Mo; Cho, Kyeongjae

2018-04-01

We have performed first-principle calculations to explore the possibility of synthesizing atomically thin transition metal (TM) layers. Buckled structures as well as planar structures of elemental 2D TM layers result in significantly higher formation energies compared with sp-bonded elemental 2D materials with similar structures, such as silicene and phosphorene. It is shown that the TM layers can be stabilized by surface passivation with HS, C6H5S2, or O, and O passivation is most effective. The surface oxygen passivation can improve stability leading to thermodynamically stable TM monolayers except Au, which is the most non-reactive metal element. Such stabilized TM monolayers also show an electronic structure transition from metallic state of free-standing TM layer to semiconducting O-passivated Mo and W monolayers with band gaps of 0.20-1.38 eV.

Deep Arctic Ocean warming during the last glacial cycle

USGS Publications Warehouse

Cronin, T. M.; Dwyer, G.S.; Farmer, J.; Bauch, H.A.; Spielhagen, R.F.; Jakobsson, M.; Nilsson, J.; Briggs, W.M.; Stepanova, A.

2012-01-01

In the Arctic Ocean, the cold and relatively fresh water beneath the sea ice is separated from the underlying warmer and saltier Atlantic Layer by a halocline. Ongoing sea ice loss and warming in the Arctic Ocean have demonstrated the instability of the halocline, with implications for further sea ice loss. The stability of the halocline through past climate variations is unclear. Here we estimate intermediate water temperatures over the past 50,000 years from the Mg/Ca and Sr/Ca values of ostracods from 31 Arctic sediment cores. From about 50 to 11 kyr ago, the central Arctic Basin from 1,000 to 2,500 m was occupied by a water mass we call Glacial Arctic Intermediate Water. This water mass was 1–2 °C warmer than modern Arctic Intermediate Water, with temperatures peaking during or just before millennial-scale Heinrich cold events and the Younger Dryas cold interval. We use numerical modelling to show that the intermediate depth warming could result from the expected decrease in the flux of fresh water to the Arctic Ocean during glacial conditions, which would cause the halocline to deepen and push the warm Atlantic Layer into intermediate depths. Although not modelled, the reduced formation of cold, deep waters due to the exposure of the Arctic continental shelf could also contribute to the intermediate depth warming.

Two receptor tyrosine phosphatases dictate the depth of axonal stabilizing layer in the visual system

PubMed Central

Takechi, Hiroki; Kawamura, Hinata

2017-01-01

Formation of a functional neuronal network requires not only precise target recognition, but also stabilization of axonal contacts within their appropriate synaptic layers. Little is known about the molecular mechanisms underlying the stabilization of axonal connections after reaching their specifically targeted layers. Here, we show that two receptor protein tyrosine phosphatases (RPTPs), LAR and Ptp69D, act redundantly in photoreceptor afferents to stabilize axonal connections to the specific layers of the Drosophila visual system. Surprisingly, by combining loss-of-function and genetic rescue experiments, we found that the depth of the final layer of stable termination relied primarily on the cumulative amount of LAR and Ptp69D cytoplasmic activity, while specific features of their ectodomains contribute to the choice between two synaptic layers, M3 and M6, in the medulla. These data demonstrate how the combination of overlapping downstream but diversified upstream properties of two RPTPs can shape layer-specific wiring. PMID:29116043

Insights into Interfacial Changes and Photoelectrochemical Stability of In(x)Ga(1-x)N (0001) Photoanode Surfaces in Liquid Environments.

PubMed

Caccamo, Lorenzo; Cocco, Giulio; Martín, Gemma; Zhou, Hao; Fundling, Sönke; Gad, Alaaeldin; Mohajerani, Matin Sadat; Abdelfatah, Mahmoud; Estradé, Sonia; Peiró, Francesca; Dziony, Wanja; Bremers, Heiko; Hangleiter, Andreas; Mayrhofer, Leonhard; Lilienkamp, Gerhard; Moseler, Michael; Daum, Winfried; Waag, Andreas

2016-03-01

The long-term stability of InGaN photoanodes in liquid environments is an essential requirement for their use in photoelectrochemistry. In this paper, we investigate the relationships between the compositional changes at the surface of n-type In(x)Ga(1-x)N (x ∼ 0.10) and its photoelectrochemical stability in phosphate buffer solutions with pH 7.4 and 11.3. Surface analyses reveal that InGaN undergoes oxidation under photoelectrochemical operation conditions (i.e., under solar light illumination and constant bias of 0.5 VRHE), forming a thin amorphous oxide layer having a pH-dependent chemical composition. We found that the formed oxide is mainly composed of Ga-O bonds at pH 7.4, whereas at pH 11.3 the In-O bonds are dominant. The photoelectrical properties of InGaN photoanodes are intimately related to the chemical composition of their surface oxides. For instance, after the formation of the oxide layer (mainly Ga-O bonds) at pH 7.4, no photocurrent flow was observed, whereas the oxide layer (mainly In-O bonds) at pH 11.3 contributes to enhance the photocurrent, possibly because of its reported high photocatalytic activity. Once a critical oxide thickness was reached, especially at pH 7.4, no significant changes in the photoelectrical properties were observed for the rest of the test duration. This study provides new insights into the oxidation processes occurring at the InGaN/liquid interface, which can be exploited to improve InGaN stability and enhance photoanode performance for biosensing and water-splitting applications.

Oriented conductive oxide electrodes on SiO2/Si and glass

DOEpatents

Jia, Quanxi; Arendt, Paul N.

2001-01-01

A thin film structure is provided including a silicon substrate with a layer of silicon dioxide on a surface thereof, and a layer of cubic oxide material deposited upon the layer of silicon dioxide by ion-beam-assisted-deposition, said layer of cubic oxide material characterized as biaxially oriented. Preferably, the cubic oxide material is yttria-stabilized zirconia. Additional thin layers of biaxially oriented ruthenium oxide or lanthanum strontium cobalt oxide are deposited upon the layer of yttria-stabilized zirconia. An intermediate layer of cerium oxide is employed between the yttria-stabilized zirconia layer and the lanthanum strontium cobalt oxide layer. Also, a layer of barium strontium titanium oxide can be upon the layer of biaxially oriented ruthenium oxide or lanthanum strontium cobalt oxide. Also, a method of forming such thin film structures, including a low temperature deposition of a layer of a biaxially oriented cubic oxide material upon the silicon dioxide surface of a silicon dioxide/silicon substrate is provided.

Effect of sorbitol and glycerol on the stability of trypsin and difference between their stabilization effects in the various solvents.

PubMed

Pazhang, Mohammad; Mehrnejad, Faramarz; Pazhang, Yaghub; Falahati, Hanieh; Chaparzadeh, Nader

2016-01-01

The effect of glycerol and sorbitol on the stability of porcine pancreas trypsin was investigated in this work. Molecular dynamics simulation and thermostability results showed that trypsin has two flexible regions, and polyols (sorbitol and glycerol) stabilize the enzyme by decreasing the flexibility of these regions. Radial distribution function results exhibited that sorbitol and glycerol were excluded from the first water layer of the enzyme, therefore decrease the flexibility of the regions by preferential exclusion. Also, results showed that the stabilization effect of sorbitol is more than glycerol. This observation could be because of the larger decrease in the fluctuations of trypsin in the presence of sorbitol. We also examined the role of solvent's hydrophobicity in enzyme stabilization by sorbitol and glycerol. To do so, the thermostability of trypsin was evaluated in the presence of solvents with different hydrophobicity (methanol, ethanol, isopropanol and n-propanol) in addition to the polyols. Our results depicted that glycerol is a better stabilizer than sorbitol in the presence of hydrophobic solvents (n-propanol), whereas sorbitol is a better stabilizer than glycerol in the presence of hydrophilic solvents (methanol). © 2015 International Union of Biochemistry and Molecular Biology, Inc.

Simultaneous enhancement of photovoltage and charge transfer in Cu{sub 2}O-based photocathode using buffer and protective layers

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

Li, Changli; Delaunay, Jean-Jacques, E-mail: jean@mech.t.u-tokyo.ac.jp; Hisatomi, Takashi

2016-07-18

Coating n-type buffer and protective layers on Cu{sub 2}O may be an effective means to improve the photoelectrochemical (PEC) water-splitting performance of Cu{sub 2}O-based photocathodes. In this letter, the functions of the buffer layer and protective layer on Cu{sub 2}O are examined. It is found that a Ga{sub 2}O{sub 3} buffer layer can form a buried junction with Cu{sub 2}O, which inhibits Cu{sub 2}O self-reduction as well as increases the photovoltage through a small conduction band offset between the two semiconductors. The introduction of a TiO{sub 2} thin protective layer not only improves the stability of the photocathode but alsomore » enhances the electron transfer from the photocathode surface into the electrolyte, thus resulting in an increase in photocurrent at positive potentials. These results show that the selection of overlayers with appropriate conduction band positions provides an effective strategy for obtaining a high photovoltage and high photocurrent in PEC systems.« less

Characterization of a Biomimetic Polymeric-Lipid Bilayer by Phase Sensitive Neutron Reflectivity

NASA Astrophysics Data System (ADS)

Perez-Salas, Ursula A.; Krueger, Susan; Majkrzak, Charles F.; Berk, Norman F.; Faucher, Keith M.; Chaikof, Elliot L.

2003-03-01

Lipid membranes, the boundaries for cellular and intracellular structures, regulate many crucial biological processes. Planar supported mimics of cell membranes are of great interest as model systems for the study of membrane structure/function phenomena in fundamental biophysics research. We studied a supported biomedically relevant membrane-mimetic system composed of a polyelectrolyte cushion, a terpolymer and a self-assembled phospholipid monolayer and obtained a detailed profile characterization of the system by neutron reflectometry. The water-swellable hydrophilic polyelectrolyte acts as a support for the biomembrane, not unlike the cytoskeletal support found in actual mammalian cell membranes. The "cushion" polymers are fixed to the flat, hard surface by having the polymer interact with it electrostatically. The terpolymer has the following desirable features: it tethers to the polyelectrolyte layer and it creates a hydrophilic and a hydrophobic region. Unilamellar phospholipid vesicle fusion on to the hydrophobic region of the terpolymer creates the hybrid tethered membrane. For added stability to external force fields (such as shear flow), the phospholipid monolayer is then polymerized in situ, effectively anchoring the lipid layer to the hydrophobic region of the terpolymer. Neutron reflectivity measurements were done on the polyelectrolyte layer, the polyelectrolyte layer plus terpolymer and the polylectrolyte layer plus terpolymer plus phospholipid. The layers were studied dry and hydrated and under 95α D_2O and 50% \\ 50% α H_2O \\ α D_2O) on the polyelectrolyte layer plus terpolymer and the polylectrolyte layer plus terpolymer plus phospholipid the distribution of water in the layers was obtained. The results will be correlated to impedance measurements flourescence measurements and infrared spectroscopy measurements made on equivalent samples.

An experimental study of the role of particle diffusive convection on the residence time of volcanic ash clouds

NASA Astrophysics Data System (ADS)

Deal, E.; Carazzo, G.; Jellinek, M.

2013-12-01

The longevity of volcanic ash clouds generated by explosive volcanic plumes is difficult to predict. Diffusive convective instabilities leading to the production of internal layering are known to affect the stability and longevity of these clouds, but the detailed mechanisms controlling particle dynamics and sedimentation are poorly understood. We present results from a series of analog experiments reproducing diffusive convection in a 2D (Hele-Shaw) geometry, which allow us to constrain conditions for layer formation, sedimentation regime and cloud residence time as a function of only the source conditions. We inject a turbulent particle-laden jet sideways into a tank containing a basal layer of salt water and an upper layer of fresh water, which ultimately spreads as a gravity current. After the injection is stopped, particles in suspension settle through the cloud to form particle boundary layers (PBL) at the cloud base. We vary the initial particle concentration of the plume and the injection velocity over a wide range of conditions to identify and characterize distinct regimes of sedimentation. Our experiments show that convective instabilities driven as a result of differing diffusivities of salt and particles lead to periodic layering over a wide range of conditions expected in nature. The flux of particles from layered clouds and the thicknesses of the layers are understood using classical theory for double diffusive convection adjusted for the hydrodynamic diffusion of particles. Although diffusive convection increases sedimentation rates for the smallest particles (<30 μm) its overall effect is to extend the cloud residence time to several hours by maintaining larger particles in suspension within the layers, which is several orders of magnitude longer than expected when considering individual settling rates.

On the Single-Layer Hydraulics Model for Flows and Ventilation over Unban Areas in Stable Stratification

NASA Astrophysics Data System (ADS)

Liu, C. H.

2015-12-01

Atmospheric stability has substantial effects on the flows and heat/mass transport processes. While extensive studies have been conducted for neutral and unstable stabilities, rather limited studies have been devoted to stable stratification. Major technical reason is the demanding spatio-temporal resolution required to solve the small scales in stratified turbulent flows. Instead of continuous density variation, we use the single-layer hydraulics model (analogous to shallow water equations for global dynamics), to simulate the stratified flows and turbulence structure over hypothetical urban areas. An array of identical ribs in cross flows is used to model an idealized urban surface and the aerodynamic resistance is controlled by the separation among the ribs. Two immiscible fluids (water and air) with a large density difference (three order of magnitude) are used to simulate the stratification. The key assumption is that the density in the (lower) single layer is uniform. As a result, the stratification is measured by the Froude number Fr (= U/(gH)1/2; where U is the flow speed, g the gravitational acceleration and H the single-layer depth). One of the characteristics of single-layer hydraulics model is hydraulic jump which occurs when the flows are slowing down from Fr > 1 (high-speed flows over smoother surfaces) to Fr < 1 (lower-speed flows over rougher surfaces). It is noteworthy that kinetic energy does not conserve across hydraulic jump that, unavoidably, cascades to turbulent kinetic energy (TKE). We thus hypotheses that the elevated TKE could modify the street-level ventilation mechanism in the stratified flows across an abrupt change in surface roughness entering urban areas. Large-eddy simulation and laboratory-scale water channel experiments are sought to improve our understanding of the occurrence of hydraulic jump and the associated street-level ventilation mechanism in the stratified flows over urban areas. Preliminary results, by comparing the dynamics at Fr = 2.4 and Fr = 2.8, demonstrate the notable changes in ventilation performance in the first several rows of ribs of urban areas. Substantial changes in the mean and fluctuating velocities are observed that contribute to the different street-level ventilation mechanism. Detailed results will be reported in the upcoming AGU fall meeting.

Intraday evaporation and heat fluxes variation at air-water interface of extremely shallow lakes in Chilean Andean Plateau

NASA Astrophysics Data System (ADS)

Vergara, Jaime; de la Fuente, Alberto

2016-04-01

Salars are landscapes formed by evapo-concentration of salts that usually have extremely shallow terminal lagoons (de la Fuente & Niño, 2010). They are located in the altiplanic region of the Andes Mountains of Chile, Argentina, Bolivia and Peru, and they sustain highly vulnerable and isolated ecosystems in the Andean Desert. These ecosystems are sustained by benthic primary production, which is directly linked to mass, heat and momentum transfer between the water column and the atmosphere (de la Fuente, 2014). Despite the importance of these transport processes across the air-water interface, there are few studies describing their intraday variation and how they are influenced by the stability of the atmospheric boundary layer in the altiplano. The main objective of this work is to analyze the intraday vertical transport variation of water vapor, temperature and momentum between the atmosphere and a shallow water body on Salar del Huasco located in northern Chile (20°19'40"S, 68°51'25"W). To achieve this goal, we measured atmospheric and water variables in a campaign realized on late October 2015, using high frequency meteorological instruments (a sonic anemometer with an incorporated infrared gas analyzer, and a standard meteorological station) and water sensors. From these data, we characterize the intraday variation of water vapor, temperature and momentum fluxes, we quantify the influence of the atmospheric boundary layer stability on them, and we estimate transfer coefficients associated to latent heat, sensible heat, hydrodynamic drag and vertical transport of water vapor. As first results, we found that latent and sensible heat fluxes are highly influenced by wind speed rather buoyancy, and we can identify four intraday intervals with different thermo-hydrodynamic features: (1) cooling under stable condition with wind speed near 0 from midnight until sunrise; (2) free convection with nearly no wind speed under unstable condition from sunrise until midday; (3) forced convection with high wind speed (near 15 m/s) and unstable condition close to neutral condition from noon to sunset; and (4) cooling under unstable conditions with significant wind speed, from sunset until midnight.

Measuring water adsorption on mineral surfaces in air, CO2, and supercritical CO2 with a quartz-crystal microbalance

NASA Astrophysics Data System (ADS)

Bryan, C. R.; Wells, R. K.; Burton, P. D.; Heath, J. E.; Dewers, T. A.; Wang, Y.

2011-12-01

Carbon sequestration via underground storage in geologic formations is a proposed approach for reducing industrial CO2 emissions. However, current models for carbon injection and long-term storage of supercritical CO2 (scCO2) do not consider the development and stability of adsorbed water films at the scCO2-hydrophilic mineral interface. The thickness and properties of the water films control the surface tension and wettability of the mineral surface, and on the core scale, affect rock permeability, saturation, and capillary properties. The film thickness is strongly dependent upon the activity of water in the supercritical fluid, which will change as initially anhydrous scCO2 absorbs water from formation brine. As described in a companion paper by the coauthors, the thickness of the adsorbed water layer is controlled by the disjoining pressure; structural and van der Waals components dominate at low water activity, while electrostatic forces become more important with increasing film thickness (higher water activities). As scCO2 water activity and water layer thickness increase, concomitant changes in mineral surface properties and reservoir/caprock hydrologic properties will affect the mobility of the aqueous phase and of scCO2. Moreover, the development of a water layer may be critical to mineral dissolution reactions in scCO2. Here, we describe the use of a quartz-crystal microbalance (QCM) to monitor adsorption of water by mineral surfaces. QCMs utilize a piezoelectrically-stimulated quartz wafer to measure adsorbed or deposited mass via changes in vibrational frequency. When used to measure the mass of adsorbed liquid films, the frequency response of the crystal must be corrected for the viscoelastic, rather than elastic, response of the adsorbed layer. Results are presented for adsorption to silica in N2 and CO2 at one bar, and in scCO2. Additional data are presented for water uptake by clays deposited on a QCM wafer. In this case, water uptake occurs by the combined processes of interlayer cation hydration, surface adsorption, and capillary condensation. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000. This work is supported by the DOE Sandia LDRD Program.

Role of structural H 2O in TiO 2 nanotubes in enhancing Pt/C direct ethanol fuel cell anode electro-catalysts

NASA Astrophysics Data System (ADS)

Song, Huanqiao; Qiu, Xinping; Guo, Daojun; Li, Fushen

TiO 2 nanotubes (TNTs) with different structural water were obtained by heat treatment under different temperatures. The role of the structural water in TNTs co-catalyzing ethanol oxidation with Pt/C catalyst was studied systematically. Electrochemical studies using cyclic voltammetry and CO stripping voltammetry indicated that more structural water in TNTs was favorable for improving the tolerance of Pt/C to poisoning species; while chronoamperometry curves and repeated cyclic voltammograms showed that slightly less structural water in TNTs actually led to higher catalytic activity and better stability of Pt/C catalysts for ethanol oxidation. This strange result has been analyzed and was ascribed to the appropriate balance of bi-functional mechanism and ethanol transfer in the catalyst layer with less structural water.

A Model for the Formation and Melting of Ice on Surface Waters.

NASA Astrophysics Data System (ADS)

de Bruin, H. A. R.; Wessels, H. R. A.

1988-02-01

Ice covers have an important influence on the hydrology of surface waters. The growth of ice layer on stationary waters, such as lakes or canals, depends primarily on meteorological parameters like temperature and humidity of the air, windspeed and radiation balance. The more complicated ice formation in rapidly flowing rivers is not considered in this study. A model is described that simulates ice growth and melting utilizing observed or forecast weather data. The model includes situations with a snow cover. Special attention is given to the optimal estimation of the net radiation and to the role of the stability of the near-surface air. Since a major practical application in the Netherlands is the use of frozen waters for recreation skating, the model is extended to include artificial ice tracks.

Determining the Effective Density and Stabilizer Layer Thickness of Sterically Stabilized Nanoparticles

PubMed Central

2016-01-01

A series of model sterically stabilized diblock copolymer nanoparticles has been designed to aid the development of analytical protocols in order to determine two key parameters: the effective particle density and the steric stabilizer layer thickness. The former parameter is essential for high resolution particle size analysis based on analytical (ultra)centrifugation techniques (e.g., disk centrifuge photosedimentometry, DCP), whereas the latter parameter is of fundamental importance in determining the effectiveness of steric stabilization as a colloid stability mechanism. The diblock copolymer nanoparticles were prepared via polymerization-induced self-assembly (PISA) using RAFT aqueous emulsion polymerization: this approach affords relatively narrow particle size distributions and enables the mean particle diameter and the stabilizer layer thickness to be adjusted independently via systematic variation of the mean degree of polymerization of the hydrophobic and hydrophilic blocks, respectively. The hydrophobic core-forming block was poly(2,2,2-trifluoroethyl methacrylate) [PTFEMA], which was selected for its relatively high density. The hydrophilic stabilizer block was poly(glycerol monomethacrylate) [PGMA], which is a well-known non-ionic polymer that remains water-soluble over a wide range of temperatures. Four series of PGMAx–PTFEMAy nanoparticles were prepared (x = 28, 43, 63, and 98, y = 100–1400) and characterized via transmission electron microscopy (TEM), dynamic light scattering (DLS), and small-angle X-ray scattering (SAXS). It was found that the degree of polymerization of both the PGMA stabilizer and core-forming PTFEMA had a strong influence on the mean particle diameter, which ranged from 20 to 250 nm. Furthermore, SAXS was used to determine radii of gyration of 1.46 to 2.69 nm for the solvated PGMA stabilizer blocks. Thus, the mean effective density of these sterically stabilized particles was calculated and determined to lie between 1.19 g cm–3 for the smaller particles and 1.41 g cm–3 for the larger particles; these values are significantly lower than the solid-state density of PTFEMA (1.47 g cm–3). Since analytical centrifugation requires the density difference between the particles and the aqueous phase, determining the effective particle density is clearly vital for obtaining reliable particle size distributions. Furthermore, selected DCP data were recalculated by taking into account the inherent density distribution superimposed on the particle size distribution. Consequently, the true particle size distributions were found to be somewhat narrower than those calculated using an erroneous single density value, with smaller particles being particularly sensitive to this artifact. PMID:27478250

Interface engineering of colloidal CdSe quantum dots thin films as acid-stable photocathodes for solar-driven hydrogen evolution

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

Li, Hui; Wen, Peng; Hoxie, Adam

Colloidal semiconductor quantum dots-based (CQD) photocathodes for solar-driven hydrogen evolution have attracted significant attention due to their tunable size, nanostructured morphology, crystalline orientation, and band-gap. Here, we report a thin film heterojunction photocathode composed of organic PEDOT:PSS as a hole transport layer, CdSe CQDs as a semiconductor light absorber, and conformal Pt layer deposited by atomic layer deposition (ALD) serving as both a passivation layer and cocatalyst for hydrogen evolution. In neutral aqueous solution, a PEDOT:PSS/CdSe/Pt heterogeneous photocathode with 200 cycles of ALD Pt produces a photocurrent density of -1.08 mA/cm 2 (AM1.5G, 100 mW/cm 2) at a potential ofmore » 0 V vs. RHE (j 0) in neutral aqueous solution, which is nearly 12 times that of the pristine CdSe photocathode. This composite photocathode shows an onset potential for water reduction at +0.46 V vs. RHE and long-term stability with negligible degradation. In acidic electrolyte (pH = 1), where the hydrogen evolution reaction is more favorable but stability is limited due to photocorrosion, a thicker Pt film (300 cycles) is shown to greatly improve the device stability and a j 0 of -2.14 mA/cm 2 is obtained with only 8.3% activity degradation after 6 h, compared to 80% degradation under the same conditions when the less conformal electrodeposition method is used to deposit the Pt layer. Electrochemical impedance spectroscopy and time-resolved photoluminescence results indicate that these enhancements stem from a lower bulk charge recombination rate, higher interfacial charge transfer rate, and faster reaction kinetics. In conclusion, we believe that these interface engineering strategies can be extended to other colloidal semiconductors to construct more efficient and stable heterogeneous photoelectrodes for solar fuel production.« less

Interface engineering of colloidal CdSe quantum dots thin films as acid-stable photocathodes for solar-driven hydrogen evolution

DOE PAGES

Li, Hui; Wen, Peng; Hoxie, Adam; ...

2018-04-30

Colloidal semiconductor quantum dots-based (CQD) photocathodes for solar-driven hydrogen evolution have attracted significant attention due to their tunable size, nanostructured morphology, crystalline orientation, and band-gap. Here, we report a thin film heterojunction photocathode composed of organic PEDOT:PSS as a hole transport layer, CdSe CQDs as a semiconductor light absorber, and conformal Pt layer deposited by atomic layer deposition (ALD) serving as both a passivation layer and cocatalyst for hydrogen evolution. In neutral aqueous solution, a PEDOT:PSS/CdSe/Pt heterogeneous photocathode with 200 cycles of ALD Pt produces a photocurrent density of -1.08 mA/cm 2 (AM1.5G, 100 mW/cm 2) at a potential ofmore » 0 V vs. RHE (j 0) in neutral aqueous solution, which is nearly 12 times that of the pristine CdSe photocathode. This composite photocathode shows an onset potential for water reduction at +0.46 V vs. RHE and long-term stability with negligible degradation. In acidic electrolyte (pH = 1), where the hydrogen evolution reaction is more favorable but stability is limited due to photocorrosion, a thicker Pt film (300 cycles) is shown to greatly improve the device stability and a j 0 of -2.14 mA/cm 2 is obtained with only 8.3% activity degradation after 6 h, compared to 80% degradation under the same conditions when the less conformal electrodeposition method is used to deposit the Pt layer. Electrochemical impedance spectroscopy and time-resolved photoluminescence results indicate that these enhancements stem from a lower bulk charge recombination rate, higher interfacial charge transfer rate, and faster reaction kinetics. In conclusion, we believe that these interface engineering strategies can be extended to other colloidal semiconductors to construct more efficient and stable heterogeneous photoelectrodes for solar fuel production.« less

Interface Engineering of Colloidal CdSe Quantum Dot Thin Films as Acid-Stable Photocathodes for Solar-Driven Hydrogen Evolution.

PubMed

Li, Hui; Wen, Peng; Hoxie, Adam; Dun, Chaochao; Adhikari, Shiba; Li, Qi; Lu, Chang; Itanze, Dominique S; Jiang, Lin; Carroll, David; Lachgar, Abdou; Qiu, Yejun; Geyer, Scott M

2018-05-23

Colloidal semiconductor quantum dot (CQD)-based photocathodes for solar-driven hydrogen evolution have attracted significant attention because of their tunable size, nanostructured morphology, crystalline orientation, and band gap. Here, we report a thin film heterojunction photocathode composed of organic PEDOT:PSS as a hole transport layer, CdSe CQDs as a semiconductor light absorber, and conformal Pt layer deposited by atomic layer deposition (ALD) serving as both a passivation layer and cocatalyst for hydrogen evolution. In neutral aqueous solution, a PEDOT:PSS/CdSe/Pt heterogeneous photocathode with 200 cycles of ALD Pt produces a photocurrent density of -1.08 mA/cm 2 (AM-1.5G, 100 mW/cm 2 ) at a potential of 0 V versus reversible hydrogen electrode (RHE) ( j 0 ) in neutral aqueous solution, which is nearly 12 times that of the pristine CdSe photocathode. This composite photocathode shows an onset potential for water reduction at +0.46 V versus RHE and long-term stability with negligible degradation. In the acidic electrolyte (pH = 1), where the hydrogen evolution reaction is more favorable but stability is limited because of photocorrosion, a thicker Pt film (300 cycles) is shown to greatly improve the device stability and a j 0 of -2.14 mA/cm 2 is obtained with only 8.3% activity degradation after 6 h, compared with 80% degradation under the same conditions when the less conformal electrodeposition method is used to deposit the Pt layer. Electrochemical impedance spectroscopy and time-resolved photoluminescence results indicate that these enhancements stem from a lower bulk charge recombination rate, higher interfacial charge-transfer rate, and faster reaction kinetics. We believe that these interface engineering strategies can be extended to other colloidal semiconductors to construct more efficient and stable heterogeneous photoelectrodes for solar fuel production.

On the effect of boundary layer growth on the stability of compressible flows

NASA Technical Reports Server (NTRS)

El-Hady, N. M.

1981-01-01

The method of multiple scales is used to describe a formally correct method based on the nonparallel linear stability theory, that examines the two and three dimensional stability of compressible boundary layer flows. The method is applied to the supersonic flat plate layer at Mach number 4.5. The theoretical growth rates are in good agreement with experimental results. The method is also applied to the infinite-span swept wing transonic boundary layer with suction to evaluate the effect of the nonparallel flow on the development of crossflow disturbances.

Stability of an oscillating boundary layer

NASA Technical Reports Server (NTRS)

Levchenko, V. Y.; Solovyev, A. S.

1985-01-01

Levchenko and Solov'ev (1972, 1974) have developed a stability theory for space periodic flows, assuming that the Floquet theory is applicable to partial differential equations. In the present paper, this approach is extended to unsteady periodic flows. A complete unsteady formulation of the stability problem is obtained, and the stability characteristics over an oscillating period are determined from the solution of the problem. Calculations carried out for an oscillating incompressible boundary layer on a plate showed that the boundary layer flow may be regarded as a locally parallel flow.

