Adsorption isotherms of water on mica: redistribution and film growth.

PubMed

Malani, Ateeque; Ayappa, K G

2009-01-29

Adsorption isotherms of water on muscovite mica are obtained using grand canonical Monte Carlo simulations over a wide range of relative vapor pressures, p/p(0) at 298 K. Three distinct stages are observed in the adsorption isotherm. A sharp rise in the water coverage occurs for 0 < p/p(0) < 0.1. This is followed by a relatively slow increase in the coverage for 0.1 < or = p/p(0) < or = 0.7. Above p/p(0) = 0.7, a second increase in the coverage occurs due to the adsorption of water with bulklike features. The derived film thickness and isotherm shape for the simple point charge (SPC) water model is in excellent agreement with recent experiments of Balmer et al. [ Langmuir 2008 , 24 , 1566 ]. A novel observation is the significant redistribution of water between adsorbed layers as the water film develops. This redistribution is most pronounced for 0.1 < or = p/p(0) < or = 0.7, where water is depleted from the inner layers and film growth is initiated on the outer layer. During this stage, potassium hydration is found to play a dominant role in the rearrangement of water near the mica surface. The analysis of structural features reveals a strongly bound first layer of water molecules occupying the ditrigonal cavities between the potassium ions. In-plane structure of oxygen in the second layer, which forms part of the first hydration shell of potassium, reveals a liquidlike structure with the oxygen-oxygen pair correlation function displaying features similar to bulk water. Isosteric heats of adsorption were found to be in good agreement with the differential microcalorimetric data of Rakhmatkariev ( Clays Clay Miner. 2006 , 54 , 402 ), over the entire range of pressures investigated. Both SPC and extended simple point charge (SPC/E) water models were found to yield qualitatively similar adsorption and structural characteristics, with the SPC/E model predicting lower coverages than the SPC model for p/p(0) > 0.7.

Super-hydrophilic copper sulfide films as light absorbers for efficient solar steam generation under one sun illumination

NASA Astrophysics Data System (ADS)

Guo, Zhenzhen; Ming, Xin; Wang, Gang; Hou, Baofei; Liu, Xinghang; Mei, Tao; Li, Jinhua; Wang, Jianying; Wang, Xianbao

2018-02-01

Solar steam technology is one of the simplest, most direct and effective ways to harness solar energy through water evaporation. Here, we report the development using super-hydrophilic copper sulfide (CuS) films with double-layer structures as light absorbers for solar steam generation. In the double-layer structure system, a porous mixed cellulose ester (MCE) membrane is used as a supporting layer, which enables water to get into the CuS light absorbers through a capillary action to provide continuous water during solar steam generation. The super-hydrophilic property of the double-layer system (CuS/MCE) leads to a thinner water film close to the air-water interface where the surface temperature is sufficiently high, leading to more efficient evaporation (˜80 ± 2.5%) under one sun illumination. Furthermore, the evaporation efficiencies still keep a steady value after 15 cycles of testing. The super-hydrophilic CuS film is promising for practical application in water purification and evaporation as a light absorption material.

Structural and mechanical properties of glassy water in nanoscale confinement.

PubMed

Lombardo, Thomas G; Giovambattista, Nicolás; Debenedetti, Pablo G

2009-01-01

We investigate the structure and mechanical properties of glassy water confined between silica-based surfaces with continuously tunable hydrophobicity and hydrophilicity by computing and analyzing minimum energy, mechanically stable configurations (inherent structures). The structured silica substrate imposes long-range order on the first layer of water molecules under hydrophobic confinement at high density (p > or = 1.0 g cm(-3)). This proximal layer is also structured in hydrophilic confinement at very low density (p approximately 0.4 g cm(-3)). The ordering of water next to the hydrophobic surface greatly enhances the mechanical strength of thin films (0.8 nm). This leads to a substantial stress anisotropy; the transverse strength of the film exceeds the normal strength by 500 MPa. The large transverse strength results in a minimum in the equation of state of the energy landscape that does not correspond to a mechanical instability, but represents disruption of the ordered layer of water next to the wall. In addition, we find that the mode of mechanical failure is dependent on the type of confinement. Under large lateral strain, water confined by hydrophilic surfaces preferentially forms voids in the middle of the film and fails cohesively. In contrast, water under hydrophobic confinement tends to form voids near the walls and fails by loss of adhesion.

Distribution of Arctic and Pacific copepods and their habitat in the northern Bering Sea and Chukchi Sea

NASA Astrophysics Data System (ADS)

Sasaki, H.; Matsuno, K.; Fujiwara, A.; Onuka, M.; Yamaguchi, A.; Ueno, H.; Watanuki, Y.; Kikuchi, T.

2015-11-01

The advection of warm Pacific water and the reduction of sea-ice extent in the western Arctic Ocean may influence the abundance and distribution of copepods, i.e., a key component in food webs. To understand the factors affecting abundance of copepods in the northern Bering Sea and Chukchi Sea, we constructed habitat models explaining the spatial patterns of the large and small Arctic copepods and the Pacific copepods, separately, using generalized additive models. Copepods were sampled by NORPAC net. Vertical profiles of density, temperature and salinity in the seawater were measured using CTD, and concentration of chlorophyll a in seawater was measured with a fluorometer. The timing of sea-ice retreat was determined using the satellite image. To quantify the structure of water masses, the magnitude of pycnocline and averaged density, temperature and salinity in upper and bottom layers were scored along three axes using principal component analysis (PCA). The structures of water masses indexed by the scores of PCAs were selected as explanatory variables in the best models. Large Arctic copepods were abundant in the water mass with high salinity water in bottom layer or with cold/low salinity water in upper layer and cold/high salinity water in bottom layer, and small Arctic copepods were abundant in the water mass with warm/saline water in upper layer and cold/high salinity water in bottom layers, while Pacific copepods were abundant in the water mass with warm/saline in upper layer and cold/high salinity water in bottom layer. All copepod groups were abundant in areas with deeper depth. Although chlorophyll a in upper and bottom layers were selected as explanatory variables in the best models, apparent trends were not observed. All copepod groups were abundant where the sea-ice retreated at earlier timing. Our study might indicate potential positive effects of the reduction of sea-ice extent on the distribution of all groups of copepods in the Arctic Ocean.

Water polygons in high-resolution protein crystal structures.

PubMed

Lee, Jonas; Kim, Sung-Hou

2009-07-01

We have analyzed the interstitial water (ISW) structures in 1500 protein crystal structures deposited in the Protein Data Bank that have greater than 1.5 A resolution with less than 90% sequence similarity with each other. We observed varieties of polygonal water structures composed of three to eight water molecules. These polygons may represent the time- and space-averaged structures of "stable" water oligomers present in liquid water, and their presence as well as relative population may be relevant in understanding physical properties of liquid water at a given temperature. On an average, 13% of ISWs are localized enough to be visible by X-ray diffraction. Of those, averages of 78% are water molecules in the first water layer on the protein surface. Of the localized ISWs beyond the first layer, almost half of them form water polygons such as trigons, tetragons, as well as expected pentagons, hexagons, higher polygons, partial dodecahedrons, and disordered networks. Most of the octagons and nanogons are formed by fusion of smaller polygons. The trigons are most commonly observed. We suggest that our observation provides an experimental basis for including these water polygon structures in correlating and predicting various water properties in liquid state.

Water polygons in high-resolution protein crystal structures

PubMed Central

Lee, Jonas; Kim, Sung-Hou

2009-01-01

We have analyzed the interstitial water (ISW) structures in 1500 protein crystal structures deposited in the Protein Data Bank that have greater than 1.5 Å resolution with less than 90% sequence similarity with each other. We observed varieties of polygonal water structures composed of three to eight water molecules. These polygons may represent the time- and space-averaged structures of “stable” water oligomers present in liquid water, and their presence as well as relative population may be relevant in understanding physical properties of liquid water at a given temperature. On an average, 13% of ISWs are localized enough to be visible by X-ray diffraction. Of those, averages of 78% are water molecules in the first water layer on the protein surface. Of the localized ISWs beyond the first layer, almost half of them form water polygons such as trigons, tetragons, as well as expected pentagons, hexagons, higher polygons, partial dodecahedrons, and disordered networks. Most of the octagons and nanogons are formed by fusion of smaller polygons. The trigons are most commonly observed. We suggest that our observation provides an experimental basis for including these water polygon structures in correlating and predicting various water properties in liquid state. PMID:19551896

Double diffusion in the frontal zones of the Yellow and East China Seas in winter

NASA Astrophysics Data System (ADS)

Oh, K.; Lee, S.

2017-12-01

Where the cold, fresh water of the Yellow Sea (YS) and the warm, salty water of the East China Sea (ECS) meet, northern and southern fronts are formed in the southeastern YS and the northwestern ECS, respectively. Strong thermohaline fronts are formed on the northern front, and a strong thermocline and a temperature reversal phenomenon are represented in this front. To understand the water structure of this thermohaline zone, we examined double diffusion in the frontal zones in February 2003 using hydrographic data. In the northern front, the warm, salty Cheju Warm Current Water (CWCW) moved northwards along the bottom layer and the cold, fresh Yellow Sea Cold Water (YSCW) flowed southward in the upper layer. As a result, strong thermohaline fronts forms in the area where the two water masses met, and the slope was developed downward across the front. In this area, a strong thermocline and temperature reversal structures were present. The cold, fresh Korean Coastal Water (KCW) was also found in the upper layer near the thermocline, and has a low-temperature, low-salinity more than surrounding water. When cold, fresh water is located over warm, salty water, heat diffuses through the interface between the two water masses, and then the diffusive-convection can be expected to occur. On the other hand, when warm, salty water overlays cold, fresh water, heat in the upper layer is preferentially transferred downward, and the salt-fingering occurs. The diffusive-convection occurs predominantly in the northern thermohaline front, where the cold, fresh YSCW is situated above the warm, salty CWCW and has the effect of strengthening stratification, so that the water column maintains a physically stable structure. In addition, this phenomenon seems to play a role in maintaining the reversal structure. The salt-fingering occurs in upper layers of the northern front where the cold, fresh YSCW is located over the most cold, fresh KCW. Near the northern thermo-halocline zone, the salt-fingering occurs simultaneously with the diffusive-convection, because three water masses, YSCW, KCW and CWCW, interact in that area. Therefore, it can be seen that the water structure of the northern frontal zone in winter is influenced mainly by the cold, fresh YSCW, the most cold, fresh KCW, and the warm, salty CWCW.

Bifunctional catalytic electrode

NASA Technical Reports Server (NTRS)

Cisar, Alan (Inventor); Murphy, Oliver J. (Inventor); Clarke, Eric (Inventor)

2005-01-01

The present invention relates to an oxygen electrode for a unitized regenerative hydrogen-oxygen fuel cell and the unitized regenerative fuel cell having the oxygen electrode. The oxygen electrode contains components electrocatalytically active for the evolution of oxygen from water and the reduction of oxygen to water, and has a structure that supports the flow of both water and gases between the catalytically active surface and a flow field or electrode chamber for bulk flow of the fluids. The electrode has an electrocatalyst layer and a diffusion backing layer interspersed with hydrophilic and hydrophobic regions. The diffusion backing layer consists of a metal core having gas diffusion structures bonded to the metal core.

Community structure of copepods in the oceanic and neritic waters off Adélie and George V Land, East Antarctica, during the austral summer of 2008

NASA Astrophysics Data System (ADS)

Tachibana, Aiko; Watanabe, Yuko; Moteki, Masato; Hosie, Graham W.; Ishimaru, Takashi

2017-06-01

Copepods are one of the most important components of the Southern Ocean food web, and are widely distributed from surface to deeper waters. We conducted discrete depth sampling to clarify the community structure of copepods from the epi- to bathypelagic layers of the oceanic and neritic waters off Adélie and George V Land, East Antarctica, in the austral summer of 2008. Notably high diversity and species numbers were observed in the meso- and bathypelagic layers. Cluster analysis based on the similarity of copepod communities identified seven cluster groups, which corresponded well with water masses. In the epi- and upper- mesopelagic layers of the oceanic zone, the SB (Southern Boundary of the Antarctic Circumpolar Current) divided copepod communities. Conversely, in the lower meso- and bathypelagic layers (500-2000 m depth), communities were consistent across the SB. In these layers, the distributions of copepod species were separated by habitat depth ranges and feeding behaviour. The different food webs occur in the epipelagic layer with habitat segregation by zooplankton in their horizontal distribution ranges.

Layered electrode for electrochemical cells

DOEpatents

Swathirajan, Swathy; Mikhail, Youssef M.

2001-01-01

There is provided an electrode structure comprising a current collector sheet and first and second layers of electrode material. Together, the layers improve catalyst utilization and water management.

Softly-confined water cluster between freestanding graphene sheets

NASA Astrophysics Data System (ADS)

Agustian, Rifan; Akaishi, Akira; Nakamura, Jun

2018-01-01

Confined water could adopt new forms not seen in the open air, such as a two-dimensional (2D) square ice trapped between two graphene sheets [Algara-Siller et al., Nature 519, 443-445 (2015)]. In this study, in order to investigate how the flexibility of graphene affects the confined structure of water molecules, we employed classical molecular dynamics simulations with Adaptive Intermolecular Reactive Empirical Bond Order (AIREBO) potential to produce a soft-confining property of graphene. We discovered various solid-like structures of water molecules ranging from two-dimensional to three-dimensional structure encapsulated between two freestanding graphene sheets even at room temperature (300K). A small amount of water encapsulation leads to a layered two-dimensional form with triangular structure. On the other hand, large amounts of water molecules take a three-dimensional flying-saucer-like form with the square ice intra-layer structure. There is also a metastable state where both two-dimensional and three-dimensional structures coexist.

Effects of sea water on elongated duration of ground motion as well as variation in its amplitude for offshore earthquakes

NASA Astrophysics Data System (ADS)

Todoriki, Masaru; Furumura, Takashi; Maeda, Takuto

2017-01-01

We investigated the effects of sea water on the propagation of seismic waves using a 3-D finite-difference-method simulation of seismic wave propagation following offshore earthquakes. When using a 1-D layered structure, the simulation results showed strong S- to P-wave conversion at the sea bottom; accordingly, S-wave energy was dramatically decreased by the sea water layer. This sea water de-amplification effect had strong frequency dependence, therefore resembling a low-pass filter in which the cut-off frequency and damping coefficients were defined by the thickness of the sea water layer. The sea water also acted to elongate the duration of Rayleigh wave packet. The importance of the sea water layer in modelling offshore earthquakes was further demonstrated by a simulation using a realistic 3-D velocity structure model with and without sea water for a shallow (h = 14 km) outer-rise Nankai Trough event, the 2004 SE Off Kii Peninsula earthquake (Mw = 7.2). Synthetic seismograms generated by the model when sea water was included were in accordance with observed seismograms for long-term longer period motions, particularly those in the shape of Rayleigh waves.

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

DOE PAGES

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

2015-07-20

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

Condensing Heat Exchanger with Hydrophilic Antimicrobial Coating

NASA Technical Reports Server (NTRS)

Thomas, Christopher M. (Inventor); Ma, Yonghui (Inventor)

2014-01-01

A multi-layer antimicrobial hydrophilic coating is applied to a substrate of anodized aluminum, although other materials may form the substrate. A silver layer is sputtered onto a thoroughly clean anodized surface of the aluminum to about 400 nm thickness. A layer of crosslinked, silicon-based macromolecular structure about 10 nm thickness overlies the silver layer, and the outermost surface of the layer of crosslinked, silicon-based macromolecular structure is hydroxide terminated to produce a hydrophilic surface with a water drop contact angle of less than 10.degree.. The coated substrate may be one of multiple fins in a condensing heat exchanger for use in the microgravity of space, which has narrow channels defined between angled fins such that the surface tension of condensed water moves water by capillary flow to a central location where it is pumped to storage. The antimicrobial coating prevents obstruction of the capillary passages.

Required Accuracy of Structural Constraints in the Inversion of Electrical Resistivity Data for Improved Water Content Estimation

NASA Astrophysics Data System (ADS)

Heinze, T.; Budler, J.; Weigand, M.; Kemna, A.

2017-12-01

Water content distribution in the ground is essential for hazard analysis during monitoring of landslide prone hills. Geophysical methods like electrical resistivity tomography (ERT) can be utilized to determine the spatial distribution of water content using established soil physical relationships between bulk electrical resistivity and water content. However, often more dominant electrical contrasts due to lithological structures outplay these hydraulic signatures and blur the results in the inversion process. Additionally, the inversion of ERT data requires further constraints. In the standard Occam inversion method, a smoothness constraint is used, assuming that soil properties change softly in space. While this applies in many scenarios, sharp lithological layers with strongly divergent hydrological parameters, as often found in landslide prone hillslopes, are typically badly resolved by standard ERT. We use a structurally constrained ERT inversion approach for improving water content estimation in landslide prone hills by including a-priori information about lithological layers. The smoothness constraint is reduced along layer boundaries identified using seismic data. This approach significantly improves water content estimations, because in landslide prone hills often a layer of rather high hydraulic conductivity is followed by a hydraulic barrier like clay-rich soil, causing higher pore pressures. One saturated layer and one almost drained layer typically result also in a sharp contrast in electrical resistivity, assuming that surface conductivity of the soil does not change in similar order. Using synthetic data, we study the influence of uncertainties in the a-priori information on the inverted resistivity and estimated water content distribution. We find a similar behavior over a broad range of models and depths. Based on our simulation results, we provide best-practice recommendations for field applications and suggest important tests to obtain reliable, reproducible and trustworthy results. We finally apply our findings to field data, compare conventional and improved analysis results, and discuss limitations of the structurally-constrained inversion approach.

Novel Swelling-Resistant Sodium Alginate Membrane Branching Modified by Glycogen for Highly Aqueous Ethanol Solution Pervaporation.

PubMed

Ji, Chen-Hao; Xue, Shuang-Mei; Xu, Zhen-Liang

2016-10-12

A novel carbohydrate chain cross-linking method of sodium alginate (SA) is proposed in which glycogen with the branched-chain structure is utilized to cross-link with SA matrix by the bridging of glutaraldehyde (GA). The active layer of SA composite ceramic membrane modified by glycogen and GA for pervaporation (PV) demonstrates great advantages. The branched structure increases the chain density of the active layer, which compresses the free volume between the carbohydrate chains of SA. Large amounts of hydroxyl groups are consumed during the reaction with GA, which reduces the hydrogen bond formation between water molecules and the polysaccharide matrix. The two factors benefit the active layer with great improvement in swelling resistance, promoting the potential of the active layer for the dehydration of an ethanol-water solution containing high water content. Meanwhile, the modified active layer is loaded on the rigid α-Al 2 O 3 ceramic membrane by dip-coating method with the enhancement of anti-deformation and controllable thickness of the active layer. Characterization techniques such as SEM, AFM, XRD, FTIR, XPS, and water contact angle are utilized to observe the composite structure and surface morphology of the composite membrane, to probe the free volume variation, and to determine the chemical composition and hydrophilicity difference of the active layer caused by the different glycogen additive amounts. The membrane containing 3% glycogen in the selective layer demonstrates the flux at 1250 g m -2 h -1 coupled with the separation factor of 187 in the 25 wt % water content feed solution at the operating temperature of 75 °C, reflecting superior pervaporation processing capacity compared with the general organic PV membranes in the same condition.

A Marine Boundary Layer Water Vapor Climatology Derived from Microwave and Near-Infrared Imagery

NASA Astrophysics Data System (ADS)

Millan Valle, L. F.; Lebsock, M. D.; Teixeira, J.

2017-12-01

The synergy of the collocated Advanced Microwave Scanning Radiometer (AMSR) and the Moderate Resolution Imaging Spectroradiometer (MODIS) provides daily global estimates of partial marine planetary boundary layer water vapor. AMSR microwave radiometry provides the total column water vapor, while MODIS near-infrared imagery provides the water vapor above the cloud layers. The difference between the two gives the vapor between the surface and the cloud top, which may be interpreted as the boundary layer water vapor. Comparisons against radiosondes, and GPS-Radio occultation data demonstrate the robustness of these boundary layer water vapor estimates. We exploit the 14 years of AMSR-MODIS synergy to investigate the spatial, seasonal, and inter-annual variations of the boundary layer water vapor. Last, it is shown that the measured AMSR-MODIS partial boundary layer water vapor can be generally prescribed using sea surface temperature, cloud top pressure and the lifting condensation level. The multi-sensor nature of the analysis demonstrates that there exists more information on boundary layer water vapor structure in the satellite observing system than is commonly assumed when considering the capabilities of single instruments. 2017 California Institute of Technology. U.S. Government sponsorship acknowledged.

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.

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

The Onset of Channelling in a Fluidized Mud Layer

NASA Astrophysics Data System (ADS)

Papanicolaou, T.; Tsakiris, A. G.; Billing, B. M.