Turbulent properties of oceanic near-surface stable boundary layers subject to wind, fresh water, and thermal forcing.

NASA Astrophysics Data System (ADS)

St. Laurent, Louis; Clayson, Carol Anne

2015-04-01

The near-surface oceanic boundary layer is generally regarded as convectively unstable due to the effects of wind, evaporation, and cooling. However, stable conditions also occur often, when rain or low-winds and diurnal warming provide buoyancy to a thin surface layer. These conditions are prevalent in the tropical and subtropical latitude bands, and are underrepresented in model simulations. Here, we evaluate cases of oceanic stable boundary layers and their turbulent processes using a combination of measurements and process modeling. We focus on the temperature, salinity and density changes with depth from the surface to the upper thermocline, subject to the influence of turbulent processes causing mixing. The stabilizing effects of freshwater from rain as contrasted to conditions of high solar radiation and low winds will be shown, with observations providing surprising new insights into upper ocean mixing in these regimes. Previous observations of freshwater lenses have demonstrated a maximum of dissipation near the bottom of the stable layer; our observations provide a first demonstration of a similar maximum near the bottom of the solar heating-induced stable layer and a fresh-water induced barrier layer. Examples are drawn from recent studies in the tropical Atlantic and Indian oceans, where ocean gliders equipped with microstructure sensors were used to measure high resolution hydrographic properties and turbulence levels. The limitations of current mixing models will be demonstrated. Our findings suggest that parameterizations of near-surface mixing rates during stable stratification and low-wind conditions require considerable revision, in the direction of larger diffusivities.

Origin of 1/f noise in hydration dynamics on lipid membrane surfaces

PubMed Central

Yamamoto, Eiji; Akimoto, Takuma; Yasui, Masato; Yasuoka, Kenji

2015-01-01

Water molecules on lipid membrane surfaces are known to contribute to membrane stability by connecting lipid molecules and acting as a water bridge. Although water structures and diffusivities near the membrane surfaces have been extensively studied, hydration dynamics on the surfaces has remained an open question. Here we investigate residence time statistics of water molecules on the surface of lipid membranes using all-atom molecular dynamics simulations. We show that hydration dynamics on the lipid membranes exhibits 1/f noise. Constructing a dichotomous process for the hydration dynamics, we find that residence times in each state follow a power-law with exponential cutoff and that the process can be regarded as a correlated renewal process where interoccurrence times are correlated. The results imply that the origin of the 1/f noise in hydration dynamics on the membrane surfaces is a combination of a power-law distribution with cutoff of interoccurrence times of switching events and a long-term correlation between the interoccurrence times. These results suggest that the 1/f noise attributed to the correlated renewal process may contribute to the stability of the hydration layers and lipid membranes. PMID:25743377

Stability, resolution, and ultra-low wear amplitude modulation atomic force microscopy of DNA: Small amplitude small set-point imaging

NASA Astrophysics Data System (ADS)

Santos, Sergio; Barcons, Victor; Christenson, Hugo K.; Billingsley, Daniel J.; Bonass, William A.; Font, Josep; Thomson, Neil H.

2013-08-01

A way to operate fundamental mode amplitude modulation atomic force microscopy is introduced which optimizes stability and resolution for a given tip size and shows negligible tip wear over extended time periods (˜24 h). In small amplitude small set-point (SASS) imaging, the cantilever oscillates with sub-nanometer amplitudes in the proximity of the sample, without the requirement of using large drive forces, as the dynamics smoothly lead the tip to the surface through the water layer. SASS is demonstrated on single molecules of double-stranded DNA in ambient conditions where sharp silicon tips (R ˜ 2-5 nm) can resolve the right-handed double helix.

Stability of core-shell nanowires in selected model solutions

NASA Astrophysics Data System (ADS)

Kalska-Szostko, B.; Wykowska, U.; Basa, A.; Zambrzycka, E.

2015-03-01

This paper presents the studies of stability of magnetic core-shell nanowires prepared by electrochemical deposition from an acidic solution containing iron in the core and modified surface layer. The obtained nanowires were tested according to their durability in distilled water, 0.01 M citric acid, 0.9% NaCl, and commercial white wine (12% alcohol). The proposed solutions were chosen in such a way as to mimic food related environment due to a possible application of nanowires as additives to, for example, packages. After 1, 2 and 3 weeks wetting in the solutions, nanoparticles were tested by Infrared Spectroscopy, Atomic Absorption Spectroscopy, Transmission Electron Microscopy and X-ray diffraction methods.

Free Energy Landscape of Cellulose as a Driving Factor in the Mobility of Adsorbed Water.

PubMed

Kulasinski, Karol

2017-06-06

The diffusion coefficient of water adsorbed in hydrophilic porous materials, such as noncrystalline cellulose, depends on water activity. Faster diffusion at higher water concentrations is observed in experimental and modeling studies. In this paper, two asymptotic water concentrations, near-vacuum and fully saturated, are investigated at the surface of crystalline cellulose with molecular dynamics simulations. An increasing water concentration leads to significant changes in the free energy landscape due to perturbation of local electrostatic potential. Smoothening of strong energy minima, corresponding to sorption sites, and formation of layered structure facilitates water transport in the vicinity of cellulose. The determined transition probabilities and hydrogen bond stability reflect the changes in the energy landscape. As a result of a concentration increase, the emerging basins of attraction and spreading out of those existing in the diluted state lead to an increase in water entropy. Thermal fluctuations of cellulose are demonstrated to rearrange the landscape in the diluted limit, increase adsorbed water entropy, and decrease the water-cellulose H-bond lifetime.

Preparation of novel stable antibacterial nanoparticles using hydroxyethylcellulose and application in paper.

PubMed

Wei, Dafu; Chen, Yan; Zhang, Youwei

2016-01-20

Taking advantage of the self-assembly between the components, novel stable antibacterial nanoparticles were efficiently fabricated via a facile one-step co-polymerization of acrylic acid (AA) and N,N'-methylenebisacrylamide (MBA) on a mixed aqueous solution of poly(hexamethylene guanidine hydrochloride) (PHMG) and hydroxyethylcellulose (HEC). The z-average hydrodynamic diameters of the nanoparticles ranged from 220 nm to 450 nm. The inner layer of the nanoparticles is composed of water-insoluble interpolymer complexes of PHMG and PAA networks, while the outer layer is composed of PHMG and HEC. The nanoparticles are stabilized by electrostatic interactions, hydrogen bonding interactions, and the chemical bonds. The nanoparticle solution remained stable in a wide pH range of 2.0-12.0 and at salt concentrations below 0.25 mol/L. The nanoparticles were incorporated into handsheets using a dipping treatment. The resulted handsheets exhibited excellent antimicrobial activities even after multiple water washing treatments. The nanoparticles are promising in fabricating paper, water-based coatings and textiles with permanent antibacterial activity. Copyright © 2015 Elsevier Ltd. All rights reserved.

Blending Cr 2O 3 into a NiO-Ni electrocatalyst for sustained water splitting

DOE PAGES

Gong, Ming; Zhou, Wu; Kenney, Michael James; ...

2015-08-24

The rising H 2 economy demands active and durable electrocatalysts based on low-cost, earth-abundant materials for water electrolysis/photolysis. Here we report nanoscale Ni metal cores over-coated by a Cr 2O 3-blended NiO layer synthesized on metallic foam substrates. The Ni@NiO/Cr 2O 3 triphase material exhibits superior activity and stability similar to Pt for the hydrogen-evolution reaction in basic solutions. The chemically stable Cr 2O 3 is crucial for preventing oxidation of the Ni core, maintaining abundant NiO/Ni interfaces as catalytically active sites in the heterostructure and thus imparting high stability to the hydrogen-evolution catalyst. The highly active and stable electrocatalystmore » enables an alkaline electrolyzer operating at 20 mA cm –2 at a voltage lower than 1.5 V, lasting longer than 3 weeks without decay. Thus, the non-precious metal catalysts afford a high efficiency of about 15 % for light-driven water splitting using GaAs solar cells.« less

Simulation of Ground-Water Flow in the Irwin Basin Aquifer System, Fort Irwin National Training Center, California

USGS Publications Warehouse

Densmore, Jill N.

2003-01-01

Ground-water pumping in the Irwin Basin at Fort Irwin National Training Center, California resulted in water-level declines of about 30 feet from 1941 to 1996. Since 1992, artificial recharge from wastewater-effluent infiltration and irrigation-return flow has stabilized water levels, but there is concern that future water demands associated with expansion of the base may cause a resumption of water-level declines. To address these concerns, a ground-water flow model of the Irwin Basin was developed to help better understand the aquifer system, assess the long-term availability and quality of ground water, and evaluate ground-water conditions owing to current pumping and to plan for future water needs at the base. Historical data show that ground-water-level declines in the Irwin Basin between 1941 and 1996, caused the formation of a pumping depression near the pumped wells, and that recharge from the wastewater-treatment facility and disposal area caused the formation of a recharge mound. There have been two periods of water-level recovery in the Irwin Basin since the development of ground water in this basin; these periods coincide with a period of decreased pumpage from the basin and a period of increased recharge of water imported from the Bicycle Basin beginning in 1967 and from the Langford Basin beginning in 1992. Since 1992, artificial recharge has exceeded pumpage in the Irwin Basin and has stabilized water-level declines. A two-layer ground-water flow model was developed to help better understand the aquifer system, assess the long-term availability and quality of ground water, and evaluate ground-water conditions owing to current pumping and to plan for future water needs at the base. Boundary conditions, hydraulic conductivity, altitude of the bottom of the layers, vertical conductance, storage coefficient, recharge, and discharge were determined using existing geohydrologic data. Rates and distribution of recharge and discharge were determined from existing data and estimated when unavailable. Results of predictive simulations indicate that in 50 years, if artificial recharge continues to exceed pumpage in Irwin Basin, water levels could rise as much as 65 feet beneath the pumping depression, and as much as 10 feet in the wastewater-treatment facility and disposal area. Particle-tracking simulations were used to determine the pathlines and the traveltimes of water high in dissolved solids into the main pumping area. The pathlines of particles from two areas with high dissolved-solids concentrations show that in 50 years water from these areas almost reaches the nearest pumped well.

Nanosized Thin SnO2 Layers Doped with Te and TeO2 as Room Temperature Humidity Sensors

PubMed Central

Georgieva, Biliana; Podolesheva, Irena; Spasov, Georgy; Pirov, Jordan

2014-01-01

In this paper the humidity sensing properties of layers prepared by a new method for obtaining doped tin oxide are studied. Different techniques—SEM, EDS in SEM, TEM, SAED, AES and electrical measurements—are used for detailed characterization of the thin layers. The as-deposited layers are amorphous with great specific area and low density. They are built up of a fine grained matrix, consisting of Sn- and Te-oxides, and a nanosized dispersed phase of Te, Sn and/or SnTe. The chemical composition of both the matrix and the nanosized particles depends on the ratio RSn/Te and the evaporation conditions. It is shown that as-deposited layers with RSn/Te ranging from 0.4 to 0.9 exhibit excellent characteristics as humidity sensors operating at room temperature—very high sensitivity, good selectivity, fast response and short recovery period. Ageing tests have shown that the layers possess good long-term stability. Results obtained regarding the type of the water adsorption on the layers' surface help better understand the relation between preparation conditions, structure, composition and humidity sensing properties. PMID:24854359

Hydrogen jet combustion in a scramjet combustor with the rearwall-expansion cavity

NASA Astrophysics Data System (ADS)

Zhang, Yan-Xiang; Wang, Zhen-Guo; Sun, Ming-Bo; Yang, Yi-Xin; Wang, Hong-Bo

2018-03-01

This study is carried out to experimentally investigate the combustion characteristics of the hydrogen jet flame stabilized by the rearwall-expansion cavity in a model scramjet combustor. The flame distributions are characterized by the OH* spontaneous emission images, and the dynamic features of the flames are studied through the high speed framing of the flame luminosity. The combustion modes are further analyzed based on the visual flame structure and wall pressure distributions. Under the present conditions, the combustion based on the rearwall-expansion cavity appears in two distinguished modes - the typical cavity shear-layer stabilized combustion mode and the lifted-shear-layer stabilized combustion mode. In contrast with the shear-layer stabilized mode, the latter holds stronger flame. The transition from shear-layer stabilized combustion mode to lifted-shear-layer stabilized mode usually occurs when the equivalence ratio is high enough. While the increases of the offset ratio and upstream injection distance both lead to weaker jet-cavity interactions, cause longer ignition delay, and thus delay the mode transition. The results reveal that the rearwall-expansion cavity with an appropriate offset ratio should be helpful in delaying mode transition and preventing thermal choke, and meanwhile just brings minor negative impact on the combustion stability and efficiency.

Phosphate uptake behavior of layered rare earth hydroxides l-RE(OH)3 (RE = Sm, Gd, Er, and Y) from water

NASA Astrophysics Data System (ADS)

Jeon, Hong-Gu; Kim, Hyunsub; Jung, Hyunjin; Byeon, Song-Ho

2018-07-01

The use of rare earths (REs) provides various advantages for removal and recovery of phosphate from water because they have high affinity to form stable complexes with phosphates even at low concentrations. Very low solubility of rare earth phosphate REPO4 in water was expected to induce a high phosphate adsorption rate and capacity. In this study, layered rare earth hydroxides, l-RE(OH)3 (RE = Sm, Gd, Er, and Y), have been employed to remove or recover phosphate from aqueous solution. This layered polymorph of l-RE(OH)3, which is composed of hydroxocation layers, exhibited a high point of zero charge (pHpzc > 10) and significantly enhanced adsorptive ability for phosphates over a wide pH range. The isotherm and kinetics of phosphate adsorption on l-RE(OH)3 were explained dominantly by the Langmuir isotherm model and pseudo-second-order kinetic model, respectively. A strong dependence of isotherm and kinetic parameters on RE demonstrated that the adsorption of phosphate on l-RE(OH)3 is a chemisorption dominated process involving the replacement of -OH by phosphate ion to be included into the coordination polyhedra of RE. The desorption of phosphate from l-RE(OH)3 was slow but the desorption efficiency for all RE members was higher than 97% in a 1.0 M NaOH solution after 4 days at room temperature. Considering high capacity and stability as well as no significant interference in recovery of phosphate from waters containing common competing anions, this rare earth adsorbent series is proposed as a promising alternative for efficient and sensitive phosphate recovery from natural and wastewaters.

Observing Tropospheric Water Vapor by Radio Occultation using the Global Positioning System

NASA Technical Reports Server (NTRS)

Kursinski, E. R.; Hajj, G. A.; Hardy, K. R.; Romans, L. J.; Schofield, J. T.

1995-01-01

Given the importance of water vapor to weather, climate and hydrology, global humidity observations from satellites are critical. At low latitudes, radio occultation observations of Earth's atmosphere using the Global Positioning System (GPS) satellites allow water vapor profiles to be retrieved with accuracies of 10 to 20% below 6 to 7 km altitude and approx. 5% or better within the boundary layer. GPS observations provide a unique combination of accuracy, vertical resolution (less than or equal to 1 km) and insensitivity to cloud and aerosol particles that is well suited to observations of the lower troposphere. These characteristics combined with the inherent stability of radio occultation observations make it an excellent candidate for the measurement of long term trends.

Design and construction control guidance for chemically stabilized pavement base layers.

DOT National Transportation Integrated Search

2013-12-01

A laboratory and field study was conducted related to chemically stabilized pavement layers, which is also : referred to as soil-cement. Soil-cement practices within MDOT related to Class 9C soils used for base layers : were evaluated in this report....

Method for transition prediction in high-speed boundary layers, phase 2

NASA Astrophysics Data System (ADS)

Herbert, T.; Stuckert, G. K.; Lin, N.

1993-09-01

The parabolized stability equations (PSE) are a new and more reliable approach to analyzing the stability of streamwise varying flows such as boundary layers. This approach has been previously validated for idealized incompressible flows. Here, the PSE are formulated for highly compressible flows in general curvilinear coordinates to permit the analysis of high-speed boundary-layer flows over fairly general bodies. Vigorous numerical studies are carried out to study convergence and accuracy of the linear-stability code LSH and the linear/nonlinear PSE code PSH. Physical interfaces are set up to analyze the M = 8 boundary layer over a blunt cone calculated by using a thin-layer Navier Stokes (TNLS) code and the flow over a sharp cone at angle of attack calculated using the AFWAL parabolized Navier-Stokes (PNS) code. While stability and transition studies at high speeds are far from routine, the method developed here is the best tool available to research the physical processes in high-speed boundary layers.

Soil stability characteristics of mulberry lands at hydro-fluctuation belt in the Three Gorges Reservoir area, China.

PubMed

Jiang, Ping; Shi, Dongmei; Hu, Xueqin; Huang, Xianzhi; Li, Yexin; Guo, Tianlei

2015-10-01

The hydro-fluctuation belt in the Three Gorges Reservoir area is a typical seasonal and artificial wetland system and ecologically fragile zone. Using the widely existing mulberry forest lands in the hydro-fluctuation belt as an example and the 180-m water-level forest land as a control, this paper analyzes the soil stability of mulberry forestlands at different water levels in the hydro-fluctuation belt by analyzing and comparing the changes between soil physical and mechanical properties. The results indicated that (1) water-level changes, such as rising, flooding, draining, and exposure, affect the soil structure in mulberry forestlands. The soil agglomeration statuses for the soil layers decreased from 180 > 175 > 170 > 165 m, and the soil agglomeration statuses at a depth of 0∼20 cm decreased by 43.79, 44.95, and 57.45% compared with the control. (2) The soil water stability index decreased as follows: 180 > 170 > 175 > 165 m, which only accounted for 50.00, 47.73, and 40.91% of the control. In addition, the soil water stability indexes for the topsoils at various water levels were 1.87 (180 m), 1.67 (175 m), 2.92 (170 m), and 1.86 (165 m) times greater than those of the subsoils; thus, the resistance to hydraulic dispersion and disintegration were greater in the topsoil than in the subsoil. (3) The soil aggregate stability index decreased from 180 > 165 > 170 > 175 m and by 22.75, 23.53, and 35.29% compared with the control. (4) The soil shear strengths (composed of the cohesive force C and the internal friction angle φ) of the topsoils at water levels of 175, 170, and 165 m were significantly lower than in the control, and the internal friction angles decreased by 10.52, 19.08, and 43.25% and the cohesive force decreased by 9.88, 16.36, and 27.51%, respectively. The stability of the soil structure was greatly influenced by the soil clay content, soil organic matter content, and waterlogging duration. The study results could provide scientific support for soil and water conservation in the hydro-fluctuation belt and for biological filter construction in the Three Gorges Reservoir area to control the transport of sediment and non-point source pollutants.

In-situ vacuum deposition technique of lithium on neutron production target for BNCT

NASA Astrophysics Data System (ADS)

Ishiyama, S.; Baba, Y.; Fujii, R.; Nakamura, M.; Imahori, Y.

2012-10-01

For the purpose of avoiding the radiation blistering of the lithium target for neutron production in BNCT (Boron Neutron Capture Therapy) device, trilaminar Li target, of which palladium thin layer was inserted between cupper substrate and Li layer, was newly designed. In-situ vacuum deposition and electrolytic coating techniques were applied to validate the method of fabrication of the Li/Pd/Cu target, and the layered structures of the synthesized target were characterized. In-situ vacuum re-deposition technique was also established for repairing and maintenance for lithium target damaged. Following conclusions were derived; (1) Uniform lithium layers with the thickness from 1.6 nm to a few hundreds nanometer were formed on Pd/Cu multilayer surface by in situ vacuum deposition technique using metallic lithium as a source material. (2) Re-deposition of lithium layer on Li surface can be achieved by in situ vacuum deposition technique. (3) Small amount of water and carbonate was observed on the top surface of Li. But the thickness of the adsorbed layer was less than monolayer, which will not affect the quality of the Li target. (4) The formation of Pd-Li alloy layer was observed at the Pd and Li interface. The alloy layer would contribute to the stability of the Li layer.

STS-55 Earth observation of the Timor Sea

NASA Technical Reports Server (NTRS)

1993-01-01

STS-55 Earth observation taken from Columbia, Orbiter Vehicle (OV) 102, shows the Timor Sea along the south coast of Timor. The sunglint pattern shows a sharp boundary in sea surface temperature, with cooler water along the coast and warmer water offshore. The sunglint brightness reveals water surface roughness with bright indicating smooth water and dark representing rough water. Cooler water is smoother because it acts to stabilize the atmospheric boundary layer, while the warm water acts to destabilize the atmosphere. Another indication of water temperature is the cloud pattern. Advection within the atmosphere as a result of warming at the sea surface forms low-level clouds with the small, popcorn-like appearance seen in upper right corner of the photograph. The cool water, on the other hand, is relatively free of the popcorn-like clouds. The distribution of the clouds indicates that the wind is blowing toward the upper right corner of the photograph. Also note the line of low-level

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

Lins, Roberto; Pereira, Cristina S.; Hunenberger, Phillipe

A variety of sugars are known to enhance the stability of biomaterials. Trehalose, a nonreducing disaccharide composed of two {alpha},{alpha}(1 {yields} 1)-linked D-glucopyranose units, appears to be one of the most effective protectants. Both in vivo and in vitro, trehalose protects biostructures such as proteins and membranes from damage due to dehydration, heat, or cold. However, despite the significant amount of experimental data on this disaccharide, no clear picture of the molecular mechanism responsible for its stabilizing properties has emerged yet. Three major hypotheses (water-trehalose hydrogen-bond replacement, coating by a trapped water layer, and mechanical inhibition of the conformational fluctuations)more » have been proposed to explain the stabilizing effect of trehalose on proteins. To investigate the nature of protein-trehalose-water interactions in solution at the molecular level, two molecular dynamics simulations of the protein lysozyme in solution at room temperature have been carried out, one in the presence (about 0.5 M) and one in the absence of trehalose. The results show that the trehalose molecules cluster and move toward the protein, but neither completely expel water from the protein surface nor form hydrogen bonds with the protein. Furthermore, the coating by trehalose does not significantly reduce the conformational fluctuations of the protein compared to the trehalose-free system. Based on these observations, a model is proposed for the interaction of trehalose molecules with a protein in moderately concentrated solutions, at room temperature and on the nanosecond timescale.« less

[Responses of soil organic carbon and its labile fractions to nitrogen and phosphorus additions in Cunninghamia lanceolata plantations in subtropical China.

PubMed

Zhang, Xiu Lan; Wang, Fang Chao; Fang, Xiang Min; He, Ping; Zhang, Yu Fei; Chen, Fu Sheng; Wang, Hui Min

2017-02-01

A series of nitrogen (N) and phosphorus (P) addition experiments using treatments of N 0 (0 kg N·hm -2 ·a -1 ), N 1 (50 kg N·hm -2 ·a -1 ), N 2 (100 kg N·hm -2 ·a -1 ), P (50 kg P·hm -2 ·a -1 ), N 1 P and N 2 P were conducted at Cunninghamia lanceolata plantations in subtropical China. The responses of soil organic carbon (SOC), particulate organic carbon (POC) and water-soluble organic carbon (WSOC) to the nutrient addition treatments after 3 years were determined. The results showed that N and P additions had no significant effects on SOC concentration in 0-20 cm soil layer, while P addition significantly decreased soil POC content in 0-5 cm soil layer by 26.1%. The responses of WSOC to N and P addition were mainly found in 0-5 cm soil layer, and low level N and P addition significantly increased the WSOC content in 0-5 cm soil layer. Nitrogen addition had no significant effect on POC/SOC, while the POC/SOC significantly decreased by 15.9% in response to P addition in 0-5 cm soil layer. In 5-10 cm and 10-20 cm soil layers, POC/SOC was not significantly altered in N and P addition treatments. Therefore, the forest soil C stability was mainly controlled by P content in subtropical areas. P addition was liable to cause the decomposition of surface soil active organic C and increased the soil C stability in the short term treatment.

Aggregate Stability and Erodibility of Purple Soil on Sloping Farmland as affected by different Soil Thickness

NASA Astrophysics Data System (ADS)

Huang, Xinjun; Zhang, Qingwen; Chen, Shanghong; Dong, Yuequn; Xiao, Meijia; Hamed, Lamy Mamdoh Mohamed

2017-04-01

Soil thickness is basic limiting condition for purple soil, not only due to its effect on crop production, but also its effect on soil structure. Steady-state of soil thickness will be achieved over time, as result the soil aggregate which the key factor of soil erodibility can be enhanced as well. However, the effect of soil thickness on aggregates stability and the characteristics of soil erodibility in sloping land have not yet fully understood.A field survey was conducted in hilly area of Sichuan region located in southeast China to study the relationship between soil aggregate stability and soil erodibility on sloping farmland under different four thickness (100cm, 80cm, 60cm, 30cm) of purple soil. Based on two different sieving methods (Dry and Wet sieving), we analyzed soil aggregate stability and its effect on soil erodibility within depth of 0-30cm soil layers. The results indicated that: Water stable aggregate on sloping farmland was ranged between 37.9% to 58.6%, where it increased with increasing the soil thickness. Moreover, fractal dimension calculated from dry-sieving and wet-sieving was 2.06-2.49 and 2.70-2.85 respectively, where it decreased with decreasing the soil thickness. The overall soil erodibility was 0.05-1.00 and a negative significant correlation was found between soil aggregate stability and erodibility(P<0.01). Moreover, farmland with thick soil profile tended to be high in soil erodibility within the top soil layer (0-30cm). The results reveal that soil thickness can affect soil aggregate stability as well as erodibility. As soil thickness increased, the top soil became more stable and less erodible. Keywords：purple soil; soil thickness; soil aggregate；soil erodibility

Layered method of electrode for solid oxide electrochemical cells

DOEpatents

Jensen, Russell R.

1991-07-30

A process for fabricating a fuel electrode comprising: slurry dipping to form layers which are structurally graded from all or mostly all stabilized zirconia at a first layer, to an outer most layer of substantially all metal powder, such an nickel. Higher performaance fuel electrodes may be achieved if sinter active stabilized zirconia doped for electronic conductivity is used.

Studies on electronic structure of interfaces between Ag and gelatin for stabilization of Ag nanoparticles

NASA Astrophysics Data System (ADS)

Tani, Tadaaki; Uchida, Takayuki

2015-06-01

Extremely high stability of Ag nanoparticles in photographic materials has forced us to study the electronic structures of the interfaces between thin layers of Ag, Au, and Pt and their surface membranes in ambient atmosphere by photoelectron yield spectroscopy in air and Kelvin probe method. Owing to the Fermi level equalization between a metal layer and a membrane coming from air, the electron transfer took place from the membrane to Pt and Au layers and from an Ag layer to the membrane, giving the reason for poor stability of Ag nanoparticles in air. The control of the Fermi level of an Ag layer with respect to that of a gelatin membrane in air could be widely made according to Nernst’s equation by changing the pH and pAg values of an aqueous gelatin solution used to form the membrane, and thus available to stabilize Ag nanoparticles in a gelatin matrix.

Structural Dynamics of Carbon Dots in Water and N, N-Dimethylformamide Probed by All-Atom Molecular Dynamics Simulations.

PubMed

Paloncýová, Markéta; Langer, Michal; Otyepka, Michal

2018-04-10

Carbon dots (CDs), one of the youngest members of the carbon nanostructure family, are now widely experimentally studied for their tunable fluorescence properties, bleaching resistance, and biocompatibility. Their interaction with biomolecular systems has also been explored experimentally. However, many atomistic details still remain unresolved. Molecular dynamics (MD) simulations enabling atomistic and femtosecond resolutions simultaneously are a well-established tool of computational chemistry which can provide useful insights into investigated systems. Here we present a full procedure for performing MD simulations of CDs. We developed a builder for generating CDs of a desired size and with various oxygen-containing surface functional groups. Further, we analyzed the behavior of various CDs differing in size, surface functional groups, and degrees of functionalization by MD simulations. These simulations showed that surface functionalized CDs are stable in a water environment through the formation of an extensive hydrogen bonding network. We also analyzed the internal dynamics of individual layers of CDs and evaluated the role of surface functional groups on CD stability. We observed that carboxyl groups interconnected the neighboring layers and decreased the rate of internal rotations. Further, we monitored changes in the CD shape caused by an excess of charged carboxyl groups or carbonyl groups. In addition to simulations in water, we analyzed the behavior of CDs in the organic solvent DMF, which decreased the stability of pure CDs but increased the level of interlayer hydrogen bonding. We believe that the developed protocol, builder, and parameters will facilitate future studies addressing various aspects of structural features of CDs and nanocomposites containing CDs.

Effects of spanwise rotation on the structure of two-dimensional fully developed turbulent channel flow.

NASA Technical Reports Server (NTRS)

Johnston, J. P.; Halleen, R. M.; Lezius, D. K.

1972-01-01

Experiments on fully developed turbulent flow in a channel which is rotating at a steady rate about a spanwise axis are described. The Coriolis force components in the region of two-dimensional mean flow affect both local and global stability. Three stability-related phenomena were observed or inferred: (1) the reduction (increase) of the rate of wall-layer streak bursting in locally stabilized (destabilized) wall layers; (2) the total suppression of transition to turbulence in a stabilized layer; (3) the development of large-scale roll cells on the destabilized side of the channel by growth of a Taylor-Gortler vortex instability. Local effects of rotational stabilization, such as reduction of the turbulent stress in wall layers, can be related to the local Richardson number in a simple way. This paper not only investigates this effect, but also, by methods of flow visualization, exposes some of the underlying structure changes caused by rotation.-

Effects of forebody geometry on subsonic boundary-layer stability

NASA Technical Reports Server (NTRS)

Dodbele, Simha S.