2012-12-01

Fluidization of a soil occurs when the drag force exerted on the soil grains by upwelling water equals the submerged weight of the soil grains, hence reducing the effective (or contact) stress between the soil grains to zero. In nature, fluidization is commonly encountered in localized portions of highly saturated mud layers found in tidal flats, estuaries and lakes, where upward flow is initiated by significant pore water pressure gradients triggered by wave or tidal action. The water propagates through the fluidized mud layer by forming channels (or vents), carrying the fluidized mud to the surface and forming mud volcano structures. The presence of these fluidization channels alters the mud layer structure with implications on its hydraulic and geotechnical properties, such as the hydraulic conductivity. Despite the importance of these channels, the conditions that lead to their formation and their effects on the mud layer structure still remain poorly documented. The present study couples experimental and theoretical methods aimed at quantifying the conditions, under which fluidization of a saturated mud layer is accompanied by the formation of channels, and assessing the effects of channeling on the mud layer structure. Fluidization and channel formation in a mud layer were reproduced in the laboratory using a carefully designed fluidization column attached to a pressurized vessel (plenum). To eliminate any effects of the material, the mud was produced from pure kaolin clay and deionized water. Local porosity measurements along the mud layer prior, during and after fluidization were conducted using an Americium-241 gamma source placed on a fully automated carriage. Different water inflow rates, q, were applied to the base of the mud layer and the plenum pressure was monitored throughout the experiment. These experiments revealed that for high q values, a single vertical channel formed and erupted at the center of the fluidization column. Instead for low q values, the experiments suggested that a channel network formed within the mud layer leading to the eruption of multiple channels on the mud layer surface. The gamma source measurements captured quantitatively the porosity increase as the channel formed. The experiments were complemented with a theoretical analysis using the two-phase, flow mass and momentum governing equations. This analysis aims to establish a relation between the applied pressure, the fluid velocity and the local porosity of mud during the formation of the channels.

Effect of abrasive water jet on the structure of the surface layer of Al-Mg alloy

NASA Astrophysics Data System (ADS)

Tabatchikova, T. I.; Tereshchenko, N. A.; Yakovleva, I. L.; Gudnev, N. Z.

2017-09-01

Optical, scanning, and transmission electron microscopy methods, and X-ray diffraction analysis have been used to study the changes in the structure and the microhardness in the surface layer of the Al-Mg (5.8-6.8 wt %) alloy after water jet cutting. The dislocation density, the sizes of coherent scattering regions, and microdistortions have been determined. The transformation of the fine structure has been revealed in the displacement from the alloy volume to the abrasive-waterjet cutting surface.

Fabrication of multilayered thin films via spin-assembly

DOEpatents

Chiarelli, Peter A.; Robinson, Jeanne M.; Casson, Joanna L.; Johal, Malkiat S.; Wang, Hsing-Lin

2007-02-20

An process of forming multilayer thin film heterostructures is disclosed and includes applying a solution including a first water-soluble polymer from the group of polyanionic species, polycationic species and uncharged polymer species onto a substrate to form a first coating layer on the substrate, drying the first coating layer on the substrate, applying a solution including a second water-soluble polymer from the group of polyanionic species, polycationic species and uncharged polymer species onto the substrate having the first coating layer to form a second coating layer on the first coating layer wherein the second water-soluble polymer is of a different material than the first water-soluble polymer, and drying the second coating layer on the first coating layer so as to form a bilayer structure on the substrate. Optionally, one or more additional applying and drying sequences can be repeated with a water-soluble polymer from the group of polyanionic species, polycationic species and uncharged polymer species, so that a predetermined plurality of layers are built up upon the substrate.

[Properties of cell water].

PubMed

Gamaleĭ, I A; Kaulin, A B; Troshin, A S

1977-01-01

An attempt was made to analyse and summarize findings concerning water properties of animal and plant cells. From the physical evidence of surface influence on the structure of vicinal water layers, a conclusion is drawn that the structure and properties of cell water are likely to be affected by intracellular interfaces.

Double-diffusive layers in the Adriatic Sea

NASA Astrophysics Data System (ADS)

Carniel, Sandro; Sclavo, Mauro; Kantha, Lakshmi; Prandke, Hartmut

2008-01-01

A microstructure profiler was deployed to make turbulence measurements in the upper layers of the southern Adriatic Sea in the Mediterranean during the Naval Research Laboratory (NRL) DART06A (Dynamics of the Adriatic in Real Time) winter cruise in March 2006. Measurements in the Po river plume along the Italian coast near the Gargano promontory displayed classic double-diffusive layers and staircase structures resulting from the relatively colder and fresher wintertime Po river outflow water masses overlying warmer and more saline water masses from the Adriatic Sea. We report here on the water mass and turbulence structure measurements made both in the double-diffusive interfaces and the adjoining mixed layers in the water columns undergoing double-diffusive convection (DDC). This dataset augments the relatively sparse observations available hitherto on the diffusive layer type of DDC. Measured turbulence diffusivities are consistent with those from earlier theoretical and experimental formulations, suggesting that the wintertime Po river plume is a convenient and easily accessible place to study double diffusive convective processes of importance to mixing in the interior of many regions of the global oceans.

Improving water content estimation on landslide-prone hillslopes using structurally-constrained inversion of electrical resistivity data

NASA Astrophysics Data System (ADS)

Heinze, Thomas; Möhring, Simon; Budler, Jasmin; Weigand, Maximilian; Kemna, Andreas

2017-04-01

Rainfall-triggered landslides are a latent danger in almost any place of the world. Due to climate change heavy rainfalls might occur more often, increasing the risk of landslides. With pore pressure as mechanical trigger, knowledge of water content distribution in the ground is essential for hazard analysis during monitoring of potentially dangerous rainfall events. Geophysical methods like electrical resistivity tomography (ERT) can be utilized to determine the spatial distribution of water content using established soil physical relationships between bulk electrical resistivity and water content. However, often more dominant electrical contrasts due to lithological structures outplay these hydraulic signatures and blur the results in the inversion process. Additionally, the inversion of ERT data requires further constraints. In the standard Occam inversion method, a smoothness constraint is used, assuming that soil properties change softly in space. This applies in many scenarios, as for example during infiltration of water without a clear saturation front. Sharp lithological layers with strongly divergent hydrological parameters, as often found in landslide prone hillslopes, on the other hand, are typically badly resolved by standard ERT. We use a structurally constrained ERT inversion approach for improving water content estimation in landslide prone hills by including a-priori information about lithological layers. Here the standard smoothness constraint is reduced along layer boundaries identified using seismic data or other additional sources. This approach significantly improves water content estimations, because in landslide prone hills often a layer of rather high hydraulic conductivity is followed by a hydraulic barrier like clay-rich soil, causing higher pore pressures. One saturated layer and one almost drained layer typically result also in a sharp contrast in electrical resistivity, assuming that surface conductivity of the soil does not change in similar order. Using synthetic data, we study the influence of uncertainties in the a-priori information on the inverted resistivity and estimated water content distribution. Based on our simulation results, we provide best-practice recommendations for field applications and suggest important tests to obtain reliable, reproducible and trustworthy results. We finally apply our findings to field data, compare conventional and improved analysis results, and discuss limitations of the structurally-constrained inversion approach.

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.

The role of the hydrophobic phase in the unique rheological properties of saponin adsorption layers.

PubMed

Golemanov, Konstantin; Tcholakova, Slavka; Denkov, Nikolai; Pelan, Eddie; Stoyanov, Simeon D

2014-09-28

Saponins are a diverse class of natural, plant derived surfactants, with peculiar molecular structure consisting of a hydrophobic scaffold and one or several hydrophilic oligosaccharide chains. Saponins have strong surface activity and are used as natural emulsifiers and foaming agents in food and beverage, pharmaceutical, ore processing, and other industries. Many saponins form adsorption layers at the air-water interface with extremely high surface elasticity and viscosity. The molecular origin of the observed unique interfacial visco-elasticity of saponin adsorption layers is of great interest from both scientific and application viewpoints. In the current study we demonstrate that the hydrophobic phase in contact with water has a very strong effect on the interfacial properties of saponins and that the interfacial elasticity and viscosity of the saponin adsorption layers decrease in the order: air > hexadecane ≫ tricaprylin. The molecular mechanisms behind these trends are analyzed and discussed in the context of the general structure of the surfactant adsorption layers at various nonpolar phase-water interfaces.

Chloride ions induce order-disorder transition at water-oxide interfaces

NASA Astrophysics Data System (ADS)

Deshmukh, Sanket; Kamath, Ganesh; Ramanathan, Shriram; Sankaranarayanan, Subramanian K. R. S.

2013-12-01

Water can form quasi-two-dimensional ordered layers near a solid interface. The solvation dynamics and ionic transport phenomena through this ordered water structure is of direct relevance to a variety of problems in interface science. Molecular dynamics simulations are used to study the impact of local fluctuation of the chloride ion density in the vicinity of an oxide surface on the structure and dynamics of water layers. We demonstrate that local increase in chloride ions beyond a threshold concentration near the water-MgO (100) interface introduces an order-disorder transition of this two-dimensional layered network into bulklike water, leading to increased diffusional characteristics and reduced hydrogen bonding lifetimes. We find that the extent of this order-disorder transition can be tuned by modifying the defect chemistry and nature of the underlying substrate. The kinetic fluidity resulting from order-disorder transition at high chloride ion concentration has significance for a broad range of phenomena, ranging from freezing point depression of brine to onset of aqueous corrosion.

Structured Water Layers Adjacent to Biological Membranes

PubMed Central

Higgins, Michael J.; Polcik, Martin; Fukuma, Takeshi; Sader, John E.; Nakayama, Yoshikazu; Jarvis, Suzanne P.

2006-01-01

Water amid the restricted space of crowded biological macromolecules and at membrane interfaces is essential for cell function, though the structure and function of this “biological water” itself remains poorly defined. The force required to remove strongly bound water is referred to as the hydration force and due to its widespread importance, it has been studied in numerous systems. Here, by using a highly sensitive dynamic atomic force microscope technique in conjunction with a carbon nanotube probe, we reveal a hydration force with an oscillatory profile that reflects the removal of up to five structured water layers from between the probe and biological membrane surface. Further, we find that the hydration force can be modified by changing the membrane fluidity. For 1,2-dipalmitoyl-sn-glycero-3-phosphocholine gel (Lβ) phase bilayers, each oscillation in the force profile indicates the force required to displace a single layer of water molecules from between the probe and bilayer. In contrast, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine fluid (Lα) phase bilayers at 60°C and 1,2-dioleoyl-sn-glycero-3-phosphocholine fluid (Lα) phase bilayers at 24°C seriously disrupt the molecular ordering of the water and result predominantly in a monotonic force profile. PMID:16798815

Water Vapor Permeation of Metal Oxide/Polymer Coated Plastic Films

NASA Astrophysics Data System (ADS)

Numata, Yukihiro; Oya, Toshiyuki; Kuwahara, Mitsuru; Ito, Katsuya

Barrier performance to water vapor permeation of ceramic coated layers deposited on flexible polymer films is of great interest to food packaging, medical device packaging and flat panel display industries. In this study, a new type film in which a ceramic layer is deposited on a polymer coated film was proposed for lower water vapor permeation. It is important how to control interfacial properties between each layer and film for good barrier performance. Several kinds of polymer coated materials were prepared for changing surface free energy of the films before and after depositing the ceramic layer. The ceramic layer, which is composed of mixed material of SiO2 and Al2O3, was adopted under the same conditions. The following results were obtained; 1) Water vapor permeation is not related to the surface energy of polymer coated films, 2) After depositing the ceramic layer, however, a strong correlation is observed between the water vapor permeation and surface free energy. 3) The phenomenon is considered that the polarity of the polymer layers plays a key role in changing the structure of ceramic coated layers.

Influence of salt and rinsing protocol on the structure of PAH/PSS polyelectrolyte multilayers.

PubMed

Feldötö, Zsombor; Varga, Imre; Blomberg, Eva

2010-11-16

A quartz crystal microbalance (QCM) and dual polarization interferometry (DPI) have been utilized to study how the structure of poly(allylamine hydrochloride) (PAH)/poly(styrene sulfonate) (PSS) multilayers is affected by the rinsing method (i.e., the termination of polyelectrolyte adsorption). The effect of the type of counterions used in the deposition solution was also investigated, and the polyelectrolyte multilayers were formed in a 0.5 M electrolyte solution (NaCl and KBr). From the measurements, it was observed that thicker layers were obtained when using KBr in the deposition solution than when using NaCl. Three different rinsing protocols have been studied: (i) the same electrolyte solution as used during multilayer formation, (ii) pure water, and (iii) first a salt solution (0.5 M) and then pure water. When the multilayer with PAH as the outermost layer was exposed to pure water, an interesting phenomenon was discovered: a large change in the energy dissipation was measured with the QCM. This could be attributed to the swelling of the layer, and from both QCM and DPI it is obvious that only the outermost PAH layer swells (to a thickness of 25-30 nm) because of a decrease in ionic strength and hence an increase in intra- and interchain repulsion, whereas the underlying layers retain a very rigid and compact structure with a low water content. Interestingly, the outermost PAH layer seems to obtain very similar thicknesses in water independent of the electrolyte used for the multilayer buildup. Another interesting aspect was that the measured thickness with the DPI evaluated by a single-layer model did not correlate with the estimated thickness from the model calculations performed on the QCM-D data. Thus, we applied a two-layer model to evaluate the DPI data and the results were in excellent agreement with the QCM-D results. To our knowledge, this evaluation of DPI data has not been done previously.

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.

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.

Permeation Properties and Pore Structure of Surface Layer of Fly Ash Concrete

PubMed Central

Liu, Jun; Qiu, Qiwen; Xing, Feng; Pan, Dong

2014-01-01

This paper presents an experimental study on the nature of permeation properties and pore structure of concrete surface layers containing fly ash. Concretes containing different dosages of fly ash as a replacement for cement (15% and 30% by weight of total cement materials, respectively) were investigated. Concrete without any fly ash added was also employed as the reference specimen. Laboratory tests were conducted to determine the surface layer properties of concrete including chloride transport, apparent water permeability and pore structure. The results demonstrate that incorporation of fly ash, for the early test period, promotes the chloride ingress at the surface layer of concrete but substituting proportions of fly ash may have little impact on it. With the process of chloride immersion, the chloride concentration at the surface layer of concrete with or without fly ash was found to be nearly the same. In addition, it is suggested that the water permeability at the concrete surface area is closely related to the fly ash contents as well as the chloride exposure time. Pore structure was characterized by means of mercury intrusion porosimetry (MIP) test and the scanning electron microscopy (SEM) images. The modification of pore structure of concrete submersed in distilled water is determined by the pozzolanic reaction of fly ash and the calcium leaching effect. The pozzolanic reaction was more dominant at the immersion time of 180 days while the calcium leaching effect became more evident after 270 days. PMID:28788677

Infrared light-induced protein crystallization. Structuring of protein interfacial water and periodic self-assembly

NASA Astrophysics Data System (ADS)

Kowacz, Magdalena; Marchel, Mateusz; Juknaité, Lina; Esperança, José M. S. S.; Romão, Maria João; Carvalho, Ana Luísa; Rebelo, Luís Paulo N.

2017-01-01

We show that a physical trigger, a non-ionizing infrared (IR) radiation at wavelengths strongly absorbed by liquid water, can be used to induce and kinetically control protein (periodic) self-assembly in solution. This phenomenon is explained by considering the effect of IR light on the structuring of protein interfacial water. Our results indicate that the IR radiation can promote enhanced mutual correlations of water molecules in the protein hydration shell. We report on the radiation-induced increase in both the strength and cooperativeness of H-bonds. The presence of a structured dipolar hydration layer can lead to attractive interactions between like-charged biomacromolecules in solution (and crystal nucleation events). Furthermore, our study suggests that enveloping the protein within a layer of structured solvent (an effect enhanced by IR light) can prevent the protein non-specific aggregation favoring periodic self-assembly. Recognizing the ability to affect protein-water interactions by means of IR radiation may have important implications for biological and bio-inspired systems.

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.

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.

Stabilization of flux during dead-end ultra-low pressure ultrafiltration.

PubMed

Peter-Varbanets, Maryna; Hammes, Frederik; Vital, Marius; Pronk, Wouter

2010-06-01

Gravity driven ultrafiltration was operated in dead-end mode without any flushing or cleaning. In contrary to general expectations, the flux value stabilized after about one week of operation and remained constant during an extended period of time (several months). Different surface water types and diluted wastewater were used as feed water and, depending on the feed water composition, stable flux values were in the range of 4-10 L h(-1) m(-2). When sodium azide was added to the feed water to diminish the biological activity, no stabilization of flux occurred, indicating that biological processes play an important role in the flux stabilization process. Confocal laser scanning microscopy revealed the presence of a biofouling layer, of which the structure changed over time, leading to relatively heterogeneous structures. It is assumed that the stabilization of flux is related to the development of heterogeneous structures in the fouling layer, due to biological processes in the layer. The phenomenon of flux stabilization opens interesting possibilities for application, for instance in simple and low-cost ultrafiltration systems for decentralized drinking water treatment in developing and transition countries, independent of energy supply, chemicals, or complex process control. 2010 Elsevier Ltd. All rights reserved.

A TWO-PROBE METHOD FOR MEASURING WATER CONTENT OF THIN FOREST FLOOR LITTER LAYERS USING TIME DOMAIN REFLECTOMETRY

EPA Science Inventory

Few methods exist that allow non-destructive in situ measurement of the water content of forest floor litter layers (Oa,Oe, and Oi horizons). Continuous non-destructive measurement is needed in studies of ecosystem processes because of the relationship between physical structure ...

Application of 3A molecular sieve layer in dye-sensitized solar cells

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

Yan, Yuan; Wang, Jinzhong, E-mail: jinzhong-wang@hit.edu.cn, E-mail: qingjiang.yu@hit.edu.cn; Yu, Qingjiang, E-mail: jinzhong-wang@hit.edu.cn, E-mail: qingjiang.yu@hit.edu.cn

2014-08-25

3A molecular sieve layer was used as dehydration and electronic-insulation layer on the TiO{sub 2} electrode of dye-sensitized solar cells. This layer diminished the effect of water in electrolyte efficiently and enhanced the performance of cells. The conversion efficiency increased from 9.58% to 10.2%. The good moisture resistance of cells was attributed to the three-dimensional interconnecting structure of 3A molecular sieve with strong adsorption of water molecule. While the performance enhancement benefited from the suppression of the charge recombination of electronic-insulation layer and scattering effect of large particles.

Natural convection heat transfer in water near its density maximum

NASA Astrophysics Data System (ADS)

Yen, Yin-Chao

1990-12-01

This monograph reviews and summarizes to date the experimental and analytical results on the effect of water density near its maximum convection, transient flow and temperature structure characteristics: (1) in a vertical enclosure; (2) in a vertical annulus; (3) between horizontal concentric cylinders; (4) in a square enclosure; (5) in a rectangular enclosure; (6) in a horizontal layer; (7) in a circular confined melt layer; and (8) in bulk water during melting. In a layer of water containing a maximum density temperature of 4 C, the onset of convection (the critical number) is found not to be a constant value as in the classical normal fluid but one that varies with the imposed thermal and hydrodynamic boundaries. In horizontal layers, a nearly constant temperature zone forms and continuously expands between the warm and cold boundaries. A minimum heat transfer exists in most of the geometries studied and, in most cases, can be expressed in terms of a density distribution parameter. The effect of this parameter on a cells formation, disappearance and transient structure is discussed, and the effect of split boundary flow on heat transfer is presented.