1990-01-01

As part of an effort to develop computational techniques for design of natural laminar flow fuselages, a computational study was made of the effect of forebody geometry on laminar boundary layer stability on axisymmetric body shapes. The effects of nose radius on the stability of the incompressible laminar boundary layer was computationally investigated using linear stability theory for body length Reynolds numbers representative of small and medium-sized airplanes. The steepness of the pressure gradient and the value of the minimum pressure (both functions of fineness ratio) govern the stability of laminar flow possible on an axisymmetric body at a given Reynolds number. It was found that to keep the laminar boundary layer stable for extended lengths, it is important to have a small nose radius. However, nose shapes with extremely small nose radii produce large pressure peaks at off-design angles of attack and can produce vortices which would adversely affect transition.

Combined effects of trapped energetic ions and resistive layer damping on the stability of the resistive wall mode

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

He, Yuling; Liu, Yue, E-mail: Yueqiang.Liu@ccfe.ac.uk, E-mail: liuyue@dlut.edu.cn; Liu, Chao

2016-01-15

A dispersion relation is derived for the stability of the resistive wall mode (RWM), which includes both the resistive layer damping physics and the toroidal precession drift resonance damping from energetic ions in tokamak plasmas. The dispersion relation is numerically solved for a model plasma, for the purpose of systematic investigation of the RWM stability in multi-dimensional plasma parameter space including the plasma resistivity, the radial location of the resistive wall, as well as the toroidal flow velocity. It is found that the toroidal favorable average curvature in the resistive layer contributes a significant stabilization of the RWM. This stabilizationmore » is further enhanced by adding the drift kinetic contribution from energetic ions. Furthermore, two traditionally assumed inner layer models are considered and compared in the dispersion relation, resulting in different predictions for the stability of the RWM.« less

Electrodeposition of thin yttria-stabilized zirconia layers using glow-discharge plasma

NASA Astrophysics Data System (ADS)

Ogumi, Zempachi; Uchimoto, Yoshiharu; Tsuji, Yoichiro; Takehara, Zen-ichiro

1992-08-01

A novel process for preparation of thin yttria-stabilized zirconia (YSZ) layers was developed. This process differs from other vapor-phase deposition methods in that a dc bias circuit, separate from the plasma-generation circuit, is used for the electrodeposition process. The YSZ layer was electrodeposited from ZrCl4 and YCl3 on a nonporous calcia-stabilized zirconia substrate. Scanning electron microscopy, electron probe microanalysis, electron spectroscopy for chemical analysis, and x-ray-diffraction measurements confirmed the electrodeposition of a smooth, pinhole-free yttria-stabilized zirconia film of about 3 μm thickness.

Characterization of Polyethylene-Graft-Sulfonated Polyarylsulfone Proton Exchange Membranes for Direct Methanol Fuel Cell Applications.

PubMed

Kim, Hyung Kyu; Zhang, Gang; Nam, Changwoo; Chung, T C Mike

2015-12-04

This paper examines polymer film morphology and several important properties of polyethylene-graft-sulfonated polyarylene ether sulfone (PE-g-s-PAES) proton exchange membranes (PEMs) for direct methanol fuel cell applications. Due to the extreme surface energy differences between a semi-crystalline and hydrophobic PE backbone and several amorphous and hydrophilic s-PAES side chains, the PE-g-s-PAES membrane self-assembles into a unique morphology, with many proton conductive s-PAES channels embedded in the stable and tough PE matrix and a thin hydrophobic PE layer spontaneously formed on the membrane surfaces. In the bulk, these membranes show good mechanical properties (tensile strength >30 MPa, Young's modulus >1400 MPa) and low water swelling (λ < 15) even with high IEC >3 mmol/g in the s-PAES domains. On the surface, the thin hydrophobic and semi-crystalline PE layer shows some unusual barrier (protective) properties. In addition to exhibiting higher through-plane conductivity (up to 160 mS/cm) than in-plane conductivity, the PE surface layer minimizes methanol cross-over from anode to cathode with reduced fuel loss, and stops the HO• and HO₂• radicals, originally formed at the anode, entering into PEM matrix. Evidently, the thin PE surface layer provides a highly desirable protecting layer for PEMs to reduce fuel loss and increase chemical stability. Overall, the newly developed PE-g-s-PAES membranes offer a desirable set of PEM properties, including conductivity, selectivity, mechanical strength, stability, and cost-effectiveness for direct methanol fuel cell applications.

Characterization of Polyethylene-Graft-Sulfonated Polyarylsulfone Proton Exchange Membranes for Direct Methanol Fuel Cell Applications

PubMed Central

Kim, Hyung Kyu; Zhang, Gang; Nam, Changwoo; Chung, T.C. Mike

2015-01-01

This paper examines polymer film morphology and several important properties of polyethylene-graft-sulfonated polyarylene ether sulfone (PE-g-s-PAES) proton exchange membranes (PEMs) for direct methanol fuel cell applications. Due to the extreme surface energy differences between a semi-crystalline and hydrophobic PE backbone and several amorphous and hydrophilic s-PAES side chains, the PE-g-s-PAES membrane self-assembles into a unique morphology, with many proton conductive s-PAES channels embedded in the stable and tough PE matrix and a thin hydrophobic PE layer spontaneously formed on the membrane surfaces. In the bulk, these membranes show good mechanical properties (tensile strength >30 MPa, Young’s modulus >1400 MPa) and low water swelling (λ < 15) even with high IEC >3 mmol/g in the s-PAES domains. On the surface, the thin hydrophobic and semi-crystalline PE layer shows some unusual barrier (protective) properties. In addition to exhibiting higher through-plane conductivity (up to 160 mS/cm) than in-plane conductivity, the PE surface layer minimizes methanol cross-over from anode to cathode with reduced fuel loss, and stops the HO• and HO2• radicals, originally formed at the anode, entering into PEM matrix. Evidently, the thin PE surface layer provides a highly desirable protecting layer for PEMs to reduce fuel loss and increase chemical stability. Overall, the newly developed PE-g-s-PAES membranes offer a desirable set of PEM properties, including conductivity, selectivity, mechanical strength, stability, and cost-effectiveness for direct methanol fuel cell applications. PMID:26690232

Sublayer of Prandtl Boundary Layers

NASA Astrophysics Data System (ADS)

Grenier, Emmanuel; Nguyen, Toan T.

2018-03-01

The aim of this paper is to investigate the stability of Prandtl boundary layers in the vanishing viscosity limit {ν \\to 0} . In Grenier (Commun Pure Appl Math 53(9):1067-1091, 2000), one of the authors proved that there exists no asymptotic expansion involving one of Prandtl's boundary layer, with thickness of order {√{ν}} , which describes the inviscid limit of Navier-Stokes equations. The instability gives rise to a viscous boundary sublayer whose thickness is of order {ν^{3/4}} . In this paper, we point out how the stability of the classical Prandtl's layer is linked to the stability of this sublayer. In particular, we prove that the two layers cannot both be nonlinearly stable in L^∞. That is, either the Prandtl's layer or the boundary sublayer is nonlinearly unstable in the sup norm.

Platinum-nanoparticle-supported core-shell polymer nanospheres with unexpected water stability and facile further modification

NASA Astrophysics Data System (ADS)

Yuan, Conghui; Xu, Yiting; Luo, Weiang; Zeng, Birong; Qiu, Wuhui; Liu, Jie; Huang, Huiling; Dai, Lizong

2012-05-01

Core-shell nanospheres (CSNSs) with hydrophobic cores and hydrophilic shells were fabricated via a simple mini-emulsion polymerization for the stabilization of platinum nanoparticles (Pt-NPs). The CSNSs showed extremely high loading capacity of Pt-NPs (the largest loading amount of the Pt-NPs was about 49.2 wt%). Importantly, the Pt-NPs/CSNSs nanocomposites had unexpected stability in aqueous solution. DLS results revealed that the CSNSs loaded with Pt-NPs exhibited almost no aggregation after standing for a long time . However, the Pt-NPs immobilized on the CSNSs were not straitlaced: they could transport and redistribute between CSNSs freely when the environmental temperature was higher than the melting point of the CSNS shell. Owing to their excellent stability in aqueous solution, the surface of the Pt-NPs/CSNSs nanocomposites could be further decorated easily. For example, polyaniline (PANI)-coated Pt-NPs/CSNSs, nickel (Ni)-coated Pt-NPs/CSNSs and PANI/Pt-NPs dual-layer hollow nanospheres were facilely fabricated from the Pt-NPs/CSNS nanocomposites.

Tailored interfaces of unencapsulated perovskite solar cells for >1,000 hour operational stability

DOE PAGES

Christians, Jeffrey A.; Schulz, Philip; Tinkham, Jonathan S.; ...

2017-11-28

Long-term device stability is the most pressing issue that impedes perovskite solar cell commercialization, given the achieved 22.7% efficiency. The perovskite absorber material itself has been heavily scrutinized for being prone to degradation by water, oxygen and ultraviolet light. To date, most reports characterize device stability in the absence of these extrinsic factors. Here we show that, even under the combined stresses of light (including ultraviolet light), oxygen and moisture, perovskite solar cells can retain 94% of peak efficiency despite 1,000 hours of continuous unencapsulated operation in ambient air conditions (relative humidity of 10-20%). Each interface and contact layer throughoutmore » the device stack plays an important role in the overall stability which, when appropriately modified, yields devices in which both the initial rapid decay (often termed burn-in) and the gradual slower decay are suppressed. This extensively modified device architecture and the understanding developed will lead towards durable long-term device performance.« less

Tailored interfaces of unencapsulated perovskite solar cells for >1,000 hour operational stability

NASA Astrophysics Data System (ADS)

Christians, Jeffrey A.; Schulz, Philip; Tinkham, Jonathan S.; Schloemer, Tracy H.; Harvey, Steven P.; Tremolet de Villers, Bertrand J.; Sellinger, Alan; Berry, Joseph J.; Luther, Joseph M.

2018-01-01

Long-term device stability is the most pressing issue that impedes perovskite solar cell commercialization, given the achieved 22.7% efficiency. The perovskite absorber material itself has been heavily scrutinized for being prone to degradation by water, oxygen and ultraviolet light. To date, most reports characterize device stability in the absence of these extrinsic factors. Here we show that, even under the combined stresses of light (including ultraviolet light), oxygen and moisture, perovskite solar cells can retain 94% of peak efficiency despite 1,000 hours of continuous unencapsulated operation in ambient air conditions (relative humidity of 10-20%). Each interface and contact layer throughout the device stack plays an important role in the overall stability which, when appropriately modified, yields devices in which both the initial rapid decay (often termed burn-in) and the gradual slower decay are suppressed. This extensively modified device architecture and the understanding developed will lead towards durable long-term device performance.

Enhancing the stability of lithium ion Li1+x+yAlxTi2-xSiyP3-yO12 glass - ceramic conductors in aqueous electrolytes

NASA Astrophysics Data System (ADS)

Ioanniti, Marina Maria; Tenhaeff, Wyatt E.

2017-12-01

The stability of NASICON-type conducting glass-ceramic electrolyte, Li1+x+yAlxTi2-xSiyP3-yO12 (Ohara LICGC) has been characterized after prolonged exposure to deionized water and HCl(aq) solutions supported with LiCl. X-ray diffraction shows that the bulk crystallographic structure of the LICGC membranes remains unchanged when exposed to these solutions. Electrochemical impedance spectroscopy (EIS) shows that the conductivity of LICGC membranes immersed in deionized water remains stable over a one month period, while there is a significant increase in resistance when exposed to the acidic solutions. When exposed to pH 4 and 2 solutions for just 24 h, the resistances of the LICGC membrane increase by a factor of 8.5 and 23.5, respectively. EIS coupled with morphological characterization by scanning electron microscopy, shows that this resistance growth is due to the development of a surface layer on the LICGC membrane. However, this substantial increase in resistance can be mitigated by adding LiCl to the HCl solutions. For a pH 4 solution supported with 6.75 M LiCl, the impedance spectrum and surface morphology are qualitatively comparable to pristine, dry LICGC material, suggesting that surface layer formation was suppressed. This was also confirmed via cyclic voltammetry measurements in four-electrode electrochemical cells.

Colloidal properties and stability of aqueous suspensions of few-layer graphene: Importance of graphene concentration

PubMed Central

Su, Yu; Yang, Guoqing; Lu, Kun; Petersen, Elijah J.; Mao, Liang

2017-01-01

Understanding the colloidal stability of graphene is essential for predicting its transport and ecological risks in aquatic environments. We investigated the agglomeration of 14C-labeled few-layer graphene (FLG) at concentrations spanning nearly four orders of magnitude (2 μg/L to 10 mg/L) using dynamic light scattering and sedimentation measurements. FLG agglomerates formed rapidly in deionized water at concentrations > 3 mg/L. From 1 mg/L to 3 mg/L, salt-induced agglomeration was decreased with dilution of FLG suspensions; the critical coagulation concentration of the more concentrated suspension (3 mg/L) was significantly lower than the dilute suspension (1 mg/L) in the presence of NaCl (1.6 mmol/L and 10 mmol/L, respectively). In contrast, FLG underwent slow agglomeration and settling at concentrations ≤ 0.1 mg/L in NaCl solutions and ambient waters with low ionic strength (< 10 mmol/L). Although salt-induced agglomeration led to 67 % reduction in number of small FLG (25 nm to 50 nm) according to atomic force microscopy characterization, transition from concentrated to dilute suspension retarded the removal of the small FLG. Additionally, the small FLG exhibited greater bioaccumulation in zebrafish embryo and stronger chorion penetration ability than larger ones. These findings suggest that FLG at more environmentally relevant concentration is relatively stable and may have implications for exposure of small FLG to ecological receptors. PMID:27720543

The influence of mixture composition, adhesion promotor and compaction degree on the groove stability of grooved Marshall asphalt

NASA Astrophysics Data System (ADS)

Vuye, Cedric; Couscheir, Karolien; Lauriks, Leen; Van den bergh, Wim; Van Bouwel, Philippe

2017-09-01

After the first rehabilitation of runway 07R/25L in 2015, runway 01/19 was reconstructed in the summer of 2016, as part of a cycle where all runway pavements at Brussels airport are completely renovated each thirty years. The top layer is a Marshall asphalt with a polymer modified bitumen. To optimize the water drainage the central part of the runway (47 m wide) is grooved instead of applying an anti-skid layer. In this paper the focus is on the durability of the grooved top layer. Two different Marshall asphalt mixtures with a different maximum granulate size (10 mm or 14 mm) are compared, both in the laboratory and in a full-scale trial. In the laboratory the resistance against rutting and raveling are investigated for both mixtures with and without adhesion promotor, which did not show a positive effect. In the full-scale trial the compactability and impact of both a longer curing period and a variation in the degree of compaction on the groove stability is investigated for both mixtures using a heavy truck. No visual differences could be found except in areas which were undercompacted and showed more damage to the grooves.

Adsorption, aggregation, and desorption of proteins on smectite particles.

PubMed

Kolman, Krzysztof; Makowski, Marcin M; Golriz, Ali A; Kappl, Michael; Pigłowski, Jacek; Butt, Hans-Jürgen; Kiersnowski, Adam

2014-10-07

We report on adsorption of lysozyme (LYS), ovalbumin (OVA), or ovotransferrin (OVT) on particles of a synthetic smectite (synthetic layered aluminosilicate). In our approach we used atomic force microscopy (AFM) and quartz crystal microbalance (QCM) to study the protein-smectite systems in water solutions at pH ranging from 4 to 9. The AFM provided insights into the adhesion forces of protein molecules to the smectite particles, while the QCM measurements yielded information about the amounts of the adsorbed proteins, changes in their structure, and conditions of desorption. The binding of the proteins to the smectite surface was driven mainly by electrostatic interactions, and hence properties of the adsorbed layers were controlled by pH. At high pH values a change in orientation of the adsorbed LYS molecules and a collapse or desorption of OVA layer were observed. Lowering pH to the value ≤ 4 caused LYS to desorb and swelling the adsorbed OVA. The stability of OVT-smectite complexes was found the lowest. OVT revealed a tendency to desorb from the smectite surface at all investigated pH. The minimum desorption rate was observed at pH close to the isoelectric point of the protein, which suggests that nonspecific interactions between OVT and smectite particles significantly contribute to the stability of these complexes.

Integrated MoSe2 with n+p-Si photocathodes for solar water splitting with high efficiency and stability

NASA Astrophysics Data System (ADS)

Huang, Guanping; Mao, Jie; Fan, Ronglei; Yin, Zhihao; Wu, Xi; Jie, Jiansheng; Kang, Zhenhui; Shen, Mingrong

2018-01-01

Many earth-abundant transition metal dichalcogenides (TMDs) have been employed as catalysts for H2 evolution reaction (HER); however, their impactful integration onto photocathodes for photoelectrochemical (PEC) HER is less developed. In this study, we directly sputtered a MoSe2 catalyst onto an n+p-Si photocathode for efficient and stable PEC-HER. An onset potential of 0.4 V vs. RHE, a saturated photocurrent of 29.3 mA/cm2, a fill factor of 0.32, and an energy conversion efficiency of 3.8% were obtained under 100 mA/cm2 Xe lamp illumination. Such superior PEC properties were ascribed to the nearly vertically standing two dimensional MoSe2 rough surface layer and the sharp interface between Si and MoSe2 with small charge transfer resistance. The balance between the reflectivity of the electrode surface and the absorptivity of MoSe2 was also discussed. In addition, the MoSe2 layer can protect the n+p-Si photocathode with a 120 h stability due to its initial growth on Si with high flatness and compactness. This study provides a path to the effective and scalable growth of TMDs onto the Si photocathode aiming for high efficiency and stability.

Warm and Humid Air Blowing over Cold Water - Grand Banks Fog

NASA Astrophysics Data System (ADS)

Taylor, P.; Weng, W.

2016-12-01

The condensation of water vapour into droplets and the formation of fog in the Earth's atmospheric boundary layer involves a complex balance between horizontal advection and vertical turbulent mixing of heat and water vapour, cloud microphysical processes and radiative transfers of heat, plus the impact of water droplets, and sometimes ice crystals, on visibility. It is a phenomenon which has been studied for many years in a variety of contexts. On land, surface cooling of the ground via long wave radiation at night is often the trigger and a number of 1-D (height and time dependent) radiative fog models have been developed. Over the waters offshore from Newfoundland a key factor is the advection of moist air from over warm gulf stream waters to colder Labrador current water - an internal boundary-layer problem. Some basic properties can be learned from a steady state 2-D (x-z) model.The WTS (Weng, Taylor and Salmon, 2010, J. Wind Eng. Ind. Aerodyn. 98, 121-132 ) model of flow above changes in surface conditions has been used to investigate planetary boundary-layer flow over water with spatial changes in temperature, and to investigate situations leading to saturation and fog formation. Our turbulence closure includes the turbulent kinetic energy equation but we prefer to specify a height, surface roughness, Rossby number and local stability dependent, "master" length scale instead of a somewhat empirical dissipation or similar equation. Results show that fog can develop and extent to heights of order 100m in some conditions, depending on upstream profiles of wind, temperature and mixing ratio, and on solar radiation and the horizontal variations in water surface temperature.Next steps will involve validation against data being collected (by AMEC-Foster Wheeler in the Hibernia Management and Development Company Metocean project) over the Grand Banks and an interface with WRF and high resolution sea surface temperature data for forecasting fog conditions over the Grand Banks.

Significance of the double-layer capacitor effect in polar rubbery dielectrics and exceptionally stable low-voltage high transconductance organic transistors.

PubMed

Wang, Chao; Lee, Wen-Ya; Kong, Desheng; Pfattner, Raphael; Schweicher, Guillaume; Nakajima, Reina; Lu, Chien; Mei, Jianguo; Lee, Tae Hoon; Wu, Hung-Chin; Lopez, Jeffery; Diao, Ying; Gu, Xiaodan; Himmelberger, Scott; Niu, Weijun; Matthews, James R; He, Mingqian; Salleo, Alberto; Nishi, Yoshio; Bao, Zhenan

2015-12-14

Both high gain and transconductance at low operating voltages are essential for practical applications of organic field-effect transistors (OFETs). Here, we describe the significance of the double-layer capacitance effect in polar rubbery dielectrics, even when present in a very low ion concentration and conductivity. We observed that this effect can greatly enhance the OFET transconductance when driven at low voltages. Specifically, when the polar elastomer poly(vinylidene fluoride-co-hexafluoropropylene) (e-PVDF-HFP) was used as the dielectric layer, despite a thickness of several micrometers, we obtained a transconductance per channel width 30 times higher than that measured for the same organic semiconductors fabricated on a semicrystalline PVDF-HFP with a similar thickness. After a series of detailed experimental investigations, we attribute the above observation to the double-layer capacitance effect, even though the ionic conductivity is as low as 10(-10) S/cm. Different from previously reported OFETs with double-layer capacitance effects, our devices showed unprecedented high bias-stress stability in air and even in water.

Significance of the double-layer capacitor effect in polar rubbery dielectrics and exceptionally stable low-voltage high transconductance organic transistors

PubMed Central

Wang, Chao; Lee, Wen-Ya; Kong, Desheng; Pfattner, Raphael; Schweicher, Guillaume; Nakajima, Reina; Lu, Chien; Mei, Jianguo; Lee, Tae Hoon; Wu, Hung-Chin; Lopez, Jeffery; Diao, Ying; Gu, Xiaodan; Himmelberger, Scott; Niu, Weijun; Matthews, James R.; He, Mingqian; Salleo, Alberto; Nishi, Yoshio; Bao, Zhenan

2015-01-01

Both high gain and transconductance at low operating voltages are essential for practical applications of organic field-effect transistors (OFETs). Here, we describe the significance of the double-layer capacitance effect in polar rubbery dielectrics, even when present in a very low ion concentration and conductivity. We observed that this effect can greatly enhance the OFET transconductance when driven at low voltages. Specifically, when the polar elastomer poly(vinylidene fluoride-co-hexafluoropropylene) (e-PVDF-HFP) was used as the dielectric layer, despite a thickness of several micrometers, we obtained a transconductance per channel width 30 times higher than that measured for the same organic semiconductors fabricated on a semicrystalline PVDF-HFP with a similar thickness. After a series of detailed experimental investigations, we attribute the above observation to the double-layer capacitance effect, even though the ionic conductivity is as low as 10–10 S/cm. Different from previously reported OFETs with double-layer capacitance effects, our devices showed unprecedented high bias-stress stability in air and even in water. PMID:26658331

Fabrication of superhydrophobic cotton fabrics using crosslinking polymerization method

NASA Astrophysics Data System (ADS)

Jiang, Bin; Chen, Zhenxing; Sun, Yongli; Yang, Huawei; Zhang, Hongjie; Dou, Haozhen; Zhang, Luhong

2018-05-01

With the aim of removing and recycling oil and organic solvent from water, a facile and low-cost crosslinking polymerization method was first applied on surface modification of cotton fabrics for water/oil separation. Micro-nano hierarchical rough structure was constructed by triethylenetetramine (TETA) and trimesoyl chloride (TMC) that formed a polymeric layer on the surface of the fabric and anchored Al2O3 nanoparticles firmly between the fabric surface and the polymer layer. Superhydrophobic property was further obtained through self-assembly grafting of hydrophobic groups on the rough surface. The as-prepared cotton fabric exhibited superoleophilicity in atmosphere and superhydrophobicity both in atmosphere and under oil with the water contact angle of 153° and 152° respectively. Water/oil separation test showed that the as-prepared cotton fabric can handle with various oil-water mixtures with a high separation efficiency over 99%. More importantly, the separation efficiency remained above 98% over 20 cycles of reusing without losing its superhydrophobicity which demonstrated excellent reusability in oil/water separation process. Moreover, the as-prepared cotton fabric possessed good contamination resistance ability and self-cleaning property. Simulation washing process test showed the superhydrophobic cotton fabric maintained high value of water contact angle above 150° after 100 times washing, indicating great stability and durability. In summary, this work provides a brand-new way to surface modification of cotton fabric and makes it a promising candidate material for oil/water separation.

Liming Poultry Manures to Kill Pathogens and Decrease Soluble Phosphorus

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

Maguire,R.; Hesterberg, D.; Gernat, A.

2006-01-01

Received for publication September 9, 2005. Stabilizing phosphorus (P) in poultry waste to reduce P losses from manured soils is important to protect surface waters, while pathogens in manures are an emerging issue. This study was conducted to evaluate CaO and Ca(OH){sub 2} for killing manure bacterial populations (pathogens) and stabilizing P in poultry wastes and to investigate the influence on soils following amendment with the treated wastes. Layer manure and broiler litter varying in moisture content were treated with CaO and Ca(OH){sub 2} at rates of 2.5, 5, 10, and 15% by weight. All treated wastes were analyzed formore » microbial plate counts, pH, and water-soluble phosphorus (WSP), while a few selected layer manures were analyzed by phosphorus X-ray absorption near edge structure (XANES). A loamy sand and a silt loam were amended with broiler litter and layer manure treated with CaO at rates of 0, 2.5, 5, 10, and 15% and soil WSP and pH were measured at times 1, 8, and 29 d. Liming reduced bacterial populations, with greater rates of lime leading to greater reductions; for example 10% CaO applied to 20% solids broiler litter reduced the plate counts from 793 000 to 6500 mL{sup -1}. Liming also reduced the WSP in the manures by over 90% in all cases where at least 10% CaO was added. Liming the manures also reduced WSP in soils immediately following application and raised soil pH. The liming process used successfully reduced plate counts and concerns about P losses in runoff following land application of these limed products due to decreased WSP.« less

Liming poultry manures to decrease soluble phosphorus and suppress the bacteria population.

PubMed

Maguire, R O; Hesterberg, D; Gernat, A; Anderson, K; Wineland, M; Grimes, J

2006-01-01

Stabilizing phosphorus (P) in poultry waste to reduce P losses from manured soils is important to protect surface waters, while pathogens in manures are an emerging issue. This study was conducted to evaluate CaO and Ca(OH)2 for killing manure bacterial populations (pathogens) and stabilizing P in poultry wastes and to investigate the influence on soils following amendment with the treated wastes. Layer manure and broiler litter varying in moisture content were treated with CaO and Ca(OH)2 at rates of 2.5, 5, 10, and 15% by weight. All treated wastes were analyzed for microbial plate counts, pH, and water-soluble phosphorus (WSP), while a few selected layer manures were analyzed by phosphorus X-ray absorption near edge structure (XANES). A loamy sand and a silt loam were amended with broiler litter and layer manure treated with CaO at rates of 0, 2.5, 5, 10, and 15% and soil WSP and pH were measured at times 1, 8, and 29 d. Liming reduced bacterial populations, with greater rates of lime leading to greater reductions; for example 10% CaO applied to 20% solids broiler litter reduced the plate counts from 793,000 to 6500 mL-1. Liming also reduced the WSP in the manures by over 90% in all cases where at least 10% CaO was added. Liming the manures also reduced WSP in soils immediately following application and raised soil pH. The liming process used successfully reduced plate counts and concerns about P losses in runoff following land application of these limed products due to decreased WSP.

A Mechanism for Recent Production of Liquid Water on Mars

NASA Technical Reports Server (NTRS)

Hecht, M. H.; Bridges, N. T.

2003-01-01

Though Mars is a cold, dry planet, with respect to the thermal stability of liquid water at low altitudes it is not terribly different from comparably cold places on Earth. In dry air such water would evaporate faster on Mars, at a rate comparable to a 60 C hot spring on Earth, but the heat loss associated with that evaporation would be mitigated by the poor thermal convection in the thin Martian air. Even at higher altitudes where the atmospheric pressure does not reach the triple point of water, liquid water might theoretically exist in a low-vapor pressure form such as wet soil, in a briny solution, or simply under a layer of dust or snow. The theoretical stability of liquid water does not suggest its occurrence, either on Mars or in Antarctica. In fact, global models have suggested that locations capable of providing sufficient heat for melting are, precisely for that reason, too dry for water to be present. However, the temperature of irregular local structures such as trenches or craters can be markedly warmer than those of the uniform surfaces of global models. The work described here suggests a plausible scenario in which seasonal liquid water might be produced locally, in sheltered locations, through a process of condensation, cold-trapping, buffering, and melting. While the amounts produced in the present climate would be small, copious amounts of meltwater may have been produced at other phases of the orbital cycle, as recently as 20,000 years ago.