Reorientation of the ‘free OH’ group in the top-most layer of air/water interface of sodium fluoride aqueous solution probed with sum-frequency generation vibrational spectroscopy

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

Feng, Ran-Ran; Guo, Yuan; Wang, Hongfei

2014-09-17

Many experimental and theoretical studies have established the specific anion, as well as cation effects on the hydrogen-bond structures at the air/water interface of electrolyte solutions. However, the ion effects on the top-most layer of the air/water interface, which is signified by the non-hydrogen-bonded so-called ‘free O-H’ group, has not been discussed or studied. In this report, we present the measurement of changes of the orientational angle of the ‘free O-H’ group at the air/water interface of the sodium fluoride (NaF) solutions at different concentrations using the interface selective sum-frequency generation vibrational spectroscopy (SFG-VS) in the ssp and ppp polarizations.more » The polarization dependent SFG-VS results show that the average tilt angle of the ‘free O-H’ changes from about 35.3 degrees ± 0.5 degrees to 43.4 degrees ± 2.1degrees as the NaF concentration increase from 0 to 0.94M (nearly saturated). Such tilt angle change is around the axis of the other O-H group of the same water molecule at the top-most layer at the air/water interface that is hydrogen-bonded to the water molecules below the top-most layer. These results provide quantitative molecular details of the ion effects of the NaF salt on the structure of the water molecules at the top-most layer of the air/water interfacial, even though both the Na+ cation and the F- anion are believed to be among the most excluded ions from the air/water interface.« less

Impact of the geological structures on the groundwater potential using geophysical techniques in West Bani Mazar area, El Minia - Western Desert, Egypt

NASA Astrophysics Data System (ADS)

Mahmoud, Hussein Hosni; Kotb, Adel Diab Mohammed

2017-06-01

Establishment of the new agricultural projects in west Bani Mazar area, El Minia, Egypt needs a good knowledge about groundwater. Groundwater serves as the unique source of water supplies in the study area. Vertical Electrical Sounding technique is a convenient tool for groundwater exploration. This technique was utilized to illustrate the geoelectric succession, vertical and spatial extensions of the encountered layers, depth to water bearing layers and the structures affecting these layers. Profiling technique was carried out along a grid pattern using different half current electrode spacings (150 m, 300 m and 500 m) to clarify changes in resistivity values throughout the study area at different depths. Geoelectric layers B1 and B2 of the saturated zone are suitable for groundwater extraction in the study area. The resistivity values of the geoelectric layer B1 decrease towards the West direction, they decrease from 23.0 Ωm to 16.0 Ωm; and its thicknesses increase towards the SE direction from 12.0 m to 18.0 m. Whereas, the resistivity values of the geoelectric layer B2 decrease towards the NW direction from 40.0 Ωm to 26.5 Ωm; and its thicknesses vary from 34.0 m to 40.0 m. The depths to the upper surface of the water bearing layer B1 increase towards the NW direction from 44.0 m to 89.4 m. Based on the results obtained from the Vertical Electrical Soundings, four two-dimensional resistivity imaging profiles were measured at the selected sites. These 2-D resistivity profiles aim to determine depths to the water bearing layers, their thicknesses and the shallow structure. The inverted models of these profiles matched with the geoelectric sequence at these sites. In addition, a normal fault is detected at the northwestern part of the study area. According to the results obtained from this study it is clear that the groundwater in the area under consideration is occurred in the fractured limestone layers that belong to Eocene Age. Resistivity values of the water bearing layers increase with depth as a result of decreasing fracture density; and these values decreased towards the northwestern direction due to their proximity from the fault zone. The groundwater potential of these layers depends mainly on the lithologic composition and the geological structures affecting these layers. The secondary porosity of these limestone layers depends mainly on the degree of fracturing and fissuring. The proper sites to drill new productive wells were recommended, and the obtained data from drilling new well in the southeastern part of the study area coincide with the interpreted data of the different geophysical techniques.

Capillary transport of water through textile-reinforced concrete applied in repairing and/or strengthening cracked RC structures

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

Lieboldt, M.; Mechtcherine, V., E-mail: mechtcherine@tu-dresden.de

2013-10-15

The use of textile-reinforced concrete (TRC) has great potential for innovative solutions in repairing, protecting, and strengthening concrete and RC structures. The article at hand reports on an investigation on composite concrete specimens made of cracked ordinary concrete as substrate and textile-reinforced concrete (TRC) as a cover layer for its strengthening and repair. The TRC cover layer was assessed with regard to its effectiveness as a protective layer against the ingress of water through capillary action. Since in real applications such TRC layers may be cracked or presumed to be so, thereby activating the load-carrying function of the textile reinforcement,more » the TRC layer was cracked for purposes of this study. The water transport in the cracked ordinary concrete specimens without the TRC layer was used as a reference. Gravimetric measurements and neutron radiography served as the testing techniques. In ordinary concrete quick and deep ingress of water through relatively wide macro-cracks of approximately 100 μm width, followed by transport through the capillary pore system, caused saturation of large areas in a rather short time. TRC applied to the RC surface reduced the ingress of water to a large extent. Its small crack widths of 15 to 20 μm changed suction behaviour fundamentally. In the cracked substrate of ordinary concrete, capillary suction was prevented, and transport through the pore system of the matrix became the prevailing transport mechanism of capillary action. Not only was the mechanism altered, but the transport of water deep into inner regions was markedly retarded as well.« less

Large-Scale Synthesis and Comprehensive Structure Study of δ-MnO 2

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

Liu, Jue; Yu, Lei; Hu, Enyuan

Layered δ-MnO 2 (birnessites) are ubiquitous in nature and have also been reported to work as promising water oxidation catalysts or rechargeable alkali-ion battery cathodes when fabricated under appropriate conditions. Although tremendous effort has been spent on resolving the structure of natural/synthetic layered δ-MnO 2 in the last few decades, no conclusive result has been reached. In this Article, we report an environmentally friendly route to synthesizing homogeneous Cu-rich layered δ-MnO 2 nanoflowers in large scale. The local and average structure of synthetic Cu-rich layered δ-MnO 2 has been successfully resolved from combined Mn/Cu K-edge extended X-ray fine structure spectroscopymore » and X-ray and neutron total scattering analysis. It is found that appreciable amounts (~8%) of Mn vacancies are present in the MnO 2 layer and Cu 2+ occupies the interlayer sites above/below the vacant Mn sites. Effective hydrogen bonding among the interlayer water molecules and adjacent layer O ions has also been observed for the first time. These hydrogen bonds are found to play the key role in maintaining the intermediate and long-range stacking coherence of MnO 2 layers. Quantitative analysis of the turbostratic stacking disorder in this compound was achieved using a supercell approach coupled with anisotropic particle-size-effect modeling. Furthermore, the present method is expected to be generally applicable to the structural study of other technologically important nanomaterials.« less

Large-Scale Synthesis and Comprehensive Structure Study of δ-MnO 2

DOE PAGES

Liu, Jue; Yu, Lei; Hu, Enyuan; ...

2018-05-30

Layered δ-MnO 2 (birnessites) are ubiquitous in nature and have also been reported to work as promising water oxidation catalysts or rechargeable alkali-ion battery cathodes when fabricated under appropriate conditions. Although tremendous effort has been spent on resolving the structure of natural/synthetic layered δ-MnO 2 in the last few decades, no conclusive result has been reached. In this Article, we report an environmentally friendly route to synthesizing homogeneous Cu-rich layered δ-MnO 2 nanoflowers in large scale. The local and average structure of synthetic Cu-rich layered δ-MnO 2 has been successfully resolved from combined Mn/Cu K-edge extended X-ray fine structure spectroscopymore » and X-ray and neutron total scattering analysis. It is found that appreciable amounts (~8%) of Mn vacancies are present in the MnO 2 layer and Cu 2+ occupies the interlayer sites above/below the vacant Mn sites. Effective hydrogen bonding among the interlayer water molecules and adjacent layer O ions has also been observed for the first time. These hydrogen bonds are found to play the key role in maintaining the intermediate and long-range stacking coherence of MnO 2 layers. Quantitative analysis of the turbostratic stacking disorder in this compound was achieved using a supercell approach coupled with anisotropic particle-size-effect modeling. Furthermore, the present method is expected to be generally applicable to the structural study of other technologically important nanomaterials.« less

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.

The mean and turbulent flow structure of a weak hydraulic jump

NASA Astrophysics Data System (ADS)

Misra, S. K.; Kirby, J. T.; Brocchini, M.; Veron, F.; Thomas, M.; Kambhamettu, C.

2008-03-01

The turbulent air-water interface and flow structure of a weak, turbulent hydraulic jump are analyzed in detail using particle image velocimetry measurements. The study is motivated by the need to understand the detailed dynamics of turbulence generated in steady spilling breakers and the relative importance of the reverse-flow and breaker shear layer regions with attention to their topology, mean flow, and turbulence structure. The intermittency factor derived from turbulent fluctuations of the air-water interface in the breaker region is found to fit theoretical distributions of turbulent interfaces well. A conditional averaging technique is used to calculate ensemble-averaged properties of the flow. The computed mean velocity field accurately satisfies mass conservation. A thin, curved shear layer oriented parallel to the surface is responsible for most of the turbulence production with the turbulence intensity decaying rapidly away from the toe of the breaker (location of largest surface curvature) with both increasing depth and downstream distance. The reverse-flow region, localized about the ensemble-averaged free surface, is characterized by a weak downslope mean flow and entrainment of water from below. The Reynolds shear stress is negative in the breaker shear layer, which shows that momentum diffuses upward into the shear layer from the flow underneath, and it is positive just below the mean surface indicating a downward flux of momentum from the reverse-flow region into the shear layer. The turbulence structure of the breaker shear layer resembles that of a mixing layer originating from the toe of the breaker, and the streamwise variations of the length scale and growth rate are found to be in good agreement with observed values in typical mixing layers. All evidence suggests that breaking is driven by a surface-parallel adverse pressure gradient and a streamwise flow deceleration at the toe of the breaker. Both effects force the shear layer to thicken rapidly, thereby inducing a sharp free surface curvature change at the toe.

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.)

Autonomous Sensing of Layered Structures in Hawaiian Waters

DTIC Science & Technology

2007-09-30

APPROACH In March of 2007 we were awarded $112,842 for the fabrication of an autonomous profiler (the SeaHorse ) for the detection of thin layers of...phytoplankton in the coastal ocean. The SeaHorse (Figures 1, 2) makes use of wave energy to power extended, high-resolution profiling of water...the sample rate of the SeaHorse profiler itself. For example, if we observe a layer at 10 m depth, we can instruct the profiler to maintain this

Using a bias aware EnKF to account for unresolved structure in an unsaturated zone model

NASA Astrophysics Data System (ADS)

Erdal, D.; Neuweiler, I.; Wollschläger, U.

2014-01-01

When predicting flow in the unsaturated zone, any method for modeling the flow will have to define how, and to what level, the subsurface structure is resolved. In this paper, we use the Ensemble Kalman Filter to assimilate local soil water content observations from both a synthetic layered lysimeter and a real field experiment in layered soil in an unsaturated water flow model. We investigate the use of colored noise bias corrections to account for unresolved subsurface layering in a homogeneous model and compare this approach with a fully resolved model. In both models, we use a simplified model parameterization in the Ensemble Kalman Filter. The results show that the use of bias corrections can increase the predictive capability of a simplified homogeneous flow model if the bias corrections are applied to the model states. If correct knowledge of the layering structure is available, the fully resolved model performs best. However, if no, or erroneous, layering is used in the model, the use of a homogeneous model with bias corrections can be the better choice for modeling the behavior of the system.

Structure and Dynamical Influence of Water Vapor in the Lower Tropical Troposphere

NASA Astrophysics Data System (ADS)

Stevens, Bjorn; Brogniez, Hélène; Kiemle, Christoph; Lacour, Jean-Lionel; Crevoisier, Cyril; Kiliani, Johannes

In situ, airborne and satellite measurements are used to characterize the structure of water vapor in the lower tropical troposphere—below the height, z *, of the triple-point isotherm, T *. The measurements are evaluated in light of understanding of how lowertropospheric water vapor influences clouds, convection and circulation, through both radiative and thermodynamic effects. Lower-tropospheric water vapor, which concentrates in the first few kilometers above the boundary layer, controls the radiative cooling profile of the boundary layer and lower troposphere. Elevated moist layers originating from a preferred level of convective detrainment induce a profile of radiative cooling that drives circulations which reinforce such features. A theory for this preferred level of cumulus termination is advanced, whereby the difference between T * and the temperature at which primary ice forms gives a `first-mover advantage' to glaciating cumulus convection, thereby concentrating the regions of the deepest convection and leading to more clouds and moisture near the triple point. A preferred level of convective detrainment near T * implies relative humidity reversals below z * which are difficult to identify using retrievals from satellite-borne microwave and infrared sounders. Isotopologues retrievals provide a hint of such features and their ability to constrain the structure of the vertical humidity profile merits further study. Nonetheless, it will likely remain challenging to resolve dynamically important aspects of the vertical structure of water vapor from space using only passive sensors.

Structure and Dynamical Influence of Water Vapor in the Lower Tropical Troposphere

NASA Astrophysics Data System (ADS)

Stevens, Bjorn; Brogniez, Hélène; Kiemle, Christoph; Lacour, Jean-Lionel; Crevoisier, Cyril; Kiliani, Johannes

2017-11-01

In situ, airborne and satellite measurements are used to characterize the structure of water vapor in the lower tropical troposphere—below the height, z_*, of the triple-point isotherm, T_*. The measurements are evaluated in light of understanding of how lower-tropospheric water vapor influences clouds, convection and circulation, through both radiative and thermodynamic effects. Lower-tropospheric water vapor, which concentrates in the first few kilometers above the boundary layer, controls the radiative cooling profile of the boundary layer and lower troposphere. Elevated moist layers originating from a preferred level of convective detrainment induce a profile of radiative cooling that drives circulations which reinforce such features. A theory for this preferred level of cumulus termination is advanced, whereby the difference between T_* and the temperature at which primary ice forms gives a `first-mover advantage' to glaciating cumulus convection, thereby concentrating the regions of the deepest convection and leading to more clouds and moisture near the triple point. A preferred level of convective detrainment near T_* implies relative humidity reversals below z* which are difficult to identify using retrievals from satellite-borne microwave and infrared sounders. Isotopologues retrievals provide a hint of such features and their ability to constrain the structure of the vertical humidity profile merits further study. Nonetheless, it will likely remain challenging to resolve dynamically important aspects of the vertical structure of water vapor from space using only passive sensors.

A two-dimensional hydrogen-bonded water layer in the structure of a cobalt(III) cubane complex.

PubMed

Qi, Ji; Zhai, Xiang-Sheng; Zhu, Hong-Lin; Lin, Jian-Li

2014-02-01

A tetranuclear Co(III) oxide complex with cubane topology, tetrakis(2,2'-bipyridine-κ(2)N,N')di-μ2-carbonato-κ(4)O:O'-tetra-μ3-oxido-tetracobalt(III) pentadecahydrate, [Co4(CO3)2O4(C10H8N2)4]·15H2O, with an unbounded hydrogen-bonded water layer, has been synthesized by reaction of CoCO3 and 2,2'-bipyridine. The solvent water molecules form a hydrogen-bonded net with tetrameric and pentameric water clusters as subunits. The Co4O4 cubane-like cores are sandwiched between the water layers, which are further stacked into a three-dimensional metallo-supramolecular network.

Remote sensing of the boundary layer over the oceans. [by IRIS measurements

NASA Technical Reports Server (NTRS)

Prabhakara, C.; Dalu, G.; Nath, N. R.; Lo, R.

1978-01-01

The paper explores the possibility of remotely sensing the boundary layer structure over the oceans by means of the Nimbus 4 IR Interferometric Spectrometer (IRIS) measurements in the water vapor bands. It is found from theoretical considerations that the moderately strong spectral lines in the 9-micron water vapor window region contain useful information about the lowest layers in the atmosphere. The difference between the observed line strength and the theoretically predicted line strength provides information about the departure in the atmospheric temperature and water vapor profiles from standard conditions. The observations of METEOR oceanographic expedition over the North and South Atlantic, and the Indian Ocean expedition make it possible to model the inversion conditions. It is concluded that significant characteristics of the temperature and water vapor profiles in the boundary layer of the atmosphere can be remotely sensed using the water vapor spectral measurements over the oceans.

Theory of lidar method for measurement of the modulation transfer function of water layers.

PubMed

Dolin, Lev S

2013-01-10

We develop a method to evaluate the modulation transfer function (MTF) of a water layer from the characteristics of lidar signal backscattered by water volume. We propose several designs of a lidar system for remote measurement of the MTF and the procedure to determine optical properties of water using the measured MTF. We discuss a laser system for sea-bottom imaging that accounts for the influence of water slab on the image structure and allows for correction of image distortions caused by light scattering in water. © 2013 Optical Society of America

Time-dependent water dynamics in hydrated uranyl fluoride

DOE PAGES

Miskowiec, Andrew J.; Anderson, Brian B.; Herwig, Kenneth W.; ...

2015-09-15

In this study, uranyl fluoride is a three-layer, hexagonal structure with significant stacking disorder in the c-direction. It supports a range of unsolved ‘thermodynamic’ hydrates with 0–2.5 water molecules per uranium atom, and perhaps more. However, the relationship between water, hydrate crystal structures, and thermodynamic results, collectively representing the chemical pathway through these hydrate structures, has not been sufficiently elucidated. We used high-resolution quasielastic neutron scattering to study the dynamics of water in partially hydrated uranyl fluoride powder over the course of 4 weeks under closed conditions. The spectra are composed of two quasielastic components: one is associated with translationalmore » diffusive motion of water that is approximately five to six times slower than bulk water, and the other is a slow (on the order of 2–300 ps), spatially bounded water motion. The translational component represents water diffusing between the weakly bonded layers in the crystal, while the bounded component may represent water trapped in subnanometre ‘pockets’ formed by the space between uranium-centred polymerisation units. Complementary neutron diffraction measurements do not show any significant structural changes, suggesting that a chemical conversion of the material does not occur in the thermodynamically isolated system on this timescale.« less

Electric-field-induced structural changes in water confined between two graphene layers

NASA Astrophysics Data System (ADS)

Sobrino Fernández, Mario; Peeters, F. M.; Neek-Amal, M.

2016-07-01

An external electric field changes the physical properties of polar liquids due to the reorientation of their permanent dipoles. Using molecular dynamics simulations, we predict that an in-plane electric field applied parallel to the channel polarizes water molecules which are confined between two graphene layers, resulting in distinct ferroelectricity and electrical hysteresis. We found that electric fields alter the in-plane order of the hydrogen bonds: Reversing the electric field does not restore the system to the nonpolar initial state, instead a residual dipole moment remains in the system. The square-rhombic structure of 2D ice is transformed into two rhombic-rhombic structures. Our study provides insights into the ferroelectric state of water when confined in nanochannels and shows how this can be tuned by an electric field.

Hybrid inorganic–organic superlattice structures with atomic layer deposition/molecular layer deposition

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

Tynell, Tommi; Yamauchi, Hisao; Karppinen, Maarit, E-mail: maarit.karppinen@aalto.fi

2014-01-15

A combination of the atomic layer deposition (ALD) and molecular layer deposition (MLD) techniques is successfully employed to fabricate thin films incorporating superlattice structures that consist of single layers of organic molecules between thicker layers of ZnO. Diethyl zinc and water are used as precursors for the deposition of ZnO by ALD, while three different organic precursors are investigated for the MLD part: hydroquinone, 4-aminophenol and 4,4′-oxydianiline. The successful superlattice formation with all the organic precursors is verified through x-ray reflectivity studies. The effects of the interspersed organic layers/superlattice structure on the electrical and thermoelectric properties of ZnO are investigatedmore » through resistivity and Seebeck coefficient measurements at room temperature. The results suggest an increase in carrier concentration for small concentrations of organic layers, while higher concentrations seem to lead to rather large reductions in carrier concentration.« less

Optimum design for effective water transport through a double-layered porous hydrogel inspired by plant leaves

NASA Astrophysics Data System (ADS)

Kim, Hyejeong; Kim, Hyeonjeong; Huh, Hyungkyu; Hwang, Hyung Ju; Lee, Sang Joon

2014-11-01

Plant leaves are generally known to have optimized morphological structure in response to environmental changes for efficient water usage. However, the advantageous features of plant leaves are not fully utilized in engineering fields yet, since the optimum design in internal structure of plant leaves is unclear. In this study, the tissue organization of the hydraulic pathways inside plant leaves was investigated. Water transport through double-layered porous hydrogel models analogous to mesophyll cells was experimentally observed. In addition, computational experiment and theoretical analysis were applied to the model systems to find the optimal design for efficient water transport. As a result, the models with lower porosity or with pores distributed widely in the structure exhibit efficient mass transport. Our theoretical prediction supports that structural features of plant leaves guarantee sufficient water supply as survival strategy. This study may provide a new framework for investigating the biophysical principles governing the morphological optimization of plant leaves and for designing microfluidic devices to enhance mass transport ability. This study was supported by the National Research Foundation of Korea and funded by the Korean government.

Pervaporation dehydration of ethanol by hyaluronic acid/sodium alginate two-active-layer composite membranes.

PubMed

Gao, Chengyun; Zhang, Minhua; Ding, Jianwu; Pan, Fusheng; Jiang, Zhongyi; Li, Yifan; Zhao, Jing

2014-01-01

The composite membranes with two-active-layer (a capping layer and an inner layer) were prepared by sequential spin-coatings of hyaluronic acid (HA) and sodium alginate (NaAlg) on the polyacrylonitrile (PAN) support layer. The SEM showed a mutilayer structure and a distinct interface between the HA layer and the NaAlg layer. The coating sequence of two-active-layer had an obvious influence on the pervaporation dehydration performance of membranes. When the operation temperature was 80 °C and water concentration in feed was 10 wt.%, the permeate fluxes of HA/Alg/PAN membrane and Alg/HA/PAN membrane were similar, whereas the separation factor were 1130 and 527, respectively. It was found that the capping layer with higher hydrophilicity and water retention capacity, and the inner layer with higher permselectivity could increase the separation performance of the composite membranes. Meanwhile, effects of operation temperature and water concentration in feed on pervaporation performance as well as membrane properties were studied. Copyright © 2013 Elsevier Ltd. All rights reserved.