A Raman Microspectroscopy Study of Water and Trehalose in Spin-Dried Cells

PubMed Central

Abazari, Alireza; Chakraborty, Nilay; Hand, Steven; Aksan, Alptekin; Toner, Mehmet

2014-01-01

Long-term storage of desiccated nucleated mammalian cells at ambient temperature may be accomplished in a stable glassy state, which can be achieved by removal of water from the biological sample in the presence of glass-forming agents including trehalose. The stability of the glass may be compromised due to a nonuniform distribution of residual water and trehalose within and around the desiccated cells. Thus, quantification of water and trehalose contents at the single-cell level is critical for predicting the glass formation and stability for dry storage. Using Raman microspectroscopy, we estimated the trehalose and residual water contents in the microenvironment of spin-dried cells. Individual cells with or without intracellular trehalose were embedded in a solid thin layer of extracellular trehalose after spin-drying. We found strong evidence suggesting that the residual water was bound at a 2:1 water/trehalose molar ratio in both the extracellular and intracellular milieus. Other than the water associated with trehalose, we did not find any more residual water in the spin-dried sample, intra- or extracellularly. The extracellular trehalose film exhibited characteristics of an amorphous state with a glass transition temperature of ∼22°C. The intracellular milieu also dried to levels suitable for glass formation at room temperature. These findings demonstrate a method for quantification of water and trehalose in desiccated specimens using confocal Raman microspectroscopy. This approach has broad use in desiccation studies to carefully investigate the relationship of water and trehalose content and distribution with the tolerance to drying in mammalian cells. PMID:25418294

Fluid-structure interaction in Taylor-Couette flow

NASA Astrophysics Data System (ADS)

Kempf, Martin Horst Willi

1998-10-01

The linear stability of a viscous fluid between two concentric, rotating cylinders is considered. The inner cylinder is a rigid boundary and the outer cylinder has an elastic layer exposed to the fluid. The subject is motivated by flow between two adjoining rollers in a printing press. The governing equations of the fluid layer are the incompressible Navier-Stokes equations, and the governing equations of the elastic layer are Navier's equations. A narrow gap, neutral stability, and axisymmetric disturbances are assumed. The solution involves a novel technique for treating two layer stability problems, where an exact solution in the elastic layer is used to isolate the problem in the fluid layer. The results show that the presence of the elastic layer has only a slight effect on the critical Taylor numbers for the elastic parameters of modern printing presses. However, there are parameter values where the critical Taylor number is dramatically different than the classical Taylor-Couette problem.

Formation of natural gas hydrates in marine sediments. Gas hydrate growth and stability conditioned by host sediment properties

USGS Publications Warehouse

Clennell, M.B.; Henry, P.; Hovland, M.; Booth, J.S.; Winters, W.J.; Thomas, M.

2000-01-01

The stability conditions of submarine gas hydrates (methane clathrates) are largely dictated by pressure, temperature, gas composition, and pore water salinity. However, the physical properties and surface chemistry of the host sediments also affect the thermodynamic state, growth kinetics, spatial distributions, and growth forms of clathrates. Our model presumes that gas hydrate behaves in a way analogous to ice in the pores of a freezing soil, where capillary forces influence the energy balance. Hydrate growth is inhibited within fine-grained sediments because of the excess internal phase pressure of small crystals with high surface curvature that coexist with liquid water in small pores. Therefore, the base of gas hydrate stability in a sequence of fine sediments is predicted by our model to occur at a lower temperature, and so nearer to the seabed than would be calculated from bulk thermodynamic equilibrium. The growth forms commonly observed in hydrate samples recovered from marine sediments (nodules, sheets, and lenses in muds; cements in sand and ash layers) can be explained by a requirement to minimize the excess of mechanical and surface energy in the system.

Miscible gravitational instability of initially stable horizontal interface in a porous medium: Non-monotonic density profiles

NASA Astrophysics Data System (ADS)

Kim, Min Chan

2014-11-01

To simulate a CO2 sequestration process, some researchers employed a water/propylene glycol (PPG) system which shows a non-monotonic density profile. Motivated by this fact, the stability of the diffusion layer of two miscible fluids saturated in a porous medium is analyzed. For a non-monotonic density profile system, linear stability equations are derived in a global domain, and then transformed into a system of ordinary differential equations in an infinite domain. Initial growth rate analysis is conducted without the quasi-steady state approximation (QSSA) and shows that initially the system is unconditionally stable for the least stable disturbance. For the time evolving case, the ordinary differential equations are solved applying the eigen-analysis and numerical shooting scheme with and without the QSSA. To support these theoretical results, direct numerical simulations are conducted using the Fourier spectral method. The results of theoretical linear stability analyses and numerical simulations validate one another. The present linear and nonlinear analyses show that the water/PPG system is more unstable than the CO2/brine one, and the flow characteristics of these two systems are quite different from each other.

Chitosan-caseinate bilayer coatings for paper packaging materials.

PubMed

Khwaldia, Khaoula; Basta, Altaf H; Aloui, Hajer; El-Saied, Houssni

2014-01-01

Papers coated with caseinate and caseinate/chitosan bilayer films were developed. Caseinate, chitosan and caseinate/chitosan films were preliminary characterized by FTIR spectroscopy and thermal stability analyses. The effects of coating weight, caseinate concentration (7%, 10%, and 12%, w/w), and coating application methods (single layer and bilayer) on the physical and mechanical properties of coated papers were studied. Increasing the concentration of caseinate led to a decrease in water vapor permeability (WVP) of the resulting coated paper sheets. Chitosan significantly (p<0.05) increased the elongation at break (%E) of coated paper. However, the application of chitosan as a second layer on wet or dry caseinate films did not significantly affect (p>0.05) the tensile strength (TS) of coated paper. The greatest reduction in paper WVP is achieved by addition of a chitosan layer to the dried preformed caseinate-coated paper. Copyright © 2013 Elsevier Ltd. All rights reserved.

Delay in the Freezing of Supercooled Water Drops on Superhydrophobic Surfaces of Silicone Rubber at Negative Temperatures

NASA Astrophysics Data System (ADS)

Bezdomnikov, A. A.; Emel'yanenko, A. M.; Emel'yanenko, K. A.; Boinovich, L. B.

2018-01-01

A method is proposed for fabricating textured superhydrophobic surfaces of silicone rubber with mechanical resistance toward liquid or freezing aqueous solutions. The anti-icing characteristics of silicone rubber samples that differ in the wetting characteristics and mechanical stability of their micro- and nanotextures are derived by analyzing the delays in the freezing of supercooled sessile water drops deposited on the sample surface. The longest delay in freezings are observed for sessile water drops on superhydrophobic surfaces prepared by laser texturing with subsequent application of a layer of a hydrophobic agent to consolidate the textural elements. Delay in freezings can be as long as tens of hours on such surfaces at T = -18°C. The prepared superhydrophobic surfaces exhibit greater anti-icing ability with respect to aqueous salt solutions than to deionized water.

Whey protein/polysaccharide-stabilized emulsions: Effect of polymer type and pH on release and topical delivery of salicylic acid.

PubMed

Combrinck, Johann; Otto, Anja; du Plessis, Jeanetta

2014-06-01

Emulsions are widely used as topical formulations in the pharmaceutical and cosmetic industries. They are thermodynamically unstable and require emulsifiers for stabilization. Studies have indicated that emulsifiers could affect topical delivery of actives, and this study was therefore designed to investigate the effects of different polymers, applied as emulsifiers, as well as the effects of pH on the release and topical delivery of the active. O/w emulsions were prepared by the layer-by-layer technique, with whey protein forming the first layer around the oil droplets, while either chitosan or carrageenan was subsequently adsorbed to the protein at the interface. Additionally, the emulsions were prepared at three different pH values to introduce different charges to the polymers. The active ingredient, salicylic acid, was incorporated into the oil phase of the emulsions. Physical characterization of the resulting formulations, i.e., droplet size, zeta potential, stability, and turbidity in the water phase, was performed. Release studies were conducted, after which skin absorption studies were performed on the five most stable emulsions, by using Franz type diffusion cells and utilizing human, abdominal skin membranes. It was found that an increase in emulsion droplet charge could negatively affect the release of salicylic acid from these formulations. Contrary, positively charged emulsion droplets were found to enhance dermal and transdermal delivery of salicylic acid from emulsions. It was hypothesized that electrostatic complex formation between the emulsifier and salicylic acid could affect its release, whereas electrostatic interaction between the emulsion droplets and skin could influence dermal/transdermal delivery of the active.

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

Christians, Jeffrey A.; Schulz, Philip; Tinkham, Jonathan S.

Long-term device stability is the most pressing issue that impedes perovskite solar cell commercialization, given the achieved 22.7% efficiency. The perovskite absorber material itself has been heavily scrutinized for being prone to degradation by water, oxygen and ultraviolet light. To date, most reports characterize device stability in the absence of these extrinsic factors. Here we show that, even under the combined stresses of light (including ultraviolet light), oxygen and moisture, perovskite solar cells can retain 94% of peak efficiency despite 1,000 hours of continuous unencapsulated operation in ambient air conditions (relative humidity of 10-20%). Each interface and contact layer throughoutmore » the device stack plays an important role in the overall stability which, when appropriately modified, yields devices in which both the initial rapid decay (often termed burn-in) and the gradual slower decay are suppressed. This extensively modified device architecture and the understanding developed will lead towards durable long-term device performance.« less

Entropic contributions enhance polarity compensation for CeO2(100) surfaces

NASA Astrophysics Data System (ADS)

Capdevila-Cortada, Marçal; López, Núria

2017-03-01

Surface structure controls the physical and chemical response of materials. Surface polar terminations are appealing because of their unusual properties but they are intrinsically unstable. Several mechanisms, namely metallization, adsorption, and ordered reconstructions, can remove thermodynamic penalties rendering polar surfaces partially stable. Here, for CeO2(100), we report a complementary stabilization mechanism based on surface disorder that has been unravelled through theoretical simulations that: account for surface energies and configurational entropies; show the importance of the ion distribution degeneracy; and identify low diffusion barriers between conformations that ensure equilibration. Disordered configurations in oxides might also be further stabilized by preferential adsorption of water. The entropic stabilization term will appear for surfaces with a high number of empty sites, typically achieved when removing part of the ions in a polar termination to make the layer charge zero. Assessing the impact of surface disorder when establishing new structure-activity relationships remains a challenge.

Multiple Steady States of Buoyancy Induced Flow in Cold Water and Their Stability.

NASA Astrophysics Data System (ADS)

El-Henawy, Ibrahim Mahmoud

In Chapters 1 and 2 the physical background and the literature related to buoyancy-induced flows are reviewed. An accurate representation, based upon experimental data, of the motion-causing buoyancy force, in the vicinity of maximum density in pure water at low temperatures, is used. This representation is an accurate and quite simple formulation due to Gebhart and Mollendorf (1977). Using the representation, we study, numerically, Chapter 3, a model for the laminar, boundary-layer flow arising from natural convection adjacent to a vertical isothermal flat surface submerged in quiescent cold water. The results demonstrate for the first time the existence of multiple steady-state solutions in a natural convection flow. The existence of these new multiple steady-state solutions led to an investigation of their stability. This is carried out in Chapter 4 by a mathematical method, different from that of the usual hydrodynamic stability approach, Lin (1955) and Razinand and Reid (1982). Three real eigenvalue and eigenvector pairs corresponding to the new steady-state -solutions were found. Each of these eigenvalues changes its algebraic sign at a particular limit point (point of vertical tangency, nose, knee) in the bifurcation diagrams found in Chapter 3. The results indicate that the new steady-state solutions are unstable and that the previously found steady-state solutions, Carey, Gebhart, and Mollendorf (1980), may be stable.

Observations of the atmospheric boundary layer height over Abu Dhabi, United Arab Emirates: Investigating boundary layer climatology in arid regions

NASA Astrophysics Data System (ADS)

Marzooqi, Mohamed Al; Basha, Ghouse; Ouarda, Taha B. M. J.; Armstrong, Peter; Molini, Annalisa

2014-05-01

Strong sensible heat fluxes and deep turbulent mixing - together with marked dustiness and a low substrate water content - represent a characteristic signature in the boundary layer over hot deserts, resulting in "thicker" mixing layers and peculiar optical properties. Beside these main features however, desert ABLs present extremely complex local structures that have been scarcely addressed in the literature, and whose understanding is essential in modeling processes such as the transport of dust and pollutants, and turbulent fluxes of momentum, heat and water vapor in hyper-arid regions. In this study, we analyze a continuous record of observations of the atmospheric boundary layer (ABL) height from a single lens LiDAR ceilometer operated at Masdar Institute Field Station (24.4oN, 54.6o E, Abu Dhabi, United Arab Emirates), starting March 2013. We compare different methods for the estimation of the ABL height from Ceilometer data such as, classic variance-, gradient-, log gradient- and second derivation-methods as well as recently developed techniques such as the Bayesian Method and Wavelet covariance transform. Our goal is to select the most suited technique for describing the climatology of the ABL in desert environments. Comparison of our results with radiosonde observations collected at the nearby airport of Abu Dhabi indicate that the WCT and the Bayesian method are the most suitable tools to accurately identify the ABL height in all weather conditions. These two methods are used for the definition of diurnal and seasonal climatologies of the boundary layer conditional to different atmospheric stability classes.

Boosting water oxidation layer-by-layer.

PubMed

Hidalgo-Acosta, Jonnathan C; Scanlon, Micheál D; Méndez, Manuel A; Amstutz, Véronique; Vrubel, Heron; Opallo, Marcin; Girault, Hubert H

2016-04-07

Electrocatalysis of water oxidation was achieved using fluorinated tin oxide (FTO) electrodes modified with layer-by-layer deposited films consisting of bilayers of negatively charged citrate-stabilized IrO2 NPs and positively charged poly(diallyldimethylammonium chloride) (PDDA) polymer. The IrO2 NP surface coverage can be fine-tuned by controlling the number of bilayers. The IrO2 NP films were amorphous, with the NPs therein being well-dispersed and retaining their as-synthesized shape and sizes. UV/vis spectroscopic and spectro-electrochemical studies confirmed that the total surface coverage and electrochemically addressable surface coverage of IrO2 NPs increased linearly with the number of bilayers up to 10 bilayers. The voltammetry of the modified electrode was that of hydrous iridium oxide films (HIROFs) with an observed super-Nernstian pH response of the Ir(III)/Ir(IV) and Ir(IV)-Ir(IV)/Ir(IV)-Ir(V) redox transitions and Nernstian shift of the oxygen evolution onset potential. The overpotential of the oxygen evolution reaction (OER) was essentially pH independent, varying only from 0.22 V to 0.28 V (at a current density of 0.1 mA cm(-2)), moving from acidic to alkaline conditions. Bulk electrolysis experiments revealed that the IrO2/PDDA films were stable and adherent under acidic and neutral conditions but degraded in alkaline solutions. Oxygen was evolved with Faradaic efficiencies approaching 100% under acidic (pH 1) and neutral (pH 7) conditions, and 88% in alkaline solutions (pH 13). This layer-by-layer approach forms the basis of future large-scale OER electrode development using ink-jet printing technology.

Superhydrophobic materials for drug delivery

NASA Astrophysics Data System (ADS)

Yohe, Stefan Thomas

Superhydrophobicity is a property of material surfaces reflecting the ability to maintain air at the solid-liquid interface when in contact with water. These surfaces have characteristically high apparent contact angles, by definition exceeding 150°, as a result of the composite material-air surface formed under an applied water droplet. Superhydrophobic surfaces were first discovered on naturally occurring substrates, and have subsequently been fabricated in the last several decades to harness these favorable surface properties for a number of emerging applications, including their use in biomedical settings. This work describes fabrication and characterization of superhydrophobic 3D materials, as well as their use as drug delivery devices. Superhydrophobic 3D materials are distinct from 2D superhydrophobic surfaces in that air is maintained not just at the surface of the material, but also within the bulk. When the superhydrophobic 3D materials are submerged in water, water infiltrates slowly and continuously as a new water-air-material interface is formed with controlled displacement of air. Electrospinning and electrospraying are used to fabricate superhydrophobic 3D materials utilizing blends of the biocompatible polymers poly(epsilon-caprolactone) and poly(caprolactone-co-glycerol monostearate) (PGC-C18). PGC-C18 is significantly more hydrophobic than PCL (contact angle of 116° versus 83° for flat materials), and further additions of PGC-C18 into electrospun meshes and electrosprayed coatings affords increased stability of the entrapped air layer. For example, PCL meshes alone (500 mum thick) take 10 days to fully wet, and with 10% or 30% PGC-C18 addition wetting rates are dramatically slowed to 60% wetted by 77 days and 4% by 75 days, respectively. Stability of the superhydrophobic materials can be further probed with a variety of physio-chemical techniques, including pressure, surfactant containing solutions, and solvents of varying surface tension. Superhydrophobicity is shown to be enhanced with further increases in PGC-C18 content and surface roughness (a decrease in fiber size). We demonstrate the utility of superhydrophobicity as a method for drug delivery. When the camptothecin derivatives SN-38 and CPT-11 are encapsulated within electrospun meshes, changes in air layer stability (due to changes in PGC-C18 content) dictate the rate of drug release by controlling the rate in which water can permeate into the porous 3D electrospun structure. Drug release can be tuned from 2 weeks to >10 weeks from 300 mum meshes, and meshes effectively kill a variety of cancer cell lines (lung, colon, breast) when utilized in a cytotoxicity assay. After determining that air could be used to control the rate of drug release, superhydrophobic 3D materials are explored for three applications. First, meshes are considered as a potential combination reinforcement-drug delivery device for use in resectable colorectal cancer. Second, removal of the air layer in superhydrophobic meshes is used as a method to trigger drug release. The pressure generated from high-intensity focused ultrasound (0.75-4.25 MPa) can remove the air layer spatially and temporally, allowing drug release to be controlled with application of a sufficient treatment. Third, "connective" electrosprayed coatings are deposited on chemically distinct material surfaces, which are both three-dimensional and mechanically robust. In summary, superhydrophobic 3D materials are fabricated and characterized, and are utilized as drug delivery devices. Controlled air removal from these materials offers an entirely new strategy for drug delivery, and is promising for the applications considered in this work as well as many others.

Stable azodye photo-alignment layer for liquid crystal devices achieved by "turning off" dye photosensitivity

NASA Astrophysics Data System (ADS)

McGinty, C.; Finnemeyer, V.; Reich, R.; Clark, H.; Berry, S.; Bos, P.

2017-11-01

We have previously proposed a low cost, versatile process for stabilizing azodye photo-alignment layers for liquid crystal devices by utilizing a surface localized reactive mesogen (RM) layer. The RM is applied by dissolving the monomer in a liquid crystal material prior to filling the cell. In this paper, we show the significant effect of azodye layer thickness on the long term stability of these alignment layers when exposed to polarized light. We demonstrate, surprisingly, that thin azodye layers (˜3 nm) provide improved stability over thicker (˜40 nm) layers. Using this process, we show cells which have been stable to exposure with polarized light through one month. Additionally, we demonstrate the use of a photo-alignment layer to align the liquid crystals that afterwards can be rendered insensitive to polarized light. This was accomplished by using the process described above with the additional step of eliminating the photosensitivity of the azodye layer through photo-bleaching; the result is an RM alignment layer that will be stable when exposed to polarized light in the dye absorption band.

Gypsum under pressure: A first-principles study

NASA Astrophysics Data System (ADS)

Giacomazzi, Luigi; Scandolo, Sandro

2010-02-01

We investigate by means of first-principles methods the structural response of gypsum (CaSO4ṡ2H2O) to pressures within and above the stability range of gypsum-I (P≤4GPa) . Structural and vibrational properties calculated for gypsum-I are in excellent agreement with experimental data. Compression within gypsum-I takes place predominantly through a reduction in the volume of the CaO8 polyhedra and through a distortion of the hydrogen bonds. The distance between CaSO4 layers becomes increasingly incompressible, indicating a mechanical limit to the packing of water molecules between the layers. We find that a structure with collapsed interlayer distances becomes more stable than gypsum-I above about 5 GPa. The collapse is concomitant with a rearrangement of the hydrogen-bond network of the water molecules. Comparison of the vibrational spectra calculated for this structure with experimental data taken above 5 GPa supports the validity of our model for the high-pressure phase of gypsum.

Microgels at the Water/Oil Interface: In Situ Observation of Structural Aging and Two-Dimensional Magnetic Bead Microrheology.

PubMed

Huang, Shilin; Gawlitza, Kornelia; von Klitzing, Regine; Gilson, Laurent; Nowak, Johannes; Odenbach, Stefan; Steffen, Werner; Auernhammer, Günter K

2016-01-26

Stimuli-responsive microgels can be used as stabilizers for emulsions. However, the details of structure and the viscoelastic property of the microgel-laden interface are still not well-known. We synthesized fluorescently labeled microgels and used confocal microscopy to observe their arrangement at the water/oil interface. The microgels aggregated spontaneously at the interface, and the aggregated structure reorganized due to thermal motion. The structure of the interfacial layer formed by microgels depended on the microgel concentration at the interface. We suggest that the structure was controlled by the aggregation and adsorption of microgels at the interface. The interparticle separation between microgels at the interface decreased over time, implying a slow aging process of the microgels at the interface. Magnetic beads were introduced at the interface and used to trigger deformation of the microgel layer. Under compression and shear the microgels in the aggregated structure rearranged, leading to plastic deformation, and some elastic responses were also observed.

Surface potential of methyl isobutyl carbinol adsorption layer at the air/water interface.

PubMed

Phan, Chi M; Nakahara, Hiromichi; Shibata, Osamu; Moroi, Yoshikiyo; Le, Thu N; Ang, Ha M

2012-01-26

The surface potential (ΔV) and surface tension (γ) of MIBC (methyl isobutyl carbinol) were measured on the subphase of pure water and electrolyte solutions (NaCl at 0.02 and 2 M). In contrast to ionic surfactants, it was found that surface potential gradually increased with MIBC concentration. The ΔV curves were strongly influenced by the presence of NaCl. The available model in literature, in which surface potential is linearly proportional to surface excess, failed to describe the experimental data. Consequently, a new model, employing a partial charge of alcohol adsorption layer, was proposed. The new model predicted the experimental data consistently for MIBC in different NaCl solutions. However, the model required additional information for ionic impurity to predict adsorption in the absence of electrolyte. Such inclusion of impurities is, however, unnecessary for industrial applications. The modeling results successfully quantify the influence of electrolytes on surface potential of MIBC, which is critical for froth stability.

The Tropopause Inversion Layer: New Observations, New Theories

NASA Astrophysics Data System (ADS)

Tandon, N.; Randel, W. J.; Pan, L.; Son, S.; Polvani, L. M.

2009-12-01

There is now great interest in the tropopause inversion inversion layer (TIL), a 1-2 km region just above the tropopause where there is a spike in static stability. Radio occultation data from the COSMIC GPS mission are providing an unprecedented level of spatial and temporal resolution with which to analyze the TIL. We start by showing the agreement between GPS data and radiosondes. We then examine the causes and consequences of the TIL. Observations from the ACE satellite and fixed dynamical heating calculations suggest strong roles for water vapor and ozone in the formation and modulation of the TIL. This agrees with observations showing a large TIL in the polar winter, where water vapor levels are persistently high. It is also clear that TIL strength is related to vorticity, but observations and models have important differences that need to be reconciled. These dynamical considerations dovetail with observations showing high TIL variability in the storm-track regions. Finally there is evidence from ozonesonde data that the TIL may be coupled to transport across the tropopause.

Direct Detection of Potential Pyrethroids in Yangtze River via an Imprinted Multilayer Phosphorescence Probe.

PubMed

Chen, Li; Lv, Xiaodong; Dai, Jiangdong; Sun, Lin; Huo, Pengwei; Li, Chunxiang; Yan, Yongsheng

2018-01-01

A novel tailored multilayer probe for monitoring potential pyrethroids in the Yangtze River was proposed. The room-temperature phosphorescence method was applied to realize a detection strategy that is superior to the fluorescence method. Efficient Mn-doped ZnS quantum dots with uniform size of 4.6 nm were firstly coated with a mesoporous silica to obtain a suitable intermediate transition layer, then an imprinted layer containing bifenthrin specific recognition sites was anchored. Characterizations verified the multilayer structure convincingly and the detection process relied on the electron transfer-induced fluorescence quenching mechanism. Optional detection time and standard detection curve were obtained within a concentration range from 5.0 to 50 μmol L -1 . The stability was verified to be good after 12 replicates. Feasibility of the probe was proved by monitoring water samples from the Zhenjiang reach of the Yangtze River. The probe offers promise for direct bifenthrin detection in unknown environmental water with an accurate and stable phosphorescence analysis strategy.

Adsorption and Distribution of Edible Gliadin Nanoparticles at the Air/Water Interface.

PubMed

Peng, Dengfeng; Jin, Weiping; Li, Jing; Xiong, Wenfei; Pei, Yaqiong; Wang, Yuntao; Li, Yan; Li, Bin

2017-03-22

Edible gliadin nanoparticles (GNPs) were fabricated using the anti-solvent method. They possessed unique high foamability and foam stability. An increasing concentration of GNPs accelerated their initial adsorption speed from the bulk phase to the interface and raised the viscoelastic modulus of interfacial films. High foamability (174.2 ± 6.4%) was achieved at the very low concentration of GNPs (1 mg/mL), which was much better than that of ovalbumin and sodium caseinate. Three stages of adsorption kinetics at the air/water interface were characterized. First, they quickly diffused and adsorbed at the interface, resulting in a fast increase of the surface pressure. Then, nanoparticles started to fuse into a film, and finally, the smooth film became a firm and rigid layer to protect bubbles against coalescence and disproportionation. These results explained that GNPs had good foamability and high foam stability simultaneously. That provides GNPs as a potential candidate for new foaming agents applied in edible and biodegradable products.

Interaction of cinnamic acid derivatives with β-cyclodextrin in water: experimental and molecular modeling studies.

PubMed

Liu, Benguo; Zeng, Jie; Chen, Chen; Liu, Yonglan; Ma, Hanjun; Mo, Haizhen; Liang, Guizhao

2016-03-01

Cyclodextrins (CDs) can be used to improve the solubility and stability of cinnamic acid derivatives (CAs). However, there was no detailed report about understanding the effects of the substituent groups in the benzene ring on the inclusion behavior between CAs and CDs in aqueous solution. Here, the interaction of β-CD with CAs, including caffeic acid, ferulic acid, and p-coumaric acid, in water was investigated by phase-solubility method, UV, fluorescence, and (1)H NMR spectroscopy, together with ONIOM (our Own N-layer Integrated Orbital molecular Mechanics)-based QM/MM (Quantum Mechanics/Molecular Mechanics) calculations. Experimental results demonstrated that CAs could form 1:1 stoichiometric inclusion complex with β-CD by non-covalent bonds, and that the maximum apparent stability constants were found in caffeic acid (176M(-1)) followed by p-coumaric acid (160M(-1)) and ferulic acid (133M(-1)). Moreover, our calculations reasonably illustrated the binding orientations of β-CD with CAs determined by experimental observations. Copyright © 2015. Published by Elsevier Ltd.

Effect of Submarine Groundwater Discharge on Relict Arctic Submarine Permafrost and Gas Hydrate

NASA Astrophysics Data System (ADS)

Frederick, J. M.; Buffett, B. A.

2014-12-01

Permafrost-associated gas hydrate deposits exist at shallow depths within the sediments of the circum-Arctic continental shelves. Degradation of this shallow water reservoir has the potential to release large quantities of methane gas directly to the atmosphere. Gas hydrate stability and the permeability of the shelf sediments to gas migration is closely linked with submarine permafrost. Submarine permafrost extent depends on several factors, such as the lithology, sea level variations, mean annual air temperature, ocean bottom water temperature, geothermal heat flux, and the salinity of the pore water. The salinity of the pore water is especially relevant because it partially controls the freezing point for both ice and gas hydrate. Measurements of deep pore water salinity are few and far between, but show that deep off-shore sediments are fresh. Deep freshening has been attributed to large-scale topographically-driven submarine groundwater discharge, which introduces fresh terrestrial groundwater into deep marine sediments. We investigate the role of submarine ground water discharge on the salinity field and its effects on the seaward extent of relict submarine permafrost and gas hydrate stability on the Arctic shelf with a 2D shelf-scale model based on the finite volume method. The model tracks the evolution of the temperature, salinity, and pressure fields given imposed boundary conditions, with latent heat of water ice and hydrate formation included. The permeability structure of the sediments is coupled to changes in permafrost. Results show that pore fluid is strongly influenced by the permeability variations imposed by the overlying permafrost layer. Groundwater discharge tends to travel horizontally off-shore beneath the permafrost layer and the freshwater-saltwater interface location displays long timescale transient behavior that is dependent on the groundwater discharge strength. The seaward permafrost extent is in turn strongly influenced by the salinity field and location of the freshwater-saltwater transition. Our results suggest that the role of salt transport and its effect on permafrost evolution can provide context for the interpretation of recent permafrost maps and methane observations in the Arctic.

Method of forming an HTS article

DOEpatents

Bhattacharya, Raghu N.; Zhang, Xun; Selvamanickam, Venkat

2014-08-19

A method of forming a superconducting article includes providing a substrate tape, forming a superconducting layer overlying the substrate tape, and depositing a capping layer overlying the superconducting layer. The capping layer includes a noble metal and has a thickness not greater than about 1.0 micron. The method further includes electrodepositing a stabilizer layer overlying the capping layer using a solution that is non-reactive to the superconducting layer. The superconducting layer has an as-formed critical current I.sub.C(AF) and a post-stabilized critical current I.sub.C(PS). The I.sub.C(PS) is at least about 95% of the I.sub.C(AF).

The ocean mixed layer under Southern Ocean sea-ice: seasonal cycle and forcing.

NASA Astrophysics Data System (ADS)

Violaine, P.; Sallee, J. B.; Schmidtko, S.; Roquet, F.; Charrassin, J. B.