Small-scale seismogenic soft sediment deformation (Hirlatzhöhle, Upper Austria)

NASA Astrophysics Data System (ADS)

Salomon, Martina Lan; Grasemann, Bernhard; Plan, Lukas; Gier, Susanne

2014-05-01

The Hirlatz Cave lies in the Dachstein Massif about 2 km SW of Hallstatt, in the Upper Austrian Salzkammergut. With a length of 101 km, this karst cave, located in the Dachstein nappe (Northern Calcareous Alps), is the second largest known cave system in Austria. Within the cave, in the so-called Lehmklamm, located 2.8 km southeast of the cave entrance, laminated (mm-scale) Quaternary clay-sized sediments with interbedded fine-grained sandy layers are preserved. In these layers, numerous soft sediment deformation structures are preserved in many layers. The unconsolidated sediments show rhythmic layering of brighter, carbonate and quartz rich, and darker, more clay mineral rich horizontal varve-like layers, that are assumed to be fluvio-lacustrine deposits. The present study focuses on a very detailed documentation of an approximately 6.8 x 3 m vertical outcrop that was cut by a small brook. Centimeter to millimeter sized water escape structures (intruded cusps and flame structures), folds (detachment folds, fault bend folds) and faults (normal faults, fault propagation folds, bookshelf faults) are described. Because of the geometric analogy to seismogenic structures which have been described at two orders of magnitude larger scales from areas close to the Dead Sea Fault, we suggest that the formation of the investigated soft-sediment structures was also triggered by seismic events. The structures were mainly formed by three different mechanism: (i) North directed gravitational gliding near the sediment surface; (ii) Liquefaction resulting in a density discontinuity and decreasing in shear strength within in the stratified layers; (iii) Extensional faulting that cut through the stratified layers. Observations of coarsening upwards into sandy layers on the top of the outcrop and current ripple indicate a north-directed flow under phreatic conditions, which is opposite to the present flow direction of the vadose water in the cave. The fact that deformation and erosion mostly occur in the uppermost meter of the outcrop wall suggests a higher seismic activity and at least periodically higher flow rates during sedimentation of the younger deposits. Since several extremely deformed layers occur between undeformed ones, we suggest that deformation of the layers occurred only in the uppermost highly water saturated sediments and that several seismic events lead to the formation of the observed structures. A possible source responsible for the seismic event is the Salzach-Ennstal-Mariazeller-Puchberger (SEMP) strike-slip fault, which accommodates the active extrusion of the Eastern Alps towards the Pannonian Basin.

A Study for the Restoration of Hong Dae-Yong Honsangui - Focusing on the structure and operating mechanism

NASA Astrophysics Data System (ADS)

Lee, Yong Sam; Kim, Sang Hyuk; Park, Je Hoon

2013-09-01

Honsangui (celestial globe) which is a water-hammering method astronomical clock is recorded in "Juhaesuyong" which is Volume VI of supplement from "Damheonseo", written by Hong Dae-Yong (1731~1783). We made out the conceptual design of Hong Dae-Yong's Honsangui through the study on its structure and working mechanism. Honsangui consist of three rings and two layers, the structure of rings which correspond to outer layer is similar to his own Tongcheonui (armillary sphere) which is a kind of armillary sphere. Honsang sphere which correspond to inner layer depicts constellations and milky way and two beads hang on it as Sun and Moon respectively for realize the celestial motion. Tongcheonui is operated by the pendulum power but Honsangui is operated by water-hammering method mechanism. This Honsangui's working mechanism is the traditional way of Joseon and it was simplified the working mechanism of Shui y'n i hsiang t'ai which is a representative astronomical clock of China. This record of Honsangui is the only historical record about the water-hammering method working mechanism of Joseon Era and it provide the study of water-hammering method mechanism with a vital clue.

Ground-Water Levels and Soil Characteristics in a Forested Typic Glossaqualf

Treesearch

Peter L. Lorio

1977-01-01

The presence of impermeable layers can affect the development of a soil and its water regime. In a forested Typic Glossaqualf in southwest Louisiana, moisture, density, and piezometer measurements revealed an impermeable layer of soil between about 1.8 and 2.8 m below the surface. A high proportion of very fine sand and development of platy structure appeared related...

New Extra-Solar Planet - thermal state and structure

NASA Astrophysics Data System (ADS)

Valencia, D.; O'Connell, R. J.; Sasselov, D.

2005-12-01

For the last decade astronomers have found more than 160 planets orbiting stars other than our sun. All but three of them are gaseous planets. The variety of characteristics of these newly discovered planets opens a new field with questions about planetary formation, structure and evolution, as well as the possibility of existence of life beyond our solar system. Planetary formation models suggested the existence of terrestrial extra-solar planets with masses up to 10 times the mass of the Earth. In June of 2005 the first Super-Earth was discovered orbiting a star 15 light years away with a mass that is about 7.5 times the mass of the Earth and a period of 1.94 days. The composition of this planet is unknown but probably has an Earth-like composition. Astronomers believe the surface temperature ranges between ~500 K and ~700 K. Liquid water can exist at temperatures above T=400K at high pressures (above 10 MPa) allowing for the possibility of a water layer on top of a rocky core. Our work focuses on determining scaling relationships with mass, internal structure parameters and thermal state. We explore the effects of a water/icy layer above a rocky core as well as other types of compositions in determining the internal structure. This water layer may convect causing the planet to have two layer convection. We explore the effects of a layer convection mode versus whole mantle convection for a Super-Earth. Due to the closeness of this planet to its parent star we can expect substantial tidal heating that can affect the thermal state of this planet. We explore the effects of tidal heating in the internal structure of a planet. Differences in composition have much larger effects in the mass-radius relationship than the uncertainties in thermodynamic parameters of the minerals composing the planet.

Water at protein surfaces studied with femtosecond nonlinear spectroscopy

NASA Astrophysics Data System (ADS)

Bakker, Huib J.

We report on an investigation of the structure and dynamics of water molecules near protein surfaces with femtosecond nonlinear spectroscopic techniques. We measured the reorientation dynamics of water molecules near the surface of several globular protein surfaces, using polarization-resolved femtosecond infrared spectroscopy. We found that water molecules near the protein surface have a much slower reorientation than water molecules in bulk liquid water. The number of slow water molecules scales scales with the size of the hydrophobic surface of the protein. When we denature the proteins by adding an increasing amount of urea to the protein solution, we observe that the water-exposed surface increases by 50% before the secondary structure of the proteins changes. This finding indicates that protein unfolding starts with the protein structure becoming less tight, thereby allowing water to enter. With surface vibrational sum frequency generation (VSFG) spectroscopy, we studied the structure of water at the surface of antifreeze protein III. The measured VSFG spectra showed the presence of ice-like water layers at the ice-binding site of the protein in aqueous solution, at temperatures well above the freezing point. This ordered ice-like hydration layers at the protein surface likely plays an important role in the specific recognition and binding of anti-freeze protein III to nascent ice crystallites, and thus in its anti-freeze mechanism. This research is supported by the ''Nederlandse organisatie voor Wetenschappelijk Onderzoek (NWO).

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

Gil, D.M.; Osiry, H.; Pomiro, F.

The hydrogen bond and π-π stacking are two non-covalent interactions able to support cooperative magnetic ordering between paramagnetic centers. This contribution reports the crystal structure and related magnetic properties for VO[Fe(CN){sub 5}NO]·2H{sub 2}O, which has a layered structure. This solid crystallizes with an orthorhombic unit cell, in the Pna2{sub 1} space group, with cell parameters a=14.1804(2), b=10.4935(1), c=7.1722(8) Å and four molecules per unit cell (Z=4). Its crystal structure was solved and refined from powder X-ray diffraction data. Neighboring layers remain linked through a network of hydrogen bonds involving a water molecule coordinated to the axial position for the Vmore » atom and the unbridged axial NO and CN ligands. An uncoordinated water molecule is found forming a triple bridge between these last two ligands and the coordinated water molecule. The magnetic measurements, recorded down to 2 K, shows a ferromagnetic interaction between V atoms located at neighboring layers, with a Curie-Weiss constant of 3.14 K. Such ferromagnetic behavior was interpreted as resulting from a superexchange interaction through the network of strong OH····O{sub H2O}, OH····N{sub CN}, and OH····O{sub NO} hydrogen bonds that connects neighboring layers. The interaction within the layer must be of antiferromagnetic nature and it was detected close to 2 K. - Graphical abstract: Coordination environment for the metals in vanadyl (II) nitroprusside dihydrate. Display Omitted - Highlights: • Crystal structure of vanadyl nitroprusside dehydrate. • Network of hydrogen bonds. • Magnetic interactions through a network of hydrogen bonds. • Layered transition metal nitroprussides.« less

Skin lipid structure controls water permeability in snake molts.

PubMed

Torri, Cristian; Mangoni, Alfonso; Teta, Roberta; Fattorusso, Ernesto; Alibardi, Lorenzo; Fermani, Simona; Bonacini, Irene; Gazzano, Massimo; Burghammer, Manfred; Fabbri, Daniele; Falini, Giuseppe

2014-01-01

The role of lipids in controlling water exchange is fundamentally a matter of molecular organization. In the present study we have observed that in snake molt the water permeability drastically varies among species living in different climates and habitats. The analysis of molts from four snake species: tiger snake, Notechis scutatus, gabon viper, Bitis gabonica, rattle snake, Crotalus atrox, and grass snake, Natrix natrix, revealed correlations between the molecular composition and the structural organization of the lipid-rich mesos layer with control in water exchange as a function of temperature. It was discovered, merging data from micro-diffraction and micro-spectroscopy with those from thermal, NMR and chromatographic analyses, that this control is generated from a sophisticated structural organization that changes size and phase distribution of crystalline domains of specific lipid molecules as a function of temperature. Thus, the results of this research on four snake species suggest that in snake skins different structured lipid layers have evolved and adapted to different climates. Moreover, these lipid structures can protect, "safety", the snakes from water lost even at temperatures higher than those of their usual habitat. Copyright © 2013 Elsevier Inc. All rights reserved.

What Does a Multilayer Canopy Model Tell Us About Our Current Understanding of Snow-Canopy Unloading?

NASA Astrophysics Data System (ADS)

McGowan, L. E.; Paw U, K. T.; Dahlke, H. E.