2016-02-01

The mixed-layer at the surface of the ocean is the gateway for all exchanges between air and sea. A vast area of the Southern Ocean is however seasonally capped by sea-ice, which alters this gateway and the characteristic the ocean mixed-layer. The interaction between the ocean mixed-layer and sea-ice plays a key role for water-mass formation and circulation, carbon cycle, sea-ice dynamics, and ultimately for the climate as a whole. However, the structure and characteristics of the mixed layer, as well as the processes responsible for its evolution, are poorly understood due to the lack of in-situ observations and measurements. We urgently need to better understand the forcing and the characteristics of the ocean mixed-layer under sea-ice if we are to understand and predict the world's climate. In this study, we combine a range of distinct sources of observation to overcome this lack in our understanding of the Polar Regions. Working on Elephant Seal-derived data as well as ship-based observations and Argo float data, we describe the seasonal cycle of the characteristics and stability of the ocean mixed layer over the entire Southern Ocean (South of 40°S), and specifically under sea-ice. Mixed-layer budgets of heat and freshwater are used to investigate the main forcings of the mixed-layer seasonal cycle. The seasonal variability of sea surface salinity and temperature are primarily driven by surface processes, dominated by sea-ice freshwater flux for the salt budget, and by air-sea flux for the heat budget. Ekman advection, vertical diffusivity and vertical entrainment play only secondary role.Our results suggest that changes in regional sea-ice distribution or sea-ice seasonal cycle duration, as currently observed, would widely affect the buoyancy budget of the underlying mixed-layer, and impacts large-scale water-mass formation and transformation.

Fronts and intrusions in the upper Deep Polar Water of the Eurasian and Makarov basins

NASA Astrophysics Data System (ADS)

Kuzmina, Natalia; Rudels, Bert; Zhurbas, Natalia; Lyzhkov, Dmitry

2013-04-01

CTD data obtained in the Arctic Basin are analyzed to describe structural features of intrusive layers and fronts encountered in the upper Deep Polar Water. This work is an extension of Arctic intrusions studies by Rudels et al. (1999) and Kuzmina et al. (2011). Numerous examples of fronts and intrusions observed in a deep layer (depth range of 600-1300 m) in the Eurasian and Makarov basins where salinity is increasing, and temperature is decreasing with depth (stable-stable thermohaline stratification), are described. The data are used to estimate hydrological parameters capable of determining different types of fronts and characterizing intrusive layers depending on the front structure. Coherence of intrusive layers is shown to get broken with the change of front structure. An evidence is found that enhanced turbulent mixing above local bottom elevations can prevent from intrusive layering. A linear stability model description of the observed intrusions is developed based on the Merryfield's (2000) assumption that interleaving is caused by differential mixing. Theoretical analysis is focused on prediction of the slopes of unstable modes at baroclinic and thermohaline fronts. Apparent vertical diffusivity due to turbulent mixing at baroclinic and thermohaline fronts is estimated on the basis of comparison of observed intrusion slopes with modeled slopes of the most unstable modes. Apparent lateral diffusivity is estimated too, based on Joyce (1980) approach. These estimates show that intrusive instability of fronts caused by differential mixing can result in sizable values of apparent lateral heat diffusivity in the deep Arctic layer that are quite comparable with those of the upper and intermediate Arctic layers (Walsh, Carmack, 2003; Kuzmina et al., 2011).

Interfacial rheology of surface-active biopolymers: Acacia senegal gum versus hydrophobically modified starch.

PubMed

Erni, Philipp; Windhab, Erich J; Gunde, Rok; Graber, Muriel; Pfister, Bruno; Parker, Alan; Fischer, Peter

2007-11-01

Acacia gum is a hybrid polyelectrolyte containing both protein and polysaccharide subunits. We study the interfacial rheology of its adsorption layers at the oil/water interface and compare it with adsorbed layers of hydrophobically modified starch, which for economic and political reasons is often used as a substitute for Acacia gum in technological applications. Both the shear and the dilatational rheological responses of the interfaces are considered. In dilatational experiments, the viscoelastic response of the starch derivative is just slightly weaker than that for Acacia gum, whereas we found pronounced differences in shear flow: The interfaces covered with the plant gum flow like a rigid, solidlike material with large storage moduli and a linear viscoelastic regime limited to small shear deformations, above which we observe apparent yielding behavior. In contrast, the films formed by hydrophobically modified starch are predominantly viscous, and the shear moduli are only weakly dependent on the deformation. Concerning their most important technological use as emulsion stabilizers, the dynamic interfacial responses imply not only distinct interfacial dynamics but also different stabilizing mechanisms for these two biopolymers.

Linear stability of three-dimensional boundary layers - Effects of curvature and non-parallelism

NASA Technical Reports Server (NTRS)

Malik, M. R.; Balakumar, P.

1993-01-01

In this paper we study the effect of in-plane (wavefront) curvature on the stability of three-dimensional boundary layers. It is found that this effect is stabilizing or destabilizing depending upon the sign of the crossflow velocity profile. We also investigate the effects of surface curvature and nonparallelism on crossflow instability. Computations performed for an infinite-swept cylinder show that while convex curvature stabilizes the three-dimensional boundary layer, nonparallelism is, in general, destabilizing and the net effect of the two depends upon meanflow and disturbance parameters. It is also found that concave surface curvature further destabilizes the crossflow instability.

Geomorphic Evidence for Martian Ground Ice and Climate Change

NASA Technical Reports Server (NTRS)

Kanner, L. C.; Allen, C. C.; Bell, M. S.

2004-01-01

Recent results from gamma-ray and neutron spectrometers on Mars Odyssey indicate the presence of a hydrogen-rich layer tens of centimeters thick in the uppermost meter in high latitudes (>60 ) on Mars. This hydrogen-rich layer correlates to regions of ice stability. Thus, the subsurface hydrogen is thought to be water ice constituting 35+/- 15% by weight near the north and south polar regions. We refine the location of subsurface ice deposits at a < km scale by combining existing spectroscopy data with surface features indicative of subsurface ice. A positive correlation between spectroscopy data and geomorphic ice indicators has been previously suggested for high latitudes. Here we expand the comparative study to northern mid latitudes (30 deg.N- 65 deg.N).

Stability of mixing layers

NASA Technical Reports Server (NTRS)

Tam, Christopher; Krothapalli, A

1993-01-01

The research program for the first year of this project (see the original research proposal) consists of developing an explicit marching scheme for solving the parabolized stability equations (PSE). Performing mathematical analysis of the computational algorithm including numerical stability analysis and the determination of the proper boundary conditions needed at the boundary of the computation domain are implicit in the task. Before one can solve the parabolized stability equations for high-speed mixing layers, the mean flow must first be found. In the past, instability analysis of high-speed mixing layer has mostly been performed on mean flow profiles calculated by the boundary layer equations. In carrying out this project, it is believed that the boundary layer equations might not give an accurate enough nonparallel, nonlinear mean flow needed for parabolized stability analysis. A more accurate mean flow can, however, be found by solving the parabolized Navier-Stokes equations. The advantage of the parabolized Navier-Stokes equations is that its accuracy is consistent with the PSE method. Furthermore, the method of solution is similar. Hence, the major part of the effort of the work of this year has been devoted to the development of an explicit numerical marching scheme for the solution of the Parabolized Navier-Stokes equation as applied to the high-seed mixing layer problem.

Perovskite Solar Cells with Inorganic Electron- and Hole-Transport Layers Exhibiting Long-Term (≈500 h) Stability at 85 °C under Continuous 1 Sun Illumination in Ambient Air.

PubMed

Seo, Seongrok; Jeong, Seonghwa; Bae, Changdeuck; Park, Nam-Gyu; Shin, Hyunjung

2018-05-22

Despite the high power conversion efficiency (PCE) of perovskite solar cells (PSCs), poor long-term stability is one of the main obstacles preventing their commercialization. Several approaches to enhance the stability of PSCs have been proposed. However, an accelerating stability test of PSCs at high temperature under the operating conditions in ambient air remains still to be demonstrated. Herein, interface-engineered stable PSCs with inorganic charge-transport layers are shown. The highly conductive Al-doped ZnO films act as efficient electron-transporting layers as well as dense passivation layers. This layer prevents underneath perovskite from moisture contact, evaporation of components, and reaction with a metal electrode. Finally, inverted-type PSCs with inorganic charge-transport layers exhibit a PCE of 18.45% and retain 86.7% of the initial efficiency for 500 h under continuous 1 Sun illumination at 85 °C in ambient air with electrical biases (at maximum power point tracking). © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lignin-assisted exfoliation of molybdenum disulfide in aqueous media and its application in lithium ion batteries

NASA Astrophysics Data System (ADS)

Liu, Wanshuang; Zhao, Chenyang; Zhou, Rui; Zhou, Dan; Liu, Zhaolin; Lu, Xuehong

2015-05-01

In this article, alkali lignin (AL)-assisted direct exfoliation of MoS2 mineral into single-layer and few-layer nanosheets in water is reported for the first time. Under optimized conditions, the concentration of MoS2 nanosheets in the obtained dispersion can be as high as 1.75 +/- 0.08 mg mL-1, which is much higher than the typical reported concentrations (<1.0 mg mL-1) using synthetic polymers or compounds as surfactants. The stabilizing mechanism primarily lies in the electrostatic repulsion between negative charged AL, as suggested by zeta-potential measurements. When the exfoliated MoS2 nanosheets are applied as electrode materials for lithium ion batteries, they show much improved electrochemical performance compared with the pristine MoS2 mineral because of the enhanced ion and electron transfer kinetics. This facile, scalable and eco-friendly aqueous-based process in combination with renewable and ultra-low-cost lignin opens up possibilities for large-scale fabrication of MoS2-based nanocomposites and devices. Moreover, herein we demonstrate that AL is also an excellent surfactant for exfoliation of many other types of layered materials, including graphene, tungsten disulfide and boron nitride, in water, providing rich opportunities for a wider range of applications.In this article, alkali lignin (AL)-assisted direct exfoliation of MoS2 mineral into single-layer and few-layer nanosheets in water is reported for the first time. Under optimized conditions, the concentration of MoS2 nanosheets in the obtained dispersion can be as high as 1.75 +/- 0.08 mg mL-1, which is much higher than the typical reported concentrations (<1.0 mg mL-1) using synthetic polymers or compounds as surfactants. The stabilizing mechanism primarily lies in the electrostatic repulsion between negative charged AL, as suggested by zeta-potential measurements. When the exfoliated MoS2 nanosheets are applied as electrode materials for lithium ion batteries, they show much improved electrochemical performance compared with the pristine MoS2 mineral because of the enhanced ion and electron transfer kinetics. This facile, scalable and eco-friendly aqueous-based process in combination with renewable and ultra-low-cost lignin opens up possibilities for large-scale fabrication of MoS2-based nanocomposites and devices. Moreover, herein we demonstrate that AL is also an excellent surfactant for exfoliation of many other types of layered materials, including graphene, tungsten disulfide and boron nitride, in water, providing rich opportunities for a wider range of applications. Electronic supplementary information (ESI) available: CV of the bulk MoS2 between 1-3 V, electrochemical performances of the exfoliated MoS2 nanosheets between 1-3 V with 10 wt% carbon black, referenced table of exfoliation of MoS2 in aqueous media. See DOI: 10.1039/c5nr01891a

Identifying Water on Mt. Baker and Mt. St. Helens, WA with Geophysics: Implications for Volcanic Landslide Hazards

NASA Astrophysics Data System (ADS)

Finn, C.; Bedrosian, P.; Wisniewski, M.; Deszcz-Pan, M.

2015-12-01

Groundwater position, abundance, and flow rates within a volcano affect the transmission of fluid pressure, transport of mass and heat and formation of mechanically weak hydrothermal alteration influencing the stability of volcanoes. In addition, eruptions can shatter volcanic rocks, weakening the edifice. Helicopter magnetic and electromagnetic (HEM) data collected over Mt. Baker and Mt. St. Helens volcanoes reveal the distribution of water, shattered volcanic rocks and hydrothermal alteration essential to evaluating volcanic landslide hazards. These data, combined with geological mapping and rock property measurements, indicate the presence of localized <100 m thick zones of water-saturated hydrothermally altered rock beneath Sherman Crater and the Dorr Fumarole Fields at Mt. Baker. Nuclear magnetic resonance data indicate that the hydrothermal clays contain ~50% bound water with no evidence for free water ponded beneath the ice. The HEM data suggest water-saturated fresh volcanic rocks from the surface to the detection limit (~100 m) over the entire summit of Mt. Baker (below the ice). A 50-100 m thick high resistivity layer (>1500 ohm-m) corresponding to domes, debris avalanche, volcanic rocks and glaciers mantles the crater at Mt. St. Helens. Shallow low resistivity layers corresponding to fresh, cold water and hot brines are observed below the high resistivity surface in EM data. Shallow ground water mainly concentrates in shattered dome material in the crater of Mt. St. Helens. Aeromagnetic data indicate the location of basalts sandwiched between debris avalanche deposits and shattered dome material. The combination of the EM and magnetic data help map the location of the shattered dome material that is considered to be the failure surface for the 1980 debris avalanche. The EM data image the regional groundwater table near the base of the volcano. The geophysical identification of groundwater and weak layers constrain landslide hazards assessments.

Fabrication of Thin Electrolytes for Second-Generation Solid Oxide Fuel Cells

DTIC Science & Technology

1999-05-05

stabilized zirconia but are equally applicable to components, have been developed. Halogen com- other oxide electrolytes. pounds such as ZrCl4 and YC13...substrates. They used ZrCl4 and an oxygen source reactant. EVD is a two-step YC13 vapor mixtures as the metal compound sources process. The first step...thin zirconia layers on ited film. In this step oxygen ions formed on the porous alumina substrates. ZrCl4 and YC13 vapor water vapor side of the

Long-term stability enhancement of Brillouin measurement in polymer optical fibers using amorphous fluoropolymer

NASA Astrophysics Data System (ADS)

Matsutani, Natsuki; Lee, Heeyoung; Mizuno, Yosuke; Nakamura, Kentaro

2018-01-01

For Brillouin-sensing applications, we develop a method for mitigating the Fresnel reflection at the perfluorinated-polymer-optical-fiber ends by covering them with an amorphous fluoropolymer (CYTOP, fiber core material) dissolved in a volatile solvent. Unlike the conventional method using water, even after solvent evaporation, the CYTOP layer remains, resulting in long-term Fresnel reduction. In addition, the high viscosity of the CYTOP solution is a practical advantage. The effectiveness of this method is experimentally proved by Brillouin measurement.

Two-step emulsification process for water-in-oil-in-water multiple emulsions stabilized by lamellar liquid crystals.

PubMed

Ito, Toshifumi; Tsuji, Yukitaka; Aramaki, Kenji; Tonooka, Noriaki

2012-01-01

Multiple emulsions, also called complex emulsions or multiphase emulsions, include water-in-oil-in-water (W/O/W)-type and oil-in-water-in-oil (O/W/O)-type emulsions. W/O/W-type multiple emulsions, obtained by utilizing lamellar liquid crystal with a layer structure showing optical anisotropy at the periphery of emulsion droplets, are superior in stability to O/W/O-type emulsions. In this study, we investigated a two-step emulsification process for a W/O/W-type multiple emulsion utilizing liquid crystal emulsification. We found that a W/O/W-type multiple emulsion containing lamellar liquid crystal can be prepared by mixing a W/O-type emulsion (prepared by primary emulsification) with a lamellar liquid crystal obtained from poly(oxyethylene) stearyl ether, cetyl alcohol, and water, and by dispersing and emulsifying the mixture in an outer aqueous phase. When poly(oxyethylene) stearyl ether and cetyl alcohol are each used in a given amount and the amount of water added is varied from 0 to 15 g (total amount of emulsion, 100 g), a W/O/W-type multiple emulsion is efficiently prepared. When the W/O/W-type multiple emulsion was held in a thermostatic bath at 25°C, the droplet size distribution showed no change 0, 30, or 60 days after preparation. Moreover, the W/O/W-type multiple emulsion strongly encapsulated Uranine in the inner aqueous phase as compared with emulsions prepared by one-step emulsification.

Confined Water in Layered Silicates: The Origin of Anomalous Thermal Expansion Behavior in Calcium-Silicate-Hydrates

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

Krishnan, N. M. Anoop; Wang, Bu; Falzone, Gabriel

Water, under conditions of nanoscale confinement, exhibits anomalous dynamics, and enhanced thermal deformations, which may be further enhanced when such water is in contact with hydrophilic surfaces. Such heightened thermal deformations of water could control the volume stability of hydrated materials containing nanoconfined structural water. Understanding and predicting the thermal deformation coefficient (TDC, often referred to as the CTE, coefficient of thermal expansion), which represents volume changes induced in materials under conditions of changing temperature, is of critical importance for hydrated solids including: hydrogels, biological tissues, and calcium silicate hydrates, as changes in their volume can result in stress development,more » and cracking. By pioneering atomistic simulations, we examine the physical origin of thermal expansion in calcium-silicate-hydrates (C–S–H), the binding agent in concrete that is formed by the reaction of cement with water. We report that the TDC of C–S–H shows a sudden increase when the CaO/SiO 2 (molar ratio; abbreviated as Ca/Si) exceeds 1.5. This anomalous behavior arises from a notable increase in the confinement of water contained in the C–S–H’s nanostructure. We identify that confinement is dictated by the topology of the C–S–H’s atomic network. Altogether, the results suggest that thermal deformations of hydrated silicates can be altered by inducing compositional changes, which in turn alter the atomic topology and the resultant volume stability of the solids.« less

Confined Water in Layered Silicates: The Origin of Anomalous Thermal Expansion Behavior in Calcium-Silicate-Hydrates.

PubMed

Krishnan, N M Anoop; Wang, Bu; Falzone, Gabriel; Le Pape, Yann; Neithalath, Narayanan; Pilon, Laurent; Bauchy, Mathieu; Sant, Gaurav

2016-12-28

Water, under conditions of nanoscale confinement, exhibits anomalous dynamics, and enhanced thermal deformations, which may be further enhanced when such water is in contact with hydrophilic surfaces. Such heightened thermal deformations of water could control the volume stability of hydrated materials containing nanoconfined structural water. Understanding and predicting the thermal deformation coefficient (TDC, often referred to as the CTE, coefficient of thermal expansion), which represents volume changes induced in materials under conditions of changing temperature, is of critical importance for hydrated solids including: hydrogels, biological tissues, and calcium silicate hydrates, as changes in their volume can result in stress development, and cracking. By pioneering atomistic simulations, we examine the physical origin of thermal expansion in calcium-silicate-hydrates (C-S-H), the binding agent in concrete that is formed by the reaction of cement with water. We report that the TDC of C-S-H shows a sudden increase when the CaO/SiO 2 (molar ratio; abbreviated as Ca/Si) exceeds 1.5. This anomalous behavior arises from a notable increase in the confinement of water contained in the C-S-H's nanostructure. We identify that confinement is dictated by the topology of the C-S-H's atomic network. Taken together, the results suggest that thermal deformations of hydrated silicates can be altered by inducing compositional changes, which in turn alter the atomic topology and the resultant volume stability of the solids.

Confined Water in Layered Silicates: The Origin of Anomalous Thermal Expansion Behavior in Calcium-Silicate-Hydrates

DOE PAGES

Krishnan, N. M. Anoop; Wang, Bu; Falzone, Gabriel; ...

2016-12-06

Water, under conditions of nanoscale confinement, exhibits anomalous dynamics, and enhanced thermal deformations, which may be further enhanced when such water is in contact with hydrophilic surfaces. Such heightened thermal deformations of water could control the volume stability of hydrated materials containing nanoconfined structural water. Understanding and predicting the thermal deformation coefficient (TDC, often referred to as the CTE, coefficient of thermal expansion), which represents volume changes induced in materials under conditions of changing temperature, is of critical importance for hydrated solids including: hydrogels, biological tissues, and calcium silicate hydrates, as changes in their volume can result in stress development,more » and cracking. By pioneering atomistic simulations, we examine the physical origin of thermal expansion in calcium-silicate-hydrates (C–S–H), the binding agent in concrete that is formed by the reaction of cement with water. We report that the TDC of C–S–H shows a sudden increase when the CaO/SiO 2 (molar ratio; abbreviated as Ca/Si) exceeds 1.5. This anomalous behavior arises from a notable increase in the confinement of water contained in the C–S–H’s nanostructure. We identify that confinement is dictated by the topology of the C–S–H’s atomic network. Altogether, the results suggest that thermal deformations of hydrated silicates can be altered by inducing compositional changes, which in turn alter the atomic topology and the resultant volume stability of the solids.« less

Perovskite solar cells with CuSCN hole extraction layers yield stabilized efficiencies greater than 20%

NASA Astrophysics Data System (ADS)

Arora, Neha; Dar, M. Ibrahim; Hinderhofer, Alexander; Pellet, Norman; Schreiber, Frank; Zakeeruddin, Shaik Mohammed; Grätzel, Michael

2017-11-01

Perovskite solar cells (PSCs) with efficiencies greater than 20% have been realized only with expensive organic hole-transporting materials. We demonstrate PSCs that achieve stabilized efficiencies exceeding 20% with copper(I) thiocyanate (CuSCN) as the hole extraction layer. A fast solvent removal method enabled the creation of compact, highly conformal CuSCN layers that facilitate rapid carrier extraction and collection. The PSCs showed high thermal stability under long-term heating, although their operational stability was poor. This instability originated from potential-induced degradation of the CuSCN/Au contact. The addition of a conductive reduced graphene oxide spacer layer between CuSCN and gold allowed PSCs to retain >95% of their initial efficiency after aging at a maximum power point for 1000 hours under full solar intensity at 60°C. Under both continuous full-sun illumination and thermal stress, CuSCN-based devices surpassed the stability of spiro-OMeTAD-based PSCs.

Protecting hydrogenation-generated oxygen vacancies in BiVO4 photoanode for enhanced water oxidation with conformal ultrathin amorphous TiO2 layer

NASA Astrophysics Data System (ADS)

Zhang, Yang; Zhang, Xintong; Wang, Dan; Wan, Fangxu; Liu, Yichun

2017-05-01

Introducing appropriate amount of oxygen vacancies by hydrogenation treatment is a simple and efficient way to improve the photoelectrochemical performance of nanostructured oxide photoanodes. However, the hydrogenation effect is often not durable due to the gradual healing of oxygen vacancies at or close to surface of photoanodes. Herein, we tackled the problem by conformal coating the hydrogenated nanoporous BiVO4 (H-BiVO4) photoanode with an ultrathin layer of amorphous TiO2. Photoelectrochemical measurements showed that a 4 nm-thick TiO2 layer could significantly improve the stability of H-BiVO4 photoanode for repeated working test, with negligible influence on the initial photocurrent compared to the uncoated one. Mott-Schottky and linear sweep voltammetry measurements showed that donor density and photocurrent density of the H-BiVO4 electrode almost decayed to the values of pristine BiVO4 electrode after 3 h test, while the amorphous TiO2-coated electrode only degraded by 6% and 5% of the initial values respectively in the same period. The investigation thus suggested that the amorphous TiO2 layer did protect the oxygen vacancies in H-BiVO4 photoanode by isolating these oxygen vacancies from environmental oxygen, while at the same time not impeding the interfacial charge transfer to water molecules due to its leaky nature.

Terahertz Pulsed Imaging and Magnetic Resonance Imaging as Tools to Probe Formulation Stability

PubMed Central

Zhang, Qilei; Gladden, Lynn F.; Avalle, Paolo; Zeitler, J. Axel; Mantle, Michael D.

2013-01-01

Dissolution stability over the entire shelf life duration is of critical importance to ensure the quality of solid dosage forms. Changes in the drug release profile during storage may affect the bioavailability of drug products. This study investigated the stability of a commercial tablet (Lescol® XL) when stored under accelerated conditions (40 °C/75% r.h.). Terahertz pulsed imaging (TPI) was used to investigate the structure of the tablet coating before and after the accelerated aging process. The results indicate that the coating was reduced in thickness and exhibited a higher density after being stored under accelerated conditions for four weeks. In situ magnetic resonance imaging (MRI) of the water penetration processes during tablet dissolution in a USP-IV dissolution cell equipped with an in-line UV-vis analyzer was carried out to study local differences in water uptake into the tablet matrix between the stressed and unstressed state. The drug release profiles of the Lescol® XL tablet before and after the accelerated storage stability testing were compared using a “difference” factor f1 and a “similarity” factor f2. The results reveal that even though the physical properties of the coating layers changed significantly during the stress testing, the coating protected the tablet matrix and the densification of the coating polymer had no adverse effect on the drug release performance. PMID:24300564

Formulating food protein-stabilized indomethacin nanosuspensions into pellets by fluid-bed coating technology: physical characterization, redispersibility, and dissolution.

PubMed

He, Wei; Lu, Yi; Qi, Jianping; Chen, Lingyun; Yin, Lifang; Wu, Wei

2013-01-01

Drug nanosuspensions are very promising for enhancing the dissolution and bioavailability of drugs that are poorly soluble in water. However, the poor stability of nanosuspensions, reflected in particle growth, aggregation/agglomeration, and change in crystallinity state greatly limits their applications. Solidification of nanosuspensions is an ideal strategy for addressing this problem. Hence, the present work aimed to convert drug nanosuspensions into pellets using fluid-bed coating technology. Indomethacin nanosuspensions were prepared by the precipitation-ultrasonication method using food proteins (soybean protein isolate, whey protein isolate, β-lactoglobulin) as stabilizers. Dried nanosuspensions were prepared by coating the nanosuspensions onto pellets. The redispersibility, drug dissolution, solid-state forms, and morphology of the dried nanosuspensions were evaluated. The mean particle size for the nanosuspensions stabilized using soybean protein isolate, whey protein isolate, and β-lactoglobulin was 588 nm, 320 nm, and 243 nm, respectively. The nanosuspensions could be successfully layered onto pellets with high coating efficiency. Both the dried nanosuspensions and nanosuspensions in their original amorphous state and not influenced by the fluid-bed coating drying process could be redispersed in water, maintaining their original particle size and size distribution. Both the dried nanosuspensions and the original drug nanosuspensions showed similar dissolution profiles, which were both much faster than that of the raw crystals. Fluid-bed coating technology has potential for use in the solidification of drug nanosuspensions.

Stabilization of ammonia-rich hydrate inside icy planets.

PubMed

Naden Robinson, Victor; Wang, Yanchao; Ma, Yanming; Hermann, Andreas

2017-08-22

The interior structure of the giant ice planets Uranus and Neptune, but also of newly discovered exoplanets, is loosely constrained, because limited observational data can be satisfied with various interior models. Although it is known that their mantles comprise large amounts of water, ammonia, and methane ices, it is unclear how these organize themselves within the planets-as homogeneous mixtures, with continuous concentration gradients, or as well-separated layers of specific composition. While individual ices have been studied in great detail under pressure, the properties of their mixtures are much less explored. We show here, using first-principles calculations, that the 2:1 ammonia hydrate, (H 2 O)(NH 3 ) 2 , is stabilized at icy planet mantle conditions due to a remarkable structural evolution. Above 65 GPa, we predict it will transform from a hydrogen-bonded molecular solid into a fully ionic phase O 2- ([Formula: see text]) 2 , where all water molecules are completely deprotonated, an unexpected bonding phenomenon not seen before. Ammonia hemihydrate is stable in a sequence of ionic phases up to 500 GPa, pressures found deep within Neptune-like planets, and thus at higher pressures than any other ammonia-water mixture. This suggests it precipitates out of any ammonia-water mixture at sufficiently high pressures and thus forms an important component of icy planets.

Nanoparticle modification by weak polyelectrolytes for pH-sensitive pickering emulsions.

PubMed

Haase, Martin F; Grigoriev, Dmitry; Moehwald, Helmuth; Tiersch, Brigitte; Shchukin, Dmitry G

2011-01-04

The affinity of weak polyelectrolyte coated oxide particles to the oil-water interface can be controlled by the degree of dissociation and the thickness of the weak polyelectrolyte layer. Thereby the oil in water (o/w) emulsification ability of the particles can be enabled. We selected the weak polyacid poly(methacrylic acid sodium salt) and the weak polybase poly(allylamine hydrochloride) for the surface modification of oppositely charged alumina and silica colloids, respectively. The isoelectric point and the pH range of colloidal stability of both particle-polyelectrolyte composites depend on the thickness of the weak polyelectrolyte layer. The pH-dependent wettability of a weak polyelectrolyte-coated oxide surface is characterized by contact angle measurements. The o/w emulsification properties of both particles for the nonpolar oil dodecane and the more polar oil diethylphthalate are investigated by measurements of the droplet size distributions. Highly stable emulsions can be obtained when the degree of dissociation of the weak polyelectrolyte is below 80%. Here the average droplet size depends on the degree of dissociation, and a minimum can be found when 15 to 45% of the monomer units are dissociated. The thickness of the adsorbed polyelectrolyte layer strongly influences the droplet size of dodecane/water emulsion droplets but has a less pronounced impact on the diethylphthalate/water droplets. We explain the dependency of the droplet size on the emulsion pH value and the polyelectrolyte coating thickness with arguments based on the particle-wetting properties, the particle aggregation state, and the oil phase polarity. Cryo-SEM visualization shows that the regularity of the densely packed particles on the oil-water interface correlates with the degree of dissociation of the corresponding polyelectrolyte.

Stability of Water Ice Beneath Porous Dust Layers of the Martian South Polar Terrain

NASA Astrophysics Data System (ADS)

Keller, H. U.; Skorov, Yu. V.; Markiewicz, W. J.; Basilevsky, A. T.

2000-08-01

The analysis of the Viking Infrared Thermal Mapper (IRTM) data show that the surface layers of the Mars south polar layered deposits have very low thermal inertia between 75 and 125 J/(sq m)(s-1/2)(K-1). This is consistent with the assumption that the surface is covered by a porous layer of fine dust. Paige and Keegan determined a slightly higher value based on a thermal model similar to that of Kieffer et al. In this model the heat transfer equation is used to estimate the thickness of the layer that protects the ground ice from seasonal and diurnal temperature variations. The physical properties of the layer are unimportant as long as it has a low thermal inertia and conductivity and keeps the temperature at the ice boundary low enough to prevent sublimation. A thickness between 20 and 4 cm was estimated. This result can be considered to be an upper limit. We assume the surface to be covered by a porous dust layer and consider the gas diffusion through it, from the ground ice and from the atmosphere. Then the depth of the layer is determined by the mass flux balance of subliming and condensing water and not by the temperature condition. The dust particles in the atmosphere are of the order 1 gm. On the surface we can expect larger grains (up to sand size). Therefore assuming an average pore size of 10 gm, a volume porosity of 0.5, a heat capacity of 1300 J/(kg-1)(K-1) leads to a thermal inertia of approx. 80 J/(sq m)(s-1/2)(K-1). With these parameters a dust layer of only 5 mm thickness is found to establish the flux balance at the ice-dust interface during spring season in the southern hemisphere at high latitudes (where Mars Polar Lander arrived). The diurnal temperature variation at the ice-dust surface is shown. The maximum of 205 K well exceeds the sublimation temperature of water ice at 198 K under the atmospheric conditions. The corresponding vapour flux during the last day is shown together with the flux condensing from the atmosphere. The calculations show that the sub-surface ice on Mars can be thermodynamically and dynamically stable even if it is protected by a porous dust layer of only a few millimetres in thickness.

Power Conversion Efficiency and Device Stability Improvement of Inverted Perovskite Solar Cells by Using a ZnO:PFN Composite Cathode Buffer Layer.

PubMed

Jia, Xiaorui; Zhang, Lianping; Luo, Qun; Lu, Hui; Li, Xueyuan; Xie, Zhongzhi; Yang, Yongzhen; Li, Yan-Qing; Liu, Xuguang; Ma, Chang-Qi

2016-07-20

We have demonstrated in this article that both power conversion efficiency (PCE) and performance stability of inverted planar heterojunction perovskite solar cells can be improved by using a ZnO:PFN nanocomposite (PFN: poly[(9,9-bis(3'-(N,N-dimethylamion)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctyl)-fluorene]) as the cathode buffer layer (CBL). This nanocomposite could form a compact and defect-less CBL film on the perovskite/PC61BM surface (PC61BM: phenyl-C61-butyric acid methyl ester). In addition, the high conductivity of the nanocomposite layer makes it works well at a layer thickness of 150 nm. Both advantages of the composite layer are helpful in reducing interface charge recombination and improving device performance. The power conversion efficiency (PCE) of the best ZnO:PFN CBL based device was measured to be 12.76%, which is higher than that of device without CBL (9.00%), or device with ZnO (7.93%) or PFN (11.30%) as the cathode buffer layer. In addition, the long-term stability is improved by using ZnO:PFN composite cathode buffer layer when compare to that of the reference cells. Almost no degradation of open circuit voltage (VOC) and fill factor (FF) was found for the device having ZnO:PFN, suggesting that ZnO:PFN is able to stabilize the interface property and consequently improve the solar cell performance stability.

Influence of shear forces on the aggregation and sedimentation behavior of cerium dioxide (CeO2) nanoparticles under different hydrochemical conditions

NASA Astrophysics Data System (ADS)

Lv, Bowen; Wang, Chao; Hou, Jun; Wang, Peifang; Miao, Lingzhan; Li, Yi; Ao, Yanhui; Yang, Yangyang; You, Guoxiang; Xu, Yi

2016-07-01

This study contributed to a better understanding of the behavior of nanoparticles (NPs) in dynamic water. First, the aggregation behavior of CeO2 NPs at different pH values in various salt solutions was examined to determine the appropriate hydrochemical conditions for hydrodynamics study. Second, the aggregation behavior of CeO2 NPs under different shear forces was investigated at pH 4 and ionic strength 0 in various salt solutions to find out whether shear forces could influence the stability of the nanoparticles and if yes, how. Also, five-stage sedimentation tests were conducted to understand the influence of shear stress on the vertical distribution of CeO2 NPs in natural waters. The aggregation test showed that the shear force could increase the collision efficiency between NPs during aggregation and cause a relatively large mass of NPs to remain in suspension. Consequently, the nanoparticles had a greater possibility of continued aggregation. The sedimentation test under static conditions indicated that a large mass of NPs (>1000 nm) sink to the bottom layer, leaving only small aggregates dispersed in the upper or middle layer of the solution. However, later sedimentation studies under stirring conditions demonstrated that shear forces can disrupt this stratification phenomenon. These results suggest that shear forces can influence the spatial distribution of NPs in natural waters, which might lead to different toxicities of CeO2 NPs to aquatic organisms distributed in the different water layers. This study contributes to a better understanding of nanomaterial toxicology and provides a way for further research.

Ceramic pore channels with inducted carbon nanotubes for removing oil from water.

PubMed

Chen, Xinwei; Hong, Liang; Xu, Yanfang; Ong, Zheng Wei

2012-04-01

Water contaminated with tiny oil emulsions is costly and difficult to treat because of the colloidal stability and deformable nature of emulsified oil. This work utilizes carbon nanotubes (CNTs) in macro/mesopore channels of ceramic membrane to remove tiny oil droplets from water. The CNTs were implanted into the porous ceramic channels by means of chemical vapor deposition. Being hydrophobic in nature and possessing an interfacial curvature at nanoscale, CNTs enabled tiny oil emulsion in submicrometer and nano scales to be entrapped while permeating through the CNTs implanted pore channels. Optimizing the growth condition of the CNTs resulted in a uniform distribution of CNT grids, which allowed the development of lipophilic layers during filtration. These lipo-layers drastically enhanced the separation performance. The filtration capability of CNT-ceramic membrane was assessed by the purification of a dilute oil-in-water (o/w) emulsion containing ca. 210 ppm mineral oil 1600 ppm emulsifier, and a trace amount of dye, a proxy polluted water source. The best CNT-tailored ceramic membrane, prepared under the optimized CNT growth condition, claimed 100% oil rejection rate and a permeation flux of 0.6 L m(-2) min(-1), driven by a pressure drop of ca. 1 bar for 3 days on the basis of UV measurement. The CNT-sustained adsorption complements the size-exclusion mechanism in removing soluble oil.

Thin-film metal coated insulation barrier in a Josephson tunnel junction. [Patent application

DOEpatents

Hawkins, G.A.; Clarke, J.

1975-10-31

A highly stable, durable, and reproducible Josephson tunnel junction consists of a thin-film electrode of a hard superconductor, a thin oxide insulation layer over the electrode constituting a Josephson tunnel junction barrier, a thin-film layer of stabilizing metal over the barrier, and a second thin-film hard superconductive electrode over the stabilizing film. The thin stabilizing metal film is made only thick enough to limit penetration of the electrode material through the insulation layer so as to prevent a superconductive short.

Facile and Green Production of Impurity-Free Aqueous Solutions of WS2 Nanosheets by Direct Exfoliation in Water.

PubMed

Pan, Long; Liu, Yi-Tao; Xie, Xu-Ming; Ye, Xiong-Ying

2016-12-01

To obtain 2D materials with large quantity, low cost, and little pollution, liquid-phase exfoliation of their bulk form in water is a particularly fascinating concept. However, the current strategies for water-borne exfoliation exclusively employ stabilizers, such as surfactants, polymers, or inorganic salts, to minimize the extremely high surface energy of these nanosheets and stabilize them by steric repulsion. It is worth noting, however, that the remaining impurities inevitably bring about adverse effects to the ultimate performances of 2D materials. Here, a facile and green route to large-scale production of impurity-free aqueous solutions of WS 2 nanosheets is reported by direct exfoliation in water. Crucial parameters such as initial concentration, sonication time, centrifugation speed, and centrifugation time are systematically evaluated to screen out an optimized condition for scaling up. Statistics based on morphological characterization prove that substantial fraction (66%) of the obtained WS 2 nanosheets are one to five layers. X-ray diffraction and Raman characterizations reveal a high quality with few, if any, structural distortions. The water-borne exfoliation route opens up new opportunities for easy, clean processing of WS 2 -based film devices that may shine in the fields of, e.g., energy storage and functional nanocomposites owing to their excellent electrochemical, mechanical, and thermal properties. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Layered double hydroxide stability. 1. Relative stabilities of layered double hydroxides and their simple counterparts

NASA Technical Reports Server (NTRS)

Boclair, J. W.; Braterman, P. S.

1999-01-01

Solutions containing di- and trivalent metal chlorides [M(II) = Mg2+, Zn2+, Co2+, Ni2+, Mn2+; M(III) = Al3+, Fe3+] were titrated with NaOH to yield hydrotalcite-like layered double hydroxides (LDH), [[M(II)]1-x[M(III)]x(OH)2][Cl]x yH2O, by way of M(III) hydroxide/hydrous oxide intermediates. Analysis of the resultant titration curves yields nominal solubility constants for the LDH. The corresponding LDH stabilities are in the order Mg < Mn < Co approximately Ni < Zn for M(II) and Al < Fe for M(III). The stability of LDH relative to the separate metal hydroxides/hydrous oxides is discussed.

Mechanisms of Polyelectrolyte Enhanced Surfactant Adsorption at the Air-Water Interface

PubMed Central

Stenger, Patrick C.; Palazoglu, Omer A.; Zasadzinski, Joseph A.

2009-01-01

Chitosan, a naturally occurring cationic polyelectrolyte, restores the adsorption of the clinical lung surfactant Survanta to the air-water interface in the presence of albumin at much lower concentrations than uncharged polymers such as polyethylene glycol. This is consistent with the positively charged chitosan forming ion pairs with negative charges on the albumin and lung surfactant particles, reducing the net charge in the double-layer, and decreasing the electrostatic energy barrier to adsorption to the air-water interface. However, chitosan, like other polyelectrolytes, cannot perfectly match the charge distribution on the surfactant, which leads to patches of positive and negative charge at net neutrality. Increasing the chitosan concentration further leads to a reduction in the rate of surfactant adsorption consistent with an over-compensation of the negative charge on the surfactant and albumin surfaces, which creates a new repulsive electrostatic potential between the now cationic surfaces. This charge neutralization followed by charge inversion explains the window of polyelectrolyte concentration that enhances surfactant adsorption; the same physical mechanism is observed in flocculation and re-stabilization of anionic colloids by chitosan and in alternate layer deposition of anionic and cationic polyelectrolytes on charged colloids. PMID:19366599

Theoretical insights into aggregation-induced helicity modulation of a perylene bisimide derivative.

PubMed

Liang, Lijun; Li, Xin

2018-02-12

Formation of helical chiroptical self-assemblies via noncovalent interaction is a widely observed phenomenon in nature, the mechanism of which remains insufficiently understood. Employing an amphiphilic perylene-sugar dyad molecule (PBI-HAG) as an example, we report that the modulatable supramolecular helicity may emerge from an aggregating process that is dominated by competition between two types of noncovalent interaction: hydrogen bonding and π-π stacking. The interplay between these two driving forces, which is greatly affected by the solvent environment, determines the morphology the supramolecular assembly of PBI-HAGs. In particular, a non-layered supramolecular structure was formed in octane owing to stabilization effects of intermolecular hydrogen bonds, whereas a layered supramolecular structure was formed in water because of energetically favorable π-π stacking of aromatic rings. The formation of distinct supramolecular architectures in different solvents was reinforced by simulated circular dichroism spectra, which show opposite signals consistent with experimental observations. The results of this study could help us understand aggregation-induced supramolecular chirality of noncovalent self-assemblies. Graphical abstract Left Typical structures of amphiphilic perylene-sugar dyad (PBI-HAG) aggregates in different octane and water. Right Simulated CD and UV-Vis spectra of core PBIs aggregates in octane and water.

Mechanisms of polyelectrolyte enhanced surfactant adsorption at the air-water interface.

PubMed

Stenger, Patrick C; Palazoglu, Omer A; Zasadzinski, Joseph A

2009-05-01

Chitosan, a naturally occurring cationic polyelectrolyte, restores the adsorption of the clinical lung surfactant Survanta to the air-water interface in the presence of albumin at much lower concentrations than uncharged polymers such as polyethylene glycol. This is consistent with the positively charged chitosan forming ion pairs with negative charges on the albumin and lung surfactant particles, reducing the net charge in the double-layer, and decreasing the electrostatic energy barrier to adsorption to the air-water interface. However, chitosan, like other polyelectrolytes, cannot perfectly match the charge distribution on the surfactant, which leads to patches of positive and negative charge at net neutrality. Increasing the chitosan concentration further leads to a reduction in the rate of surfactant adsorption consistent with an over-compensation of the negative charge on the surfactant and albumin surfaces, which creates a new repulsive electrostatic potential between the now cationic surfaces. This charge neutralization followed by charge inversion explains the window of polyelectrolyte concentration that enhances surfactant adsorption; the same physical mechanism is observed in flocculation and re-stabilization of anionic colloids by chitosan and in alternate layer deposition of anionic and cationic polyelectrolytes on charged colloids.

Cellulose nanoparticles as modifiers for rheology and fluid loss in bentonite water-based fluids.

PubMed

Li, Mei-Chun; Wu, Qinglin; Song, Kunlin; Qing, Yan; Wu, Yiqiang

2015-03-04

Rheological and filtration characteristics of drilling fluids are considered as two critical aspects to ensure the success of a drilling operation. This research demonstrates the effectiveness of cellulose nanoparticles (CNPs), including microfibrillated cellulose (MFC) and cellulose nanocrystals (CNCs) in enhancing the rheological and filtration performances of bentonite (BT) water-based drilling fluids (WDFs). CNCs were isolated from MFC through sulfuric acid hydrolysis. In comparison with MFC, the resultant CNCs had much smaller dimensions, more negative surface charge, higher stability in aqueous solutions, lower viscosity, and less evident shear thinning behavior. These differences resulted in the distinctive microstructures between MFC/BT- and CNC/BT-WDFs. A typical "core-shell" structure was created in CNC/BT-WDFs due to the strong surface interactions among BT layers, CNCs, and immobilized water molecules. However, a similar structure was not formed in MFC/BT-WDFs. As a result, CNC/BT-WDFs had superior rheological properties, higher temperature stability, less fluid loss volume, and thinner filter cakes than BT and MFC/BT-WDFs. Moreover, the presence of polyanionic cellulose (PAC) further improved the rheological and filtration performances of CNC/BT-WDFs, suggesting a synergistic effect between PAC and CNCs.

Atmospheric stability analysis over statically and dynamically rough surfaces

NASA Astrophysics Data System (ADS)

Maric, Emina; Metzger, Meredith; Singha, Arindam; Sadr, Reza

2011-11-01

The ratio of buoyancy flux to turbulent kinetic energy production in the atmospheric surface layer is investigated experimentally for air flow over two types of surfaces characterized by static and dynamic roughness. In this study, ``static'' refers to the time-invariant nature of naturally-occurring roughness over a mud/salt playa; while, ``dynamic'' refers to the behavior of water waves along an air-water interface. In both cases, time-resolved measurements of the momentum and heat fluxes were acquired from synchronized 3D sonic anemometers mounted on a vertical tower. Field campaigns were conducted at two sites, representing the ``statically'' and ``dynamically'' rough surfaces, respectively: (1) the SLTEST facility in Utah's western desert, and (2) the new Doha airport in Qatar under construction along the coast of the Persian Gulf. Note, at site 2, anemometers were located directly above the water by extension from a tower secured to the end of a 1 km-long pier. Comparisons of the Monin-Obukhov length, flux Richardson number, and gradient Richardson number are presented, and discussed in the context of the observed evolution of the turbulent spectra in response to diurnal variations of atmospheric stability. Supported by the Qatar National Research Fund.

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

Szcześ, Aleksandra, E-mail: aszczes@poczta.umcs.lublin.pl; Czemierska, Magdalena; Jarosz-Wilkołazka, Anna

Extracellular polymeric substance (EPS) extracted from Rhodococcus opacus bacterial strain was used as a matrix for calcium carbonate precipitation using the vapour diffusion method. The total exopolymer and water-soluble exopolymer fraction of different concentrations were spread on the mica surface by the spin-coating method. The obtained layers were characterized using the atomic force microscopy measurement and XPS analysis. The effects of polymer concentration, initial pH of calcium chloride solution and precipitation time on the obtained crystals properties were investigated. Raman spectroscopy and scanning electron microscopy were used to characterize the precipitated minerals. It was found that the type of precipitatedmore » CaCO{sub 3} polymorph and the crystal size depend on the kind of EPS fraction. The obtained results indicates that the water soluble fraction favours vaterite dissolution and calcite growth, whereas the total EPS stabilizes vaterite and this effect is stronger at basic pH. It seems to be due to different contents of the functional group of EPS fractions. - Highlights: • CaCO{sub 3} crystal size and polymorph can be controlled by EPS substance obtained from R. opacus. • The water soluble fraction favours vaterite dissolution and calcite growth. • The total EPS stabilizes vaterite. • This effect is stronger at basic pH.« less

Surface modification of poly(vinylidene fluoride) hollow fibre membranes for biogas purification in a gas-liquid membrane contactor system.

PubMed

Jin, Pengrui; Huang, Chuan; Li, Jiaxiang; Shen, Yadong; Wang, Liao

2017-11-01

The wetting of hollow fibre membranes decreases the performance of the liquid-gas membrane contactor for CO 2 capture in biogas upgrading. To solve this problem, in this work, a poly(vinylidene fluoride) (PVDF) hollow fibre membrane for a liquid-gas membrane contactor was coated with a superhydrophobic layer composed of a combination of hydrophobic SiO 2 nanoparticles and polydimethylsiloxane (PDMS) by the method of spray deposition. A rough layer of SiO 2 deposited on the PVDF membrane resulted in an enhanced surface hydrophobicity. The surface structure of the pristine PVDF significantly affected the homogeneity of the generated SiO 2 layer. A uniform surface coating on the PVDF upper layer resulted from the presence of micrometre and nanometre-sized roughness on the surface of the PVDF membrane, which was achieved with a SiO 2 concentration of 4.44 mg ml -1 (0.2 g/45 ml) in the coating solution. As a result, the water contact angle of the modified surface was recorded as 155 ± 3°, which is higher than that of the pristine surface. The high contact angle is advantageous for reducing the wetting of the membrane. Additional mass transfer resistance was introduced by the superhydrophobic layer. In addition, continuous CO 2 absorption tests were carried out in original and modified PVDF hollow fibre membrane contactors, using monoethanolamine (MEA) solution as the absorbent. A long-term stability test revealed that the modified PVDF hollow fibre membrane contactor was able to outperform the original membrane contactor and demonstrated outstanding long-term stability, suggesting that spray deposition is a promising approach to obtain superhydrophobic PVDF membranes for liquid-gas membrane absorption.

Surface modification of poly(vinylidene fluoride) hollow fibre membranes for biogas purification in a gas–liquid membrane contactor system

PubMed Central

Huang, Chuan; Li, Jiaxiang; Shen, Yadong; Wang, Liao

2017-01-01

The wetting of hollow fibre membranes decreases the performance of the liquid–gas membrane contactor for CO2 capture in biogas upgrading. To solve this problem, in this work, a poly(vinylidene fluoride) (PVDF) hollow fibre membrane for a liquid–gas membrane contactor was coated with a superhydrophobic layer composed of a combination of hydrophobic SiO2 nanoparticles and polydimethylsiloxane (PDMS) by the method of spray deposition. A rough layer of SiO2 deposited on the PVDF membrane resulted in an enhanced surface hydrophobicity. The surface structure of the pristine PVDF significantly affected the homogeneity of the generated SiO2 layer. A uniform surface coating on the PVDF upper layer resulted from the presence of micrometre and nanometre-sized roughness on the surface of the PVDF membrane, which was achieved with a SiO2 concentration of 4.44 mg ml−1 (0.2 g/45 ml) in the coating solution. As a result, the water contact angle of the modified surface was recorded as 155 ± 3°, which is higher than that of the pristine surface. The high contact angle is advantageous for reducing the wetting of the membrane. Additional mass transfer resistance was introduced by the superhydrophobic layer. In addition, continuous CO2 absorption tests were carried out in original and modified PVDF hollow fibre membrane contactors, using monoethanolamine (MEA) solution as the absorbent. A long-term stability test revealed that the modified PVDF hollow fibre membrane contactor was able to outperform the original membrane contactor and demonstrated outstanding long-term stability, suggesting that spray deposition is a promising approach to obtain superhydrophobic PVDF membranes for liquid–gas membrane absorption. PMID:29291117

Localization and reactivity of a hydrophobic solute in lecithin and caseinate stabilized solid lipid nanoparticles and nanoemulsions.

PubMed

Yucel, Umut; Elias, Ryan J; Coupland, John N

2013-03-15

The distribution and reactivity of the lipophilic spin probe 4-phenyl-2,2,5,5-tetramethyl-3-imidazoline-1-oxyl nitroxide (PTMIO) in tetradecane (C14)- and eicosane (C20)-in-water emulsions and solid lipid nanoparticles (SLN) respectively, were investigated by electron paramagnetic resonance (EPR) spectroscopy. The lipid phase (10 wt% C14 or C20) was emulsified into either caseinate solutions (1 wt%) or lecithin+bile salt dispersions (2.4 wt%+0.6 wt%) at 70-75 °C. In C14 emulsions stabilized with lecithin+bile salt, three populations of PTMIO were observed: a population in the lipid phase (~60%, a(N)~13.9 G), an aqueous phase population (~20%, a(N)~15.4 G) with high mobility, and an immobilized surface layer population (~20%, a(N)~14.2 G) with low mobility. However, in C14 emulsions stabilized by caseinate, only two distinct populations of PTMIO were seen: a lipid phase population (~70%, a(N)~13.8 G) and an aqueous phase population (~30%, a(N)~15.5 G) with high mobility. In C20 SLN stabilized with either lecithin+bile salt or caseinate, PTMIO was excluded from the lipid phase. In lecithin+bile salt-stabilized C20 SLN, the majority of the probe (~77%) was in the interfacial layer. For both surfactant systems the rate of PTMIO reduction by aqueous iron/ascorbate was greater for C20 SLN than C14 emulsions. Lecithin affects the properties of emulsions and SLN as delivery systems by providing a distinct environment for small molecules. Copyright © 2013 Elsevier Inc. All rights reserved.

Examining Differences in Arctic and Antarctic Sea Ice Change

NASA Astrophysics Data System (ADS)

Nghiem, S. V.; Rigor, I. G.; Clemente-Colon, P.; Neumann, G.; Li, P.

2015-12-01

The paradox of the rapid reduction of Arctic sea ice versus the stability (or slight increase) of Antarctic sea ice remains a challenge in the cryospheric science research community. Here we start by reviewing a number of explanations that have been suggested by different researchers and authors. One suggestion is that stratospheric ozone depletion may affect atmospheric circulation and wind patterns such as the Southern Annular Mode, and thereby sustaining the Antarctic sea ice cover. The reduction of salinity and density in the near-surface layer may weaken the convective mixing of cold and warmer waters, and thus maintaining regions of no warming around the Antarctic. A decrease in sea ice growth may reduce salt rejection and upper-ocean density to enhance thermohalocline stratification, and thus supporting Antarctic sea ice production. Melt water from Antarctic ice shelves collects in a cool and fresh surface layer to shield the surface ocean from the warmer deeper waters, and thus leading to an expansion of Antarctic sea ice. Also, wind effects may positively contribute to Antarctic sea ice growth. Moreover, Antarctica lacks of additional heat sources such as warm river discharge to melt sea ice as opposed to the case in the Arctic. Despite of these suggested explanations, factors that can consistently and persistently maintains the stability of sea ice still need to be identified for the Antarctic, which are opposed to factors that help accelerate sea ice loss in the Arctic. In this respect, using decadal observations from multiple satellite datasets, we examine differences in sea ice properties and distributions, together with dynamic and thermodynamic processes and interactions with land, ocean, and atmosphere, causing differences in Arctic and Antarctic sea ice change to contribute to resolving the Arctic-Antarctic sea ice paradox.

Quantifying the Impact of Background Atmospheric Stability on Air-Ice-Ocean Interactions the Arctic Ocean During the Fall Freeze-Up

NASA Astrophysics Data System (ADS)

Guest, P. S.; Persson, O. P. G.; Blomquist, B.; Fairall, C. W.

2016-02-01

"Background" stability refers to the effect of vertical virtual temperature variations above the surface layer on fluxes within the surface layer. This is different from the classical surface layer stability quantified by the Obhukhov length scale. In most locations, changes in the background stability do not have a significant direct impact on surface fluxes. However in polar regions, where there is usually a strong low-level temperature inversion capping the boundary layer, changes in background stability can have big impacts on surface fluxes. Therefore, in the Arctic, there is potential for a positive feedback effect between ice cover and surface wind speed (and momentum flux) due to the background stability effects. As the surface becomes more ice free, heat fluxes from the surface weaken the temperature inversion which in turn increases the surface wind speed which further increases the surface turbulent heat fluxes and removes more sea ice by melting or advection. It is not clear how important feedbacks involving the background stability are during the fall freeze up of the Arctic Ocean; that will be the focus of this study. As part of an ONR-sponsored cruise in the fall of 2015 to examine sea state and boundary layer processes in the Beaufort Sea on the R/V Sikuliaq, the authors will perform a variety of surface layer and upper level atmospheric measurements of temperature, humidity and wind vector using ship platform instruments, radiosonde weather balloons, tethered balloons, kites, and miniature quad-rotor unmanned aerial vehicles. In addition, the authors will deploy a full suite of turbulent and radiational flux measurements from the vessel. These measurements will be used to quantify the impact of changing surface conditions on atmospheric structure and vice-versa. The goal is to directly observe how the surface and atmosphere above the surface layer interact and feedback with each other through radiational and turbulent fluxes.

Mechanism of aquaporin-4's fast and highly selective water conduction and proton exclusion.

PubMed

Tani, Kazutoshi; Mitsuma, Tadanori; Hiroaki, Yoko; Kamegawa, Akiko; Nishikawa, Kouki; Tanimura, Yukihiro; Fujiyoshi, Yoshinori

2009-06-19

Members of the aquaporin (AQP) family are expressed in almost every organism, including 13 homologues in humans. Based on the electron crystallographic structure of AQP1, the hydrogen-bond isolation mechanism was proposed to explain why AQPs are impermeable to protons despite their very fast water conduction. The mechanism by which AQPs exclude protons remained controversial, however. Here we present the structure of AQP4 at 2.8 A resolution obtained by electron crystallography of double-layered two-dimensional crystals. The resolution has been improved from the previous 3.2 A, with accompanying improvement in data quality resulting in the ability to identify individual water molecules. Our structure of AQP4, the predominant water channel in the brain, reveals eight water molecules in the channel. The arrangement of the waters provides support for the hydrogen-bond isolation mechanism. Our AQP4 structure also visualizes five lipids, showing that direct interactions of the extracellular surface of AQP4 with three lipids in the adjoining membrane help stabilize the membrane junction.

The Interface Between Chemical and Oxide Materials in the DSPEC

NASA Astrophysics Data System (ADS)

Meyer, Thomas; Alibabaei, Leila; Sherman, Benjamin; Sheridan, Matthew; Ashford, Dennis; Lapides, Alex; Brennaman, Kyle; Nayak, Animesh; Roy, Subhangi

Significant challenges exist for both chemical and oxide materials in the Dye Sensitized Photoelectrosynthesis Cell (DSPEC) for water oxidation or CO2 reduction. They arise from light absorption, the energetics of electron or hole injection, the accumulation of multiple redox equivalents at catalysts for water oxidation or water/CO2 reduction in competition with back electron transfer, and sustained, long term performance. These challenges are being met by the use of a variety of chromophores (metal complexes, organic dyes, porphyrins), broad application of nanoparticle mesoscopic oxide films, atomic layer deposition (ALD) to prepare core/shell and stabilizing overlayer structures, and recent advances in the molecular catalysis of water oxidation and CO2 reduction. UNC EFRC Center for Solar Fuels, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001011.

Low-noise humidity controller for imaging water mediated processes in atomic force microscopy

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

Gaponenko, I., E-mail: iaroslav.gaponenko@unige.ch; Gamperle, L.; Herberg, K.

2016-06-15

We demonstrate the construction of a novel low-noise continuous flow humidity controller and its integration with a commercial variable-temperature atomic force microscope fluid cell, allowing precise control of humidity and temperature at the sample during nanoscale measurements. Based on wet and dry gas mixing, the design allows a high mechanical stability to be achieved by means of an ultrasonic atomiser for the generation of water-saturated gas, improving upon previous bubbler-based architectures. Water content in the flow is measured both at the inflow and outflow of the fluid cell, enabling the monitoring of water condensation and icing, and allowing controlled variationmore » of the sample temperature independently of the humidity. To benchmark the performance of the controller, the results of detailed noise studies and time-based imaging of the formation of ice layers on highly oriented pyrolytic graphite are shown.« less

Sensitivity of boundary-layer stability to base-state distortions at high Mach numbers

NASA Astrophysics Data System (ADS)

Park, Junho; Zaki, Tamer

2017-11-01

The stability diagram of high-speed boundary layers has been established by evaluating the linear instability modes of the similarity profile, over wide ranges of Reynolds and Mach numbers. In real flows, however, the base state can deviate from the similarity profile. Both the base velocity and temperature can be distorted, for example due to roughness and thermal wall treatments. We review the stability problem of high-speed boundary layer, and derive a new formulation of the sensitivity to base-state distortion using forward and adjoint parabolized stability equations. The new formulation provides qualitative and quantitative interpretations on change in growth rate due to modifications of mean-flow and mean-temperature in heated high-speed boundary layers, and establishes the foundation for future control strategies. This work has been funded by the Air Force Office of Scientific Research (AFOSR) Grant: FA9550-16-1-0103.