2017-12-01

In the Western U.S., future water resources depend on the forested mountain snowpack. The variations in and estimates of forest mountain snow volume are vital to projecting annual water availability; yet, snow forest processes are not fully known. Most snow models calculate snow-canopy unloading based on time, temperature, Leaf Area Index (LAI), and/or wind speed. While models crudely consider the canopy shape via LAI, current models typically do not consider the vertical canopy structure or varied energetics within multiple canopy layers. Vertical canopy structure influences the spatiotemporal distribution of snow, and therefore ultimately determines the degree and extent by which snow alters both the surface energy balance and water availability. Within the canopy both the snowpack and energetic exposures to the snowpack (wind, shortwave and longwave radiation, turbulent heat fluxes etc.) vary widely in the vertical. The water and energy balance in each layer is dependent on all other layers. For example, increased snow canopy content in the top of the canopy will reduce available shortwave radiation at the bottom and snow unloading in a mid-layer can cascade and remove snow from all the lower layers. We examined vertical interactions and structures of the forest canopy on the impact of unloading utilizing the Advanced Canopy-Atmosphere-Soil-Algorithm (ACASA), a multilayer soil-vegetation-atmosphere numerical model based on higher-order closure of turbulence equations. Our results demonstrate how a multilayer model can be used to elucidate the physical processes of snow unloading, and could help researchers better parameterize unloading in snow-hydrology models.

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

Stern Layer Structure and Energetics at Mica-Water Interfaces

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

Bourg, Ian C.; Lee, Sang Soo; Fenter, Paul

2017-04-11

The screening of surface charge by dissolved ions at solid liquid interfaces in the region of interfacial fluid known as the electrical double layer (EDL)-plays a recurrent role in surface science, from ion adsorption to colloidal mechanics to the transport properties of nanoporous media. A persistent unknown in theories of EDL-related phenomena is the structure of the Stern layer, the near-surface portion of the EDL where water molecules and adsorbed ions form specific short-range interactions with surface atoms. Here, we describe a set of synchrotron X-ray reflectivity (XRR) experiments and molecular dynamics (MD) simulations carried out under identical conditions formore » a range of 0.1 M alkali chloride (Li-, Na-, K-, Rb-, or CsCl) solutions on the basal surface of muscovite mica, a mineral isostructural to phyllosilicate clay minerals and one of the most widely studied reference surfaces in interfacial science. Our XRR and MD simulation results provide a remarkably consistent view of the structure and energetics of the Stern layer, with some discrepancy on the fraction of the minor outer-sphere component of Rb and on the adsorption energetics of Li. The results of both techniques, along with surface complexation model calculations, provide insight into the sensitivity of water structure and ion adsorption to surface topography and the type of adsorbed counterion.« less

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

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

What Governs Friction of Silicon Oxide in Humid Environment: Contact Area between Solids, Water Meniscus around the Contact, or Water Layer Structure?

PubMed

Chen, Lei; Xiao, Chen; Yu, Bingjun; Kim, Seong H; Qian, Linmao

2017-09-26

In order to understand the interfacial parameters governing the friction force (F t ) between silicon oxide surfaces in humid environment, the sliding speed (v) and relative humidity (RH) dependences of F t were measured for a silica sphere (1 μm radius) sliding on a silicon oxide (SiO x ) surface, using atomic force microscopy (AFM), and analyzed with a mathematical model describing interfacial contacts under a dynamic condition. Generally, F t decreases logarithmically with increasing v to a cutoff value below which its dependence on interfacial chemistry and sliding condition is relatively weak. Above the cutoff value, the logarithmic v dependence could be divided into two regimes: (i) when RH is lower than 50%, F t is a function of both v and RH; (ii) in contrast, at RH ≥ 50%, F t is a function of v only, but not RH. These complicated v and RH dependences were hypothesized to originate from the structure of the water layer adsorbed on the surface and the water meniscus around the annulus of the contact area. This hypothesis was tested by analyzing F t as a function of the water meniscus area (A m ) and volume (V m ) estimated from a thermally activated water-bridge formation model. Surprisingly, it was found that F t varies linearly with V m and correlates poorly with A m at RH < 50%; and then its V m dependence becomes weaker as RH increases above 50%. Comparing the friction data with the attenuated total reflection infrared (ATR-IR) spectroscopy analysis result of the adsorbed water layer, it appeared that the solidlike water layer structure formed on the silica surface plays a critical role in friction at RH < 50% and its contribution diminishes at RH ≥ 50%. These findings give a deeper insight into the role of water condensation in friction of the silicon oxide single asperity contact under ambient conditions.

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.

Production of a textile reinforced concrete protective layers with non-woven polypropylene fabric

NASA Astrophysics Data System (ADS)

Žák, J.; Štemberk, P.; Vodička, J.

2017-09-01

Textile concrete with nonwoven polypropylene fabric can be used for protective layers of reinforced concrete structures, reducing the thickness of the cover layer or reducing the water penetration rate into the structure. The material consists of cement matrix with finegrained aggregate and nonwoven textile reinforcement. The maximum grain size of the mixture suitable for the nonwoven textile infiltration is 0.25 mm. The interlayer contains larger aggregates and short fibers. Tensile loading causes a large amount of microcracks in the material. The material can withstand strain over 25% without collapsing. Increased quality and water-cement ratio reduction was achieved using the plasticizers and distribution of the mixture into a fabric using a vibrating trowel. It is possible to make flat plates and even curved structures from this material. Larger curvatures of structures should be solved by cutting and overlapping the fabric. Small curvatures can be solved within the deformability of the fabric. Proper infiltration of the cement mixture into the fabric is the most important task in producing this material.

Ordered microporous layered lanthanide 1,3,5-benzenetriphosphonates pillared with cationic organic molecules.

PubMed

Araki, Takahiro; Kondo, Atsushi; Maeda, Kazuyuki

2015-04-13

Novel isomorphous pillared-layer-type crystalline lanthanide 1,3,5-benzenetriphosphonates were prepared with bpy and dbo as organic pillars (LnBP-bpy and LnBP-dbo; Ln: Ce, Pr, and Nd). Ab initio crystal structure solution using synchrotron X-ray powder diffraction data revealed that the organic pillars do not exist as neutral coordinating ligands but as cationic molecules. Especially the LnBP-dbo phases have ordered interlayer space filled with water molecules between the dbo pillars, and the interlayer water is successfully removed by heating under vacuum with slightly distorted but basically retained pillared layer structures. Microporosity of the materials is confirmed by adsorption of nitrogen, carbon dioxide, and hydrogen gases. Such microporous layered metal phosphonates pillared with cationic molecules should be unprecedented and should offer new strategies to design ordered microporous materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Well logging evaluation of water-flooded layers and distribution rule of remaining oil in marine sandstone reservoirs of the M oilfield in the Pearl River Mouth basin

NASA Astrophysics Data System (ADS)

Li, Xiongyan; Qin, Ruibao; Gao, Yunfeng; Fan, Hongjun

2017-03-01

In the marine sandstone reservoirs of the M oilfield the water cut is up to 98%, while the recovery factor is only 35%. Additionally, the distribution of the remaining oil is very scattered. In order to effectively assess the potential of the remaining oil, the logging evaluation of the water-flooded layers and the distribution rule of the remaining oil are studied. Based on the log response characteristics, the water-flooded layers can be qualitatively identified. On the basis of the mercury injection experimental data of the evaluation wells, the calculation model of the initial oil saturation is built. Based on conventional logging data, the evaluation model of oil saturation is established. The difference between the initial oil saturation and the residual oil saturation can be used to quantitatively evaluate the water-flooded layers. The evaluation result of the water-flooded layers is combined with the ratio of the water-flooded wells in the marine sandstone reservoirs. As a result, the degree of water flooding in the marine sandstone reservoirs can be assessed. On the basis of structural characteristics and sedimentary environments, the horizontal and vertical water-flooding rules of the different types of reservoirs are elaborated upon, and the distribution rule of the remaining oil is disclosed. The remaining oil is mainly distributed in the high parts of the structure. The remaining oil exists in the top of the reservoirs with good physical properties while the thickness of the remaining oil ranges from 2-5 m. However, the thickness of the remaining oil of the reservoirs with poor physical properties ranges from 5-8 m. The high production of some of the drilled horizontal wells shows that the above distribution rule of the remaining oil is accurate. In the marine sandstone reservoirs of the M oilfield, the research on the well logging evaluation of the water-flooded layers and the distribution rule of the remaining oil has great practical significance to the prediction of the distribution of the remaining oil and the optimization of well locations.

Nutrient interleaving below the mixed layer of the Kuroshio Extension Front

NASA Astrophysics Data System (ADS)

Nagai, Takeyoshi; Clayton, Sophie

2017-08-01

Nitrate interleaving structures were observed below the mixed layer during a cruise to the Kuroshio Extension in October 2009. In this paper, we investigate the formation mechanisms for these vertical nitrate anomalies, which may be an important source of nitrate to the oligotrphoc surface waters south of the Kuroshio Extension Front. We found that nitrate concentrations below the main stream of the Kuroshio Extension were elevated compared to the ambient water of the same density ( σ 𝜃 = 23.5-25). This appears to be analogous to the "nutrient stream" below the mixed layer, associated with the Gulf Stream. Strong turbulence was observed above the vertical nitrate anomaly, and we found that this can drive a large vertical turbulent nitrate flux >O (1 mmol N m-2 day-1). A realistic, high-resolution (2 km) numerical simulation reproduces the observed Kuroshio nutrient stream and nitrate interleaving structures, with similar lateral and vertical scales. The model results suggest that the nitrate interleaving structures are first generated at the western side of the meander crest on the south side of the Kuroshio Extension, where the southern tip of the mixed layer front is under frontogenesis. Lagrangian analyses reveal that the vertical shear of geostrophic and subinertial ageostrophic flow below the mixed layer tilts the existing along-isopycnal nitrate gradient of the Kuroshio nutrient stream to form nitrate interleaving structures. This study suggests that the multi-scale combination of (i) the lateral stirring of the Kuroshio nutrient stream by developed mixed layer fronts during fall to winter, (ii) the associated tilting of along-isopycnal nitrate gradient of the nutrient stream by subinertial shear, which forms vertical interleaving structures, and (iii) the strong turbulent diffusion above them, may provide a route to supply nutrients to oligotrophic surface waters on the south side of the Kuroshio Extension.

In silico studies of the properties of water hydrating a small protein

NASA Astrophysics Data System (ADS)

Sinha, Sudipta Kumar; Jana, Madhurima; Chakraborty, Kausik; Bandyopadhyay, Sanjoy