[Abnormal of tear lipid layer and recent advances in clinical study of dry eye].

PubMed

Xiao, Xin-Ye; Liu, Zu-Guo

2012-03-01

Dry eye is a common disease in the ophthalmological clinic, which is related to the dysfunction of tear film. The tear film is composed of lipid layer, aqueous layer and mucin layer (or lipid layer, aqueous/mucin layer). The lipid of the outmost layer derived from Meibomian gland and distributed on the tear film after blinking can decrease the evaporation and stabilize the tear film. The thickness, quality, and distribution of lipid layer are impaired in many dry eye patients, hence restoring the physiological function of lipid layer may be crucial for the treatment of this kind of dry eye. The lipid artificial tears manifest great effects on increasing lipid layer thickness, stabilizing tear film, improving Meibomian gland dysfunction, and promoting tear film distribution.

Hydrological Effects of Recent Wildfires in the Southern Appalachian Mountains

NASA Astrophysics Data System (ADS)

Chen, J.; Stewart, R. D.

2017-12-01

In 2016, intense wildfires occurred throughout the southern Appalachian Mountains region due to severe drought conditions and high fuel loads. Most previous work on the effects of forest wildfire has concentrated on the western United States, and has shown that wildfires can induce a number of physical, chemical and biological changes in soils, including creating water repellency (hydrophobicity), altering color, decreasing structural stability, and altering nutrient availability. Drought intensity and wildfire activity are both predicted to increase in the southeastern United States, making it important to understand hydrological effects of wildfire in the forests of this region. In this study, we evaluated the effect of wildfire on soil hydrophobicity and soil water storage in two locations: Mount Pleasant Wildlife Refuge, Virginia, and Chimney Rock State Park, North Carolina. In each location unburned, moderately burned, and heavily burned sites were selected. Soil hydrophobicity was measured both in the field using water drop penetration time method at 0 cm, 2 cm, and 5 cm depth, and in the lab using WDPT method and water-solid contact angle method. Soil water content and unsaturated infiltration processes were also measured in the field using mini-disk infiltrometers. The results showed that hydrophobicity was detected after wildfires in both southeastern forests: the Mount Pleasant site had the highest hydrophobic layer in surface layer, while the Chimney Rock site had highest hydrophobicity at the 2 cm depth. Lab results were in accordance with the field results, and in both cases hysteresis between hydrophobicity and soil water content was observed. Burned soils had consistently lower soil water contents than unburned soils. The burned soils in the Mount Pleasant site had lower infiltration rates than the unburned sites, whereas in the Chimney Rock site the burned soils had higher infiltration rates. We hypothesize that the differences between the two sites may be related to the positions of hydrophobic layers in each (i.e., surface versus subsurface). Altogether, these results highlight the hydrological impacts of unprecedented wildfire activity in the southern Appalachians.

Activity and conformation of lysozyme in molecular solvents, protic ionic liquids (PILs) and salt-water systems.

PubMed

Wijaya, Emmy C; Separovic, Frances; Drummond, Calum J; Greaves, Tamar L

2016-09-21

Improving protein stabilisation is important for the further development of many applications in the pharmaceutical, specialty chemical, consumer product and agricultural sectors. However, protein stabilization is highly dependent on the solvent environment and, hence, it is very complex to tailor protein-solvent combinations for stable protein maintenance. Understanding solvent features that govern protein stabilization will enable selection or design of suitable media with favourable solution environments to retain protein native conformation. In this work the structural conformation and activity of lysozyme in 29 solvent systems were investigated to determine the role of various solvent features on the stability of the enzyme. The solvent systems consisted of 19 low molecular weight polar solvents and 4 protic ionic liquids (PILs), both at different water content levels, and 6 aqueous salt solutions. Small angle X-ray scattering, Fourier transform infrared spectroscopy and UV-vis spectroscopy were used to investigate the tertiary and secondary structure of lysozyme along with the corresponding activity in various solvation systems. At low non-aqueous solvent concentrations (high water content), the presence of solvents and salts generally maintained lysozyme in its native structure and enhanced its activity. Due to the presence of a net surface charge on lysozyme, electrostatic interactions in PIL-water systems and salt solutions enhanced lysozyme activity more than the specific hydrogen-bond interactions present in non-ionic molecular solvents. At higher solvent concentrations (lower water content), solvents with a propensity to exhibit the solvophobic effect, analogous to the hydrophobic effect in water, retained lysozyme native conformation and activity. This solvophobic effect was observed particularly for solvents which contained hydroxyl moieties. Preferential solvophobic effects along with bulky chemical structures were postulated to result in less competition with water at the specific hydration layer around the protein, thus reducing protein-solvent interactions and retaining lysozyme's native conformation. The structure-property links established in this study are considered to be applicable to other proteins.

Enhancement of switching stability of tunneling magnetoresistance system with artificial ferrimagnet

NASA Astrophysics Data System (ADS)

You, Chun-Yeol; Bader, Sam. D.; Scheinfein, M. R.

2002-03-01

In the study of spin dependent magnetic tunneling junctions, the switching stability of the magnetically hard layer is a crucial issue in magnetic random access memory applications[1]. After repeated cycling of the soft layer, the magnetization of the hard layer is demagnetized by the stray field from the domain wall created during the switching[2]. The magnitude of the stray field from the soft layer is large enough to switch a domain in the hard layer. Therefore, reducing this stray field is necessary to increase the switching stability. In this study, we explore an artificial ferrimagnet to replace the usual soft layer in order to reduce stray field. The ferrimagnet consists of an antiferromagnetically coupled trilayer that has two ferromagnetic layers of unequal thickness and opposite magnetization orientation. Since the sign of stray field of the two ferromagnetic layers is opposed, the total stray field is greatly reduced. [Supported by the US DOE, BES-MS, under Contract W-31-109-ENG-38.] [1] S. Gider et al. Science 281, 797 (1998). [2] L. Thomas et al. Phys. Rev. Lett. 84, 1816 (2000).

Diaminoethane adsorption and water substitution on hydrated TiO2: a thermochemical study based on first-principles calculations.

PubMed

Hémeryck, Anne; Motta, Alessandro; Swiatowska, Jolanta; Pereira-Nabais, Catarina; Marcus, Philippe; Costa, Dominique

2013-07-14

Epoxy-amines are used as structural adhesives deposited on Ti. The amine adhesion to a Ti surface depends highly on the surface state (oxidation, hydroxylation). Amines may adsorb above preadsorbed water molecules or substitute them to bind directly to surface Ti(4+) Lewis acid sites. The adsorption of a model amine molecule, diaminoethane (DAE), on a model surface, hydrated TiO2-anatase (101) surface, is investigated using Density Functional Theory including Dispersive forces (DFT-D) calculations. DAE adsorption and water substitution by DAE are exothermic processes and turn nearly isoenergetic at high coverage with adsorption-substitution energies around -0.3 eV (including dispersion forces and ZPE). Complementary ab initio molecular dynamics studies also suggest that the formation of an amine-water interaction induces water desorption from the surface at room temperature, a preliminary step towards the amine-Ti bond formation. An atomistic thermodynamic approach is developed to evaluate the interfacial free energy balance of both processes (adsorption and substitution). The main contributions to the energetic balance are dispersive interactions between molecules and the surface on the exergonic side, translational and rotational entropic contributions on the endergonic one. The substitution process is stabilized by 0.55 eV versus the adsorption one when free solvation, rotational and vibrational energies are considered. The main contribution to this free energy gain is due to water solvation. The calculations suggest that in toluene solvent with a water concentration of 10(-4) M or less, a full DAE layer replaces a preadsorbed water layer for a threshold concentration of DAE ≥ 0.1 M.

Hypersonic Boundary Layer Stability Experiments in a Quiet Wind Tunnel with Bluntness Effects

NASA Technical Reports Server (NTRS)

Lachowicz, Jason T.; Chokani, Ndaona

1996-01-01

Hypersonic boundary layer measurements over a flared cone were conducted in a Mach 6 quiet wind tunnel at a freestream unit Reynolds number of 2.82 million/ft. This Reynolds number provided laminar-to-transitional flow over the cone model in a low-disturbance environment. Four interchangeable nose-tips, including a sharp-tip, were tested. Point measurements with a single hot-wire using a novel constant voltage anemometer were used to measure the boundary layer disturbances. Surface temperature and schlieren measurements were also conducted to characterize the transitional state of the boundary layer and to identify instability modes. Results suggest that second mode disturbances were the most unstable and scaled with the boundary layer thickness. The second mode integrated growth rates compared well with linear stability theory in the linear stability regime. The second mode is responsible for transition onset despite the existence of a second mode subharmonic. The subharmonic disturbance wavelength also scales with the boundary layer thickness. Furthermore, the existence of higher harmonics of the fundamental suggests that nonlinear disturbances are not associated with 'high' free stream disturbance levels. Nose-tip radii greater than 2.7% of the base radius completely stabilized the second mode.

Stability of high-speed boundary layers in oxygen including chemical non-equilibrium effects

NASA Astrophysics Data System (ADS)

Klentzman, Jill; Tumin, Anatoli

2013-11-01

The stability of high-speed boundary layers in chemical non-equilibrium is examined. A parametric study varying the edge temperature and the wall conditions is conducted for boundary layers in oxygen. The edge Mach number and enthalpy ranges considered are relevant to the flight conditions of reusable hypersonic cruise vehicles. Both viscous and inviscid stability formulations are used and the results compared to gain insight into the effects of viscosity and thermal conductivity on the stability. It is found that viscous effects have a strong impact on the temperature and mass fraction perturbations in the critical layer and in the viscous sublayer near the wall. Outside of these areas, the perturbations closely match in the viscous and inviscid models. The impact of chemical non-equilibrium on the stability is investigated by analyzing the effects of the chemical source term in the stability equations. The chemical source term is found to influence the growth rate of the second Mack mode instability but not have much of an effect on the mass fraction eigenfunction for the flow parameters considered. This work was supported by the AFOSR/NASA/National Center for Hypersonic Laminar-Turbulent Transition Research.

Boundary Layer Observations of Water Vapor and Aerosol Profiles with an Eye-Safe Micro-Pulse Differential Absorption Lidar (DIAL)

NASA Astrophysics Data System (ADS)

Nehrir, A. R.; Repasky, K. S.; Carlsten, J.; Ismail, S.

2011-12-01

Measurements of real-time high spatial and temporal resolution profiles of combined water vapor and aerosols in the boundary layer have been a long standing observational challenge to the meteorological, weather forecasting, and climate science communities. To overcome the high reoccurring costs associated with radiosondes as well as the lack of sufficient water vapor measurements over the continental united states, a compact and low cost eye-safe all semiconductor-based micro-pulse differential absorption lidar (DIAL) has been developed for water vapor and aerosol profiling in the lower troposphere. The laser transmitter utilizes two continuous wave external cavity diode lasers operating in the 830 nm absorption band as the online and offline seed laser sources. An optical switch is used to sequentially injection seed a tapered semiconductor optical amplifier (TSOA) with the two seed laser sources in a master oscillator power amplifier (MOPA) configuration. The TSOA is actively current pulsed to produce up to 7 μJ of output energy over a 1 μs pulse duration (150 m vertical resolution) at a 10 kHz pulse repetition frequency. The measured laser transmitter spectral linewidth is less than 500 kHz while the long term frequency stability of the stabilized on-line wavelength is ± 55 MHz. The laser transmitter spectral purity was measured to be greater than 0.9996, allowing for simultaneous measurements of water vapor in the lower and upper troposphere. The DIAL receiver utilizes a commercially available full sky-scanning capable 35 cm Schmidt-Cassegrain telescope to collect the scattered light from the laser transmitter. Light collected by the telescope is spectrally filtered to suppress background noise and is coupled into a fiber optic cable which acts as the system field stop and limits the full angle field of view to 140 μrad. The light is sampled by a fiber coupled APD operated in a Geiger mode. The DIAL instrument is operated autonomously where water vapor and aerosol profiles are displayed in real-time. The transmitter is capable of operating at any spectral position along the selected water vapor absorption line allowing for year round operation at various geographical locations using a single line. Water vapor and aerosol profiles have been recorded up to 6 km and 15 km with 10 m and 1 m temporal averaging, respectively, allowing for mesoscale monitoring of boundary layer dynamics during both daytime and nighttime operation. A brief description of the current status of the water vapor DIAL instrument will be presented. Nighttime and daytime water vapor and aerosol profiles/inversions from the DIAL instrument will also be presented and favorable comparisons against collocated radiosonde, in situ, and column averaged data from SUOMINET and AERONET will also be discussed. A future outlook towards instrument enhancements that will allow the diode-laser-based DIAL technique/technology to become a viable candidate for deployment in multi-point sensor networks will also be discussed.

Characterization of Platinum and Iridium Oxyhydrate Surface Layers from Platinum and Iridium Foils.

PubMed

Johnson, Benjamin; Ranjan, Chinmoy; Greiner, Mark; Arrigo, Rosa; Schuster, Manfred Erwin; Höpfner, Britta; Gorgoi, Mihaela; Lauermann, Iver; Willinger, Marc; Knop-Gericke, Axel; Schlögl, Robert

2016-07-07

Platinum and iridium polycrystalline foils were oxidized electrochemically through anodization to create thin platinum and iridium hydrous oxide layers, which were analyzed through laboratory photoelectron spectroscopy during heating and time series (temperature-programmed spectroscopy). The films contain oxygen in the form of bound oxides, water, and hydroxides and were investigated by depth profiling with high-energy photoelectron spectroscopy. The Pt films are unstable and begin to degrade immediately after removal from the electrolyte to form core-shell structures with a metallic inner core and a hydrous oxide outer shell almost devoid of Pt. However, evidence was found for metastable intermediate states of degradation; therefore, it may be possible to manufacture PtOx phases with increased stability. Heating the film to even 100 °C causes accelerated degradation, which shows that stoichiometric oxides such as PtO2 or PtO are not the active species in the electrolyte. The Ir films exhibit increased stability and higher surface Ir content, and gentle heating at low temperatures leads to a decrease in defect density. Although both layers are based on noble metals, their surface structures are markedly different. The complexity of such hydrous oxide systems is discussed in detail with the goal of identifying the film composition more precisely. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Integrating AgI/AgBr biphasic heterostructures encased by few layer h-BN with enhanced catalytic activity and stability.

PubMed

Wu, Wen; Lv, Xiaomeng; Wang, Jiaxi; Xie, Jimin

2017-06-15

Using freshly prepared water-soluble KBr crystal as facile, low-cost sacrificial template, AgBr nanocubes were synthesized through one-pot precipitation method, then navy bean shaped AgI/AgBr biphasic heterostructures were synthesized through anion-exchange reaction and encased within few-layer h-BN to obtain final product. The obtained heterostructured AgI/AgBr/h-BN composite without plasmonic noble metal nanoparticles was used as stable and high active photocatalyst for dye degradation under visible light irradiation, comparing both with self-prepared normal AgBr, AgBr cubes, AgI/AgBr navy beans and other related catalysts reported in the literature. The significant boosting of activity was attributed to the formation of AgI/AgBr interface and the coupling of few-layer h-BN, the latter of which not only effectively suppresses the reduction of silver ions but greatly enhance the charge separation. Furthermore, it was suggested that the photogenerated holes and superoxide radical were the main active species according to photoelectron chemical measurements, electron spin resonance spin-trap analysis and radical trapping experiments. Finally, the possible mechanism of enhanced photocatalytic activity and stability was discussed and proposed. The work demonstrates that engineering Ag-based semiconductor coupling with h-BN would profit the design strategy for low-cost, solar-driven photocatalysts. Copyright © 2017 Elsevier Inc. All rights reserved.

Use of Bacteria To Stabilize Archaeological Iron

PubMed Central

Comensoli, Lucrezia; Maillard, Julien; Albini, Monica; Sandoz, Frederic

2017-01-01

ABSTRACT Iron artifacts are common among the findings of archaeological excavations. The corrosion layer formed on these objects requires stabilization after their recovery, without which the destruction of the item due to physicochemical damage is likely. Current technologies for stabilizing the corrosion layer are lengthy and generate hazardous waste products. Therefore, there is a pressing need for an alternative method for stabilizing the corrosion layer on iron objects. The aim of this study was to evaluate an alternative conservation-restoration method using bacteria. For this, anaerobic iron reduction leading to the formation of stable iron minerals in the presence of chlorine was investigated for two strains of Desulfitobacterium hafniense (strains TCE1 and LBE). Iron reduction was observed for soluble Fe(III) phases as well as for akaganeite, the most troublesome iron compound in the corrosion layer of archaeological iron objects. In terms of biogenic mineral production, differential efficiencies were observed in assays performed on corroded iron coupons. Strain TCE1 produced a homogeneous layer of vivianite covering 80% of the corroded surface, while on the coupons treated with strain LBE, only 10% of the surface was covered by the same mineral. Finally, an attempt to reduce iron on archaeological objects was performed with strain TCE1, which led to the formation of both biogenic vivianite and magnetite on the surface of the artifacts. These results demonstrate the potential of this biological treatment for stabilizing archaeological iron as a promising alternative to traditional conservation-restoration methods. IMPORTANCE Since the Iron Age, iron has been a fundamental material for the building of objects used in everyday life. However, due to its reactivity, iron can be easily corroded, and the physical stability of the object built is at risk. This is particularly true for archaeological objects on which a potentially unstable corrosion layer is formed during the time the object is buried. After excavation, changes in environmental conditions (e.g., higher oxygen concentration or lower humidity) alter the stability of the corrosion layer and can lead to the total destruction of the object. In this study, we demonstrate the feasibility of an innovative treatment based on bacterial iron reduction and biogenic mineral formation to stabilize the corrosion layer and protect these objects. PMID:28283522

Magnetite solubility and phase stability in alkaline media at elevated temperatures

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

Ziemniak, S.E.; Jones, M.E.; Combs, K.E.S.

Magnetite, Fe{sub 3}O{sub 4}, is the dominant oxide constituent of the indigenous corrosion layers that form on iron base alloys in high purity, high temperature water. The apparent simultaneous stability of two distinct oxidation states of iron in this metal oxide is responsible for its unique solubility behavior. The present work was undertaken to extend the experimental and theoretical bases for estimating solubilities of an iron corrosion product (Fe{sub 3}O{sub 4}/Fe(OH){sub 2}) over a broader temperature range and in the presence of complexing, pH-controlling reagents. These results indicate that a surface layer of ferrous hydroxide controls magnetite solubility behavior atmore » low temperatures in much the same manner as a surface layer of nickel(II) hydroxide was previously reported to control the low temperature solubility behavior of NiO. The importance of Fe(III) ion complexes implies not only that most previously-derived thermodynamic properties of the Fe(OH){sub 3}{sup {minus}} ion are incorrect, but that magnetite phase stability probably shifts to favor a sodium ferric hydroxyphosphate compound in alkaline sodium phosphate solutions at elevated temperatures. The test methodology involved pumping alkaline solutions of known composition through a bed of Fe{sub 3}O{sub 4} granules and analyzing the emerging solution for Fe. Two pH-controlling reagents were tested: sodium phosphate and ammonia. Equilibria for the following reactions were described in thermodynamic terms: (a) Fe(OH){sub 2}/Fe{sub 3}O{sub 4} dissolution and transformation, (b) Fe(II) and Fe(III) ion hydroxocomplex formation (hydrolysis), (c) Fe(II) ion amminocomplex formation, and (d) Fe(II) and Fe(III) ion phosphatocomplex formation. 36 refs.« less

Potential role of surface wettability on the long-term stability of dentin bonds after surface biomodification

PubMed Central

Leme, Ariene A.; Vidal, Cristina M. P.; Hassan, Lina Saleh; Bedran-Russo, Ana K.

2015-01-01

Degradation of the adhesive interface contributes to the failure of resin composite restorations. The hydrophilicity of the dentin matrix during and after bonding procedures may result in an adhesive interface that is more prone to degradation over time. This study assessed the effect of chemical modification of dentin matrix on the wettability and the long-term reduced modulus of elasticity (Er) of the adhesive interfaces. Human molars were divided into groups according to the priming solutions: distilled water (control), 6.5% Proanthocyanidin-rich grape seed extract (PACs), 5.75% 1-ethyl-3-[3-dimethylaminopropyl] carbodiimide hydrochloride/1.4% n-hydroxysuccinimide (EDC/NHS) and 5% Glutaraldehyde (GA). The water-surface contact angle was verified before and after chemical modification of the dentin matrix. The demineralized dentin surface was treated with the priming solutions and restored with One Step Plus (OS) and Single Bond Plus (SB) and resin composite. The Er of the adhesive, hybrid layer and underlying dentin was evaluated after 24 h and 30 months in artificial saliva. The dentin hydrophilicity significantly decreased after application of the priming solutions. Aging significantly decreased the Er in the hybrid layer and underlying dentin of control groups. The Er of GA groups remained stable over time at the hybrid layer and underlying dentin. Significant higher Er was observed for PACs and EDC/NHS groups at the hybrid layer after 24 h. The decreased hydrophilicity of the modified dentin matrix likely influence the immediate mechanical properties of the hybrid layer. Dentin biomodification prevented substantial aging at the hybrid layer and underlying dentin after 30 months storage. PMID:25869721

Stability results for multi-layer radial Hele-Shaw and porous media flows

NASA Astrophysics Data System (ADS)

Gin, Craig; Daripa, Prabir

2015-01-01

Motivated by stability problems arising in the context of chemical enhanced oil recovery, we perform linear stability analysis of Hele-Shaw and porous media flows in radial geometry involving an arbitrary number of immiscible fluids. Key stability results obtained and their relevance to the stabilization of fingering instability are discussed. Some of the key results, among many others, are (i) absolute upper bounds on the growth rate in terms of the problem data; (ii) validation of these upper bound results against exact computation for the case of three-layer flows; (iii) stability enhancing injection policies; (iv) asymptotic limits that reduce these radial flow results to similar results for rectilinear flows; and (v) the stabilizing effect of curvature of the interfaces. Multi-layer radial flows have been found to have the following additional distinguishing features in comparison to rectilinear flows: (i) very long waves, some of which can be physically meaningful, are stable; and (ii) eigenvalues can be complex for some waves depending on the problem data, implying that the dispersion curves for one or more waves can contact each other. Similar to the rectilinear case, these results can be useful in providing insight into the interfacial instability transfer mechanism as the problem data are varied. Moreover, these can be useful in devising smart injection policies as well as controlling the complexity of the long-term dynamics when drops of various immiscible fluids intersperse among each other. As an application of the upper bound results, we provide stabilization criteria and design an almost stable multi-layer system by adding many layers of fluid with small positive jumps in viscosity in the direction of the basic flow.

A quantum mechanical study of water adsorption on the (110) surfaces of rutile SnO₂ and TiO₂: investigating the effects of intermolecular interactions using hybrid-exchange density functional theory.

PubMed

Patel, M; Sanches, F F; Mallia, G; Harrison, N M

2014-10-21

Periodic hybrid-exchange density functional theory calculations are used to explore the first layer of water at model oxide surfaces, which is an important step for understanding the photocatalytic reactions involved in solar water splitting. By comparing the structure and properties of SnO2(110) and TiO2(110) surfaces in contact with water, the effects of structural and electronic differences on the water chemistry are examined. The dissociative adsorption mode at low coverage (1/7 ML) up to monolayer coverage (1 ML) on both SnO2 and TiO2(110) surfaces is analysed. To investigate further the intermolecular interactions between adjacent adsorbates, monolayer adsorption on each surface is explored in terms of binding energies and bond lengths. Analysis of the water adsorption geometry and energetics shows that the relative stability of water adsorption on SnO2(110) is governed largely by the strength of the chemisorption and hydrogen bonds at the surface of the adsorbate-substrate system. However on TiO2(110), a more complicated scenario of the first layer of water on its surface arises in which there is an interplay between chemisorption, hydrogen bonding and adsorbate-induced atomic displacements in the surface. Furthermore the projected density of states of each surface in contact with a mixture of adsorbed water molecules and adsorbed hydroxyls is presented and sheds some light on the nature of the crystalline chemical bonds as well as on why adsorbed water has often been reported to be unstable on rutile SnO2(110).

Geomorphic Evidence for Martian Ground Ice and Climate Change

NASA Technical Reports Server (NTRS)

Kanner, L. C.; Allen, C. C.; Bell, M. S.

2004-01-01

Recent results from gamma-ray and neutron spectrometers on Mars Odyssey indicate the presence of a hydrogen-rich layer tens of centimeters thick in the uppermost meter in high latitudes (greater than 60) on Mars. This hydrogen-rich layer correlates to regions of ice stability. Thus, the subsurface hydrogen is thought to be water ice constituting 35 plus or minus 15% by weight near the north and south polar regions. We refine the location of subsurface ice deposits at a less than km scale by combining existing spectroscopy data with surface features indicative of subsurface ice. A positive correlation between spectroscopy data and geomorphic ice indicators has been previously suggested for high latitudes. Here we expand the comparative study to northern mid latitudes (30 degrees N- 65 degrees N).

Printed biotin-functionalised polythiophene films as biorecognition layers in the development of paper-based biosensors

NASA Astrophysics Data System (ADS)

Ihalainen, Petri; Pesonen, Markus; Sund, Pernilla; Viitala, Tapani; Määttänen, Anni; Sarfraz, Jawad; Wilén, Carl-Erik; Österbacka, Ronald; Peltonen, Jouko

2016-02-01

The integration of flexible electronic sensors in clinical diagnostics is visioned to significantly reduce the cost of many diagnostic tests and ultimately make healthcare more accessible. This study concentrates on the characterisation of inkjet-printed bio-functionalised polythiophene films on paper-based ultrathin gold film (UTGF) electrodes and their possible application as biorecognition layers. Physicochemical surface properties (topography, chemistry, and wetting) and electrochemical characteristics of water-soluble regioirregular tetraethylene-glycol polythiophene (TEGPT) and biotin-functionalised TEGPT (b-TEGPT) films were examined and compared. In addition, their specificity towards streptavidin protein was tested. The results show that stable supramolecular biorecognition layers of insulating b-TEGPT and streptavidin were successfully fabricated on a paper-based UTGF by inkjet-printing. Good adhesion of thiophene to UTGF can be attributed to covalent linkage between sulphur and gold, whereas the stability of the streptavidin layer is due to the high affinity between biotin and streptavidin. The device introduced can be utilised in the development of biosensors for clinically relevant analytes e.g. for detecting complementary DNA oligomers or antibody-antigen complexes.

Origin of Shear Stability and Compressive Ductility Enhancement of Metallic Glasses by Metal Coating

PubMed Central

Sun, B. A.; Chen, S. H.; Lu, Y. M.; Zhu, Z. G.; Zhao, Y. L.; Yang, Y.; Chan, K. C.; Liu, C. T.

2016-01-01

Metallic glasses (MGs) are notorious for the poor macroscopic ductility and to overcome the weakness various intrinsic and extrinsic strategies have been proposed in past decades. Among them, the metal coating is regarded as a flexible and facile approach, yet the physical origin is poorly understood due to the complex nature of shear banding process. Here, we studied the origin of ductile enhancement in the Cu-coating both experimentally and theoretically. By examining serrated shear events and their stability of MGs, we revealed that the thin coating layer plays a key role in stopping the final catastrophic failure of MGs by slowing down shear band dynamics and thus retarding its attainment to a critical instable state. The mechanical analysis on interplay between the coating layer and shear banding process showed the enhanced shear stability mainly comes from the lateral tension of coating layer induced by the surface shear step and the bonding between the coating layer and MGs rather than the layer thickness is found to play a key role in contributing to the shear stability. PMID:27271435

Novel procedure to enhance PLA surface properties by chitosan irreversible immobilization

NASA Astrophysics Data System (ADS)

Stoleru, Elena; Dumitriu, Raluca Petronela; Munteanu, Bogdanel Silvestru; Zaharescu, Traian; Tănase, Elisabeta Elena; Mitelut, Amalia; Ailiesei, Gabriela-Liliana; Vasile, Cornelia

2016-03-01

A novel two step procedure was applied for poly(lactic acid) (PLA) functionalization consisting in the exposure to cold radiofrequency plasma in nitrogen atmosphere or to gamma irradiation followed by ;grafting to; of a chitosan layer using carbodiimide chemistry. The adhesion and stability of the deposited surface layer was assured by plasma/gamma irradiation treatment while the chitosan layer offers antifungal/antibacterial/antioxidant activities. Chitosan with different viscosities/deacetylation degree was deposited by electrospinning or immersion methods. Correlations between rheological behavior of chitosan solutions and chitosan layer deposition conditions are made. The PLA surface properties were investigated by water contact angle measurements, ATR-FTIR spectroscopy, AFM, chemiluminiscence, etc. It has been established that the surface roughness increases direct proportional with cold plasma duration and gamma irradiation dose and further increases by chitosan coating which at its turn depends on chitosan characteristics (viscosity and deacetylation degree) and method of deposition. Nano-fibers with relatively homogeneous and reproducible features are obtained by electrospinning of highly viscous chitosan while with the other two types of chitosan both microparticles and nano-fibers are formed. The chitosan coating obtained by immersion is more homogenous and compact and has a better antibacterial activity than the electrospun layer as fiber meshes.

Tuning the structure of thermosensitive gold nanoparticle monolayers.

PubMed

Rezende, Camila A; Shan, Jun; Lee, Lay-Theng; Zalczer, Gilbert; Tenhu, Heikki

2009-07-23

Gold nanoparticles grafted with poly(N-isopropylacrylamide) (PNIPAM) are rendered amphiphilic and thermosensitive. When spread on the surface of water, they form stable Langmuir monolayers that exhibit surface plasmon resonance. Using Langmuir balance and contrast-matched neutron reflectivity, the detailed structural properties of these nanocomposite monolayers are revealed. At low surface coverage, the gold nanoparticles are anchored to the interface by an adsorbed PNIPAM layer that forms a thin and compact pancake structure. Upon isothermal compression (T=20 degrees C), the adsorbed layer thickens with partial desorption of polymer chains to form brush structures. Two distinct polymer conformations thus coexist: an adsorbed conformation that assures stability of the monolayer, and brush structures that dangle in the subphase. An increase in temperature to 30 degrees C results in contractions of both adsorbed and brush layers with a concomitant decrease in interparticle distance, indicating vertical as well as lateral contractions of the graft polymer layer. The reversibility of this thermal response is also shown by the contraction-expansion of the polymer layers in heating-cooling cycles. The structure of the monolayer can thus be tuned by compression and reversibly by temperature. These compression and thermally induced conformational changes are discussed in relation to optical properties.

Removal of Cu(II) ions from contaminated waters using a conducting microfiltration membrane.

PubMed

Wang, Xueye; Wang, Zhiwei; Chen, Haiqin; Wu, Zhichao

2017-10-05

Efficient removal of toxic metals using low-pressure membrane processes from contaminated waters is an important but challenging task. In the present work, a conducting microfiltration membrane prepared by embedding a stainless steel mesh in the active layer of a polyvinylidene fluoride membrane is developed to remove Cu(II) ions from contaminated waters. Results showed that the conducting membrane had favorable electrochemical properties and stability as cathode. Batch tests showed that Cu(II) removal efficiency increased with the increase of voltages and leveled off with the further enhancement of electric field. The optimal voltages were determined to be 1.0V and 2.0V for the influent Cu(II) concentrations of 5mg/L and 30mg/L, respectively. X-ray photoelectron spectroscopy and X-ray diffraction results demonstrated the presence of Cu(0) and Cu(OH) 2 on the membrane surface. The removal mechanisms involved the intrinsic adsorption of membrane, electrosorption of membrane, adsorption of deposited layer, chemical precipitation of Cu(OH) 2 and deposition of Cu(0) which were aided by electrophoresis and electrochemical oxidation-reduction. Long-term tests showed that the major contributors for Cu(II) removal were the deposition of Cu(0) by electrochemical reduction-oxidation (47.3%±8.5%) and chemical precipitation (41.1%±0.2%), followed by electrosorption, adsorption by the fouling layer and membrane intrinsic sorption. Copyright © 2017 Elsevier B.V. All rights reserved.

The Prospect of Y2SiO5-Based Materials as Protective Layer in Environmental Barrier Coatings

NASA Astrophysics Data System (ADS)

García, E.; Miranzo, P.; Osendi, M. I.

2013-06-01

Bulk yttrium monosilicate (Y2SiO5) possesses interesting properties, such as low thermal expansion coefficient and stability in water vapor atmospheres, which make it a promising protective layer for SiC-based composites, intended for the hottest parts in the future gas turbines. Because protective layers are commonly applied by thermal spraying techniques, it is important to analyze the changes in structure and properties that these methods may produce in yttrium silicate coatings. In this work, two SiO2-Y2O3 compositions were flame sprayed in the form of coatings and beads. In parallel, the beads were spark plasma sintered at relatively low temperature to obtain partially amorphous bulk specimens that are used as model bulk material. The thermal aging—air and water vapor atmosphere—caused extensive nucleation of Y2SiO5 and Y2Si2O7 in both the bulk and coating. The rich water vapor condition caused the selective volatilization of SiO2 from Y2Si2O7 at the specimen surface leaving a very characteristic micro-ridged Y2SiO5 zones—either in coatings or sintered bodies. An important increase in the thermal conductivity of the aged materials was measured. The results of this work may be used as a reference body for the production of Y2SiO5 coatings using thermal spraying techniques.

Fast dissolution of poorly water soluble drugs from fluidized bed coated nanocomposites: Impact of carrier size.

PubMed

Azad, Mohammad; Moreno, Jacqueline; Bilgili, Ecevit; Davé, Rajesh

2016-11-20

Formation of core-shell nanocomposites of Fenofibrate and Itraconazole, model poorly water soluble drugs, via fluidized bed (FB) coating of their well-stabilized high drug loaded nanosuspensions is investigated. Specifically, the extent of dissolution enhancement, when fine carrier particles (sub-50μm) as opposed to the traditional large carrier particles (>300μm) are used, is examined. This allows testing the hypothesis that greatly increased carrier surface area and more importantly, thinner shell for finer carriers at the same drug loading can significantly increase the dissolution rate when spray-coated nanosuspensions are well-stabilized. Fine sub-50μm lactose (GranuLac ® 200) carrier particles were made fluidizable via dry coating with nano-silica, enabling decreased cohesion, fluidization and subsequent nanosuspension coating. For both drugs, 30% drug loaded suspensions were prepared via wet-stirred media milling using hydroxypropyl methyl cellulose and sodium dodecyl sulfate as stabilizers. The stabilizer concentrations were varied to affect the milled particle size and prepare a stable nanosuspension. The suspensions were FB coated onto hydrophilic nano-silica (M-5P) dry coated sub-50μm lactose (GranuLac ® 200) carrier particles or larger carrier particles of median size >300μm (PrismaLac ® 40). The resulting finer composite powders (sub-100μm) based on GranuLac ® 200 were freely flowing, had high bulk density, and had much faster, immediate dissolution of the poorly water-soluble drugs, in particular for Itraconazole. This is attributed to a much higher specific surface area of the carrier and corresponding thinner coating layer for fine carriers as opposed to those for large carrier particles. Copyright © 2016 Elsevier B.V. All rights reserved.

Relating the variation of secondary structure of gelatin at fish oil-water interface to adsorption kinetics, dynamic interfacial tension and emulsion stability.

PubMed

Liu, Huihua; Wang, Bo; Barrow, Colin J; Adhikari, Benu

2014-01-15

The objectives of this study were to quantify the relationship between secondary structure of gelatin and its adsorption at the fish-oil/water interface and to quantify the implication of the adsorption on the dynamic interfacial tension (DST) and emulsion stability. The surface hydrophobicity of the gelatin solutions decreased when the pH increased from 4.0 to 6.0, while opposite tend was observed in the viscosity of the solution. The DST values decreased as the pH increased from 4.0 to 6.0, indicating that higher positive charges (measured trough zeta potential) in the gelatin solution tended to result in higher DST values. The adsorption kinetics of the gelatin solution was examined through the calculated diffusion coefficients (Deff). The addition of acid promoted the random coil and β-turn structures at the expense of α-helical structure. The addition of NaOH decreased the β-turn and increased the α-helix and random coil. The decrease in the random coil and triple helix structures in the gelatin solution resulted into increased Deff values. The highest diffusion coefficients, the highest emulsion stability and the lowest amount of random coil and triple helix structures were observed at pH=4.8. The lowest amount of random coil and triple helix structures in the interfacial protein layer correlated with the highest stability of the emulsion (highest ESI value). The lower amount of random coil and triple helix structures allowed higher coverage of the oil-water interface by relatively highly ordered secondary structure of gelatin. Copyright © 2013 Elsevier Ltd. All rights reserved.

Nanostructure templating using low temperature atomic layer deposition

DOEpatents

Grubbs, Robert K [Albuquerque, NM; Bogart, Gregory R [Corrales, NM; Rogers, John A [Champaign, IL

2011-12-20

Methods are described for making nanostructures that are mechanically, chemically and thermally stable at desired elevated temperatures, from nanostructure templates having a stability temperature that is less than the desired elevated temperature. The methods comprise depositing by atomic layer deposition (ALD) structural layers that are stable at the desired elevated temperatures, onto a template employing a graded temperature deposition scheme. At least one structural layer is deposited at an initial temperature that is less than or equal to the stability temperature of the template, and subsequent depositions made at incrementally increased deposition temperatures until the desired elevated temperature stability is achieved. Nanostructure templates include three dimensional (3D) polymeric templates having features on the order of 100 nm fabricated by proximity field nanopatterning (PnP) methods.

Delay of Transition Using Forced Damping

NASA Technical Reports Server (NTRS)

Exton, Reginald J.

2014-01-01

Several experiments which have reported a delay of transition are analyzed in terms of the frequencies of the induced disturbances generated by different flow control elements. Two of the experiments employed passive stabilizers in the boundary layer, one leading-edge bluntness, and one employed an active spark discharge in the boundary layer. It is found that the frequencies generated by the various elements lie in the damping region of the associated stability curve. It is concluded that the creation of strong disturbances in the damping region stabilizes the boundary-layer and delays the transition from laminar to turbulent flow.

Charts and Tables for Estimating the Stability of the Compressible Laminar Boundary Layer with Heat Transfer and Arbitrary Pressure Gradient

NASA Technical Reports Server (NTRS)

Tetervin, Neal

1959-01-01

The minimum critical Reynolds numbers for the similar solutions of the compressible laminar boundary layer computed by Cohen and Reshotko and also for the Falkner and Skan solutions as recomputed by Smith have been calculated by Lin's rapid approximate method for two-dimensional disturbances. These results enable the stability of the compressible laminar boundary layer with heat transfer and pressure gradient to be easily estimated after the behavior of the boundary layer has been computed by the approximate method of Cohen and Reshotko. The previously reported unusual result (NACA Technical Note 4037) that a highly cooled stagnation point flow is more unstable than a highly cooled flat-plate flow is again encountered. Moreover, this result is found to be part of the more general result that a favorable pressure gradient is destabilizing for very cool walls when the Mach number is less than that for complete stability. The minimum critical Reynolds numbers for these wall temperature ratios are, however, all larger than any value of the laminar-boundary-layer Reynolds number likely to be encountered. For Mach numbers greater than those for which complete stability occurs a favorable pressure gradient is stabilizing, even for very cool walls.

Foaming and adsorption behavior of bovine and camel proteins mixed layers at the air/water interface.

PubMed

Lajnaf, Roua; Picart-Palmade, Laetitia; Attia, Hamadi; Marchesseau, Sylvie; Ayadi, M A

2017-03-01

The aim of this work was to examine foaming and interfacial behavior of three milk protein mixtures, bovine α-lactalbumin-β-casein (M1), camel α-lactalbumin-β-casein (M2) and β-lactoglobulin-β-casein (M3), alone and in binary mixtures, at the air/water interface in order to better understand the foaming properties of bovine and camel milks. Different mixture ratios (100:0; 75:25; 50:50; 25:75; 0:100) were used during foaming tests and interfacial protein interactions were studied with a pendant drop tensiometer. Experimental results evidenced that the greatest foam was obtained with a higher β-casein amount in all camel and bovine mixtures. Good correlation was observed with the adsorption and the interfacial rheological properties of camel and bovine protein mixtures. The proteins adsorbed layers are mainly affected by the presence of β-casein molecules, which are probably the most abundant protein at interface and the most efficient in reducing the interfacial properties. In contrast of, the globular proteins, α-lactalbumin and β-lactoglobulin that are involved in the protein layer composition, but could not compact well at the interface to ensure foams creation and stabilization because of their rigid molecular structure. Copyright © 2016 Elsevier B.V. All rights reserved.

Lignin-assisted exfoliation of molybdenum disulfide in aqueous media and its application in lithium ion batteries.

PubMed

Liu, Wanshuang; Zhao, Chenyang; Zhou, Rui; Zhou, Dan; Liu, Zhaolin; Lu, Xuehong

2015-06-07

In this article, alkali lignin (AL)-assisted direct exfoliation of MoS2 mineral into single-layer and few-layer nanosheets in water is reported for the first time. Under optimized conditions, the concentration of MoS2 nanosheets in the obtained dispersion can be as high as 1.75 ± 0.08 mg mL(-1), which is much higher than the typical reported concentrations (<1.0 mg mL(-1)) using synthetic polymers or compounds as surfactants. The stabilizing mechanism primarily lies in the electrostatic repulsion between negative charged AL, as suggested by zeta-potential measurements. When the exfoliated MoS2 nanosheets are applied as electrode materials for lithium ion batteries, they show much improved electrochemical performance compared with the pristine MoS2 mineral because of the enhanced ion and electron transfer kinetics. This facile, scalable and eco-friendly aqueous-based process in combination with renewable and ultra-low-cost lignin opens up possibilities for large-scale fabrication of MoS2-based nanocomposites and devices. Moreover, herein we demonstrate that AL is also an excellent surfactant for exfoliation of many other types of layered materials, including graphene, tungsten disulfide and boron nitride, in water, providing rich opportunities for a wider range of applications.

Floating elementary osmotic pump tablet (FEOPT) for controlled delivery of diethylcarbamazine citrate: a water-soluble drug.

PubMed

Khan, Zulfequar Ahamad; Tripathi, Rahul; Mishra, Brahmeshwar

2011-12-01

The present work investigates the feasibility of the design of a novel floating elementary osmotic pump tablet (FEOPT) to prolong the gastric residence of a highly water-soluble drug. Diethylcarbamazine citrate (DEC) was chosen as a model drug. The FEOPT consisted of an osmotic core (DEC, mannitol, and hydrophilic polymers) coated with a semipermeable layer (cellulose acetate) and a gas-generating gelling layer (sodium bicarbonate, hydrophilic polymers) followed by a polymeric film (Eudragit RL 30D). The effect of formulation variables such as concentration of polymers, types of diluent, and coat thickness of semipermeable membrane was evaluated in terms of physical parameters, floating lag time, duration of floatation, and in vitro drug release. The Fourier transform infrared and X-ray diffraction analysis were carried out to study the physicochemical changes in the drug excipients powder blend. The integrity of the orifice and polymeric film layer was confirmed from scanning electron microscopy image. All the developed FEOPT showed floating lag time of less than 8 min and floating duration of 24 h. A zero-order drug release could be attained for DEC. The formulations were found to be stable up to 3 months of stability testing at 40°C/75% relative humidity.

Formation of Soil Water Repellency by Laboratory Burning and Its Effect on Soil Evaporation

NASA Astrophysics Data System (ADS)

Ahn, Sujung; Im, Sangjun

2010-05-01

Fire-induced soil water repellency can vary with burning conditions, and may lead to significant changes in soil hydraulic properties. However, isolation of the effects of soil water repellency from other factors is difficult, particularly under field conditions. This study was conducted to (i) investigate the effects of burning using different plant leaf materials and (ii) of different burning conditions on the formation of soil water repellency, and (iii) isolate the effects of the resulting soil water repellency on soil evaporation from other factors. Burning treatments were performed on the surface of homogeneous fully wettable sand soil contained in a steel frame (60 x 60 cm; 40 cm depth). As controls a sample without a heat treatment, and a heated sample without fuel, were also used. Ignition and heat treatments were carried out with a gas torch. For comparing the effects of different burning conditions, fuel types included oven-dried pine needles (fresh needles of Pinus densiflora), pine needle litter (litter on a coniferous forest floor, P. densiflora + P. rigida), and broad-leaf litter (Quercus mongolica + Q. aliena + Prunus serrulata var. spontanea + other species); fuel loads were 200 g, 300 g, and 500 g; and heating duration was 40 s, 90 s and 180 s. The heating duration was adjusted to control the temperature, based on previous experiments. The temperature was measured continuously at 3-second intervals and logged with two thermometers. After burning, undisturbed soil columns were sampled for subsequent experiments. Water Drop Penetration Time (WDPT) test was performed at every 1 mm depth of the soil columns to measure the severity of soil water repellency and its vertical extent. Soil water repellency was detected following all treatments. As the duration of heating increased, the thickness of the water repellent layer increased, whilst the severity of soil water repellency decreased. As regards fuel amount, the most severe soil water repellency was formed at a fuel load of 300 g. Pine needle litter formed the most severe soil water repellency and fresh pine needle formed the thickest water repellent layer, whilst broad-leaf litter did only cause water repellency on the surface of the sand. The soil evaporation rate was measured by a gravitational method at an isothermal condition. Undisturbed soil columns were sealed after adding 50 ml of tap water through the bottom. After twelve hours of stabilization, the columns were opened and covered with filter paper. The rate of soil evaporation through the soil surface was measured by the hourly weight change at 45° C. The initial 65 hours' evaporation rate was analyzed, while the slope of cumulative evaporation over time maintained its linearity. It was found that as the thickness of the water repellent layer increased, the evaporation rate tended to decrease. These two variables showed a good correlation (Pearson's correlation coefficient =-0.8916, p=0.0170) and a large coefficient of determination (R2=0.795) in the linear regression. This suggests that a layer of water repellent soil can affect water evaporation rate and that the rate is negatively correlated with the thickness of the repellent layer.

Active volcanism beneath the West Antarctic ice sheet and implications for ice-sheet stability

USGS Publications Warehouse

Blankenship, D.D.; Bell, R.E.; Hodge, S.M.; Brozena, J.M.; Behrendt, John C.; Finn, C.A.

1993-01-01

IT is widely understood that the collapse of the West Antarctic ice sheet (WAIS) would cause a global sea level rise of 6 m, yet there continues to be considerable debate about the detailed response of this ice sheet to climate change1-3. Because its bed is grounded well below sea level, the stability of the WAIS may depend on geologically controlled conditions at the base which are independent of climate. In particular, heat supplied to the base of the ice sheet could increase basal melting and thereby trigger ice streaming, by providing the water for a lubricating basal layer of till on which ice streams are thought to slide4,5. Ice streams act to protect the reservoir of slowly moving inland ice from exposure to oceanic degradation, thus enhancing ice-sheet stability. Here we present aerogeophysical evidence for active volcanism and associated elevated heat flow beneath the WAIS near the critical region where ice streaming begins. If this heat flow is indeed controlling ice-stream formation, then penetration of ocean waters inland of the thin hot crust of the active portion of the West Antarctic rift system could lead to the disappearance of ice streams, and possibly trigger a collapse of the inland ice reservoir.

Controlling Microstructure of Yttria-Stabilized Zirconia Prepared from Suspensions and Solutions by Plasma Spraying with High Feed Rates

NASA Astrophysics Data System (ADS)

Musalek, Radek; Medricky, Jan; Tesar, Tomas; Kotlan, Jiri; Pala, Zdenek; Lukac, Frantisek; Illkova, Ksenia; Hlina, Michal; Chraska, Tomas; Sokolowski, Pawel; Curry, Nicholas

2017-12-01

Introduction of suspension and solution plasma spraying led to a breakthrough in the deposition of yttria-stabilized zirconia (YSZ) coatings and enabled preparation of new types of layers. However, their deposition with high feed rates needed, for example, for the deposition of thermal barrier coatings (TBCs) on large-scale components, is still challenging. In this study, possibility of high-throughput plasma spraying of YSZ coatings is demonstrated for the latest generation of high-enthalpy hybrid water-stabilized plasma (WSP-H) torch technology. The results show that microstructure of the coatings prepared by WSP-H may be tailored for specific applications by the choice of deposition conditions, in particular formulation of the liquid feedstock. Porous and columnar coatings with low thermal conductivity (0.5-0.6 W/mK) were prepared from commercial ethanol-based suspension. Dense vertically cracked coatings with higher thermal conductivity but also higher internal cohesion were deposited from suspension containing ethanol/water mixture and coarser YSZ particles. Spraying of solution formulated from diluted zirconium acetate and yttrium nitrate hexahydrate led also to the successful deposition of YSZ coating combining regions of porous and denser microstructure and providing both low thermal conductivity and improved cohesion of the coating. Enthalpy content, liquid-plasma interaction and coating buildup mechanisms are also discussed.

Laser synthesis of aluminium nanoparticles in biocompatible polymer solutions

NASA Astrophysics Data System (ADS)

Singh, Rina; Soni, R. K.

2014-08-01

Pulsed laser ablation of Aluminium (Al) in pure water rapidly forms a thin alumina (Al2O3) layer which drastically modifies surface plasmon resonance (SPR) absorption characteristics in deep-UV region. Initially, pure aluminium nanoparticles (NPs) are generated in water without any stabilizers or surfactants at low laser fluence which gradually transform to stable Al-Al2O3 core-shell nanostructure with increasing either residency time or fluence. The role of laser wavelength and fluence on the SPR properties and oxidation characteristics of Al NPs has been investigated in detail. We also present a one-step in situ synthesis of oxide-free stable Al NPs in biocompatible polymer solutions using laser ablation in liquid method. We have used nonionic polymers (PVP, PVA and PEG) and anionic surfactant (SDS) stabilizer to suppress the Al2O3 formation and studied the effect of polymer functional group, polymeric chain length, polymer concentration and anionic surfactant on the incipient embryonic aluminium particles and their sizes. The different functional groups of polymers resulted in different oxidation states of Al. PVP and PVA polymers resulted in pure Al NPs; however, PEG and SDS resulted in alumina-modified Al NPs. The Al nanoparticles capped with PVP, PVA, and PEG show a good correlation between nanoparticle stability and monomeric length of the polymer chain.

Perovskite Solar Cells for High-Efficiency Tandems

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

McGehee, Michael; Buonassisi, Tonio

The first monolithic perovskite/silicon tandem was made with a diffused silicon p-n junction, a tunnel junction made of n ++ hydrogenated amorphous silicon, a titania electron transport layer, a methylammonium lead iodide absorber, and a Spiro-OMeTAD hole transport layer (HTL). The power conversion efficiency (PCE) was only 13.7% due to excessive parasitic absorption of light in the HTL, limiting the matched current density to 11.5 mA/cm 2. Werner et al. 15 raised the PCE to a record 21.2% by switching to a silicon heterojunction bottom cell and carefully tuning layer thicknesses to achieve lower optical loss and a higher currentmore » density of 15.9 mA/cm 2. It is clear from these reports that minimizing parasitic absorption in the window layers is crucial to achieving higher current densities and efficiencies in monolithic tandems. To this end, the window layers through which light first passes before entering the perovskite and silicon absorber materials must be highly transparent. The front electrode must also be conductive to carry current laterally across the top of the device. Indium tin oxide (ITO) is widely utilized as a transparent electrode in optoelectronic devices such as flat-panel displays, smart windows, organic light-emitting diodes, and solar cells due to its high conductivity and broadband transparency. ITO is typically deposited through magnetron sputtering; however, the high kinetic energy of sputtered particles can damage underlying layers. In perovskite solar cells, a sputter buffer layer is required to protect the perovskite and organic carrier extraction layers from damage during sputter deposition. The ideal buffer layer should also be energetically well aligned so as to act as a carrier-selective contact, have a wide bandgap to enable high optical transmission, and have no reaction with the halides in the perovskite. Additionally, this buffer layer should act as a diffusion barrier layer to prevent both organic cation evolution and moisture penetration to overcome the often-reported thermal and environmental instability of metal halide perovskites. Previous perovskite-containing tandems utilized molybdenum oxide (MoO x) as a sputter buffer layer, but this has raised concerns over long-term stability, as the iodide in the perovskite can chemically react with MoO x. Mixed-cation perovskite solar cells have consistently outperformed their single-cation counterparts. The first perovskite device to exceed 20% PCE was fabricated with a mixture of methylammonium (MA) and formamidinium (FA). Recent reports have shown promising results with the introduction of cesium mixtures, enabling high efficiencies with improved photo-, moisture, and thermal stability. The increased moisture and thermal stability are especially important as they broaden the parameter space for processing on top of the perovskite, enabling the deposition of metal oxide contacts through atomic layer deposition (ALD) or chemical vapor deposition (CVD) that may require elevated temperatures or water as a counter reagent. Both titanium dioxide (TiO 2) and tin oxide (SnO 2) have consistently proven to be effective electron-selective contacts for perovskite solar cells and both can be deposited via ALD at temperatures below 150 °C. We introduced a bilayer of SnO 2 and zinc tin oxide (ZTO) that can be deposited by either low-temperature ALD or pulsed-CVD as a window layer with minimal parasitic absorption, efficient electron extraction, and sufficient buffer properties to prevent the organic and perovskite layers from damage during the subsequent sputter deposition of a transparent ITO electrode. We explored pulsed-CVD as a modified ALD process with a continual, rather than purely step-wise, growth component in order to considerably reduce the process time of the SnO 2 deposition process and minimize potential perovskite degradation. These layers, when used in an excellent mixed-cation perovskite solar cell atop a silicon solar cell tuned to the infrared spectrum, enable highly efficient perovskite-silicon tandem solar cells with enhanced thermal and environmental stability.« less

Boron carbon nitride nanostructures from salt melts: tunable water-soluble phosphors.

PubMed

Lei, Weiwei; Portehault, David; Dimova, Rumiana; Antonietti, Markus

2011-05-11

A simple, high yield, chemical process is developed to fabricate layered h-BN nanosheets and BCNO nanoparticles with a diameter of ca. 5 nm at 700 °C. The use of the eutectic LiCl/KCl salt melt medium enhances the kinetics of the reaction between sodium borohydride and urea or guanidine as well as the dispersion of the nanoparticles in water. The carbon content can be tuned from 0 to 50 mol % by adjusting the reactant ratio, thus providing precise control of the light emission of the particles in the range 440-528 nm while reaching a quantum yield of 26%. Because of their green synthesis, low toxicity, small size, and stability against aggregation in water, the as-obtained photoluminescent BCNO nanoparticles show promise for diagnostics and optoelectronics. © 2011 American Chemical Society

Hydrophilic cobalt sulfide nanosheets as a bifunctional catalyst for oxygen and hydrogen evolution in electrolysis of alkaline aqueous solution.

PubMed

Zhu, Mingchao; Zhang, Zhongyi; Zhang, Hu; Zhang, Hui; Zhang, Xiaodong; Zhang, Lixue; Wang, Shicai

2018-01-01

Hydrophilic medium and precursors were used to synthesize a hydrophilic electro-catalyst for overall water splitting. The cobalt sulfide (Co 3 S 4 ) catalyst exhibits a layered nanosheet structure with a hydrophilic surface, which can facilitate the diffusion of aqueous substrates into the electrode pores and towards the active sites. The Co 3 S 4 catalyst shows excellent bifunctional catalytic activity for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline solution. The assembled water electrolyzer based on Co 3 S 4 exhibits better performance and stability than that of Pt/C-RuO 2 catalyst. Thereforce the hydrophilic Co 3 S 4 is a highly promising bifunctional catalyst for the overall water splitting reaction. Copyright © 2017 Elsevier Inc. All rights reserved.

Thermomechanical behavior of mica layers with lenticular fissures

NASA Astrophysics Data System (ADS)

Yang, Michael Xinyi

The thermomechanical behavior of natural phlogopite mica specimens from seven different origins is characterized. An initial heat treatment, to a temperature between 300°C and 400°C, is found to form fissures that stabilize in the material. Following the initial heat treatment, all the phlogopite specimens, regardless of their origin and polytype, exhibit the extraordinarily large thermal expansion (intumescence), more than 200% at 600°C, in the direction perpendicular to the basal planes. This phenomenon is strictly reproducible when tested under a range of thermal conditions including thermal shock, multiple thermal fatigue cycles, varying heating or cooling rates and isothermal heating over an extensive period of time at different temperatures up to 585°C. The hysteresis, associated with the thermal cycle, is increased when the specimen is heated or cooled at a faster rate. The maximum coefficient of linear thermal expansion, approximately 10 -2°C-1, is observed over the temperature range 100--120°C. This is due to the non-structural water, entrapped within the layer structure, which undergoes a phase transition and causes the mica layers to expand abruptly. A model of lenticular fissures is developed based on thin-plate mechanics and thermodynamics assumptions. The state of a lenticular fissure with water vapor molecules is determined to correlate the experimental parameters with the material properties. The average density of water vapor molecules within a lenticular fissure is calculated to be ˜1025 m 3 for the temperature interval between 100°C and 275°C. The concentration of non-structure water, based on the model calculation, is less than 0.1% by weight. Acoustic emission (AE) signals have been reported by Pranevicius et al. (1995) to correspond to the microstructure changes as the internal lenticular fissures develop in phlogopite. This technique has also been proven feasible to characterize the thermomechanical behavior of other layer structures (Pranevicius 1995). Other layer structures are reviewed to determine their potential reversible thermomechanical properties. When phlogopite is used as a model specimen to relate microstructure to intumescence, two criteria are established for selection of the layer structures of potential intumescence. The first is the need for flexible and elastic layers to withstand the strain imposed by large lateral expansion. The second is the requirement of a high degree for intercalation. Possible candidates that fit these two criteria are identified. Finally, a few potential applications of layer structures of intumescence are discussed, and future research in this area is proposed. (Abstract shortened by UMI.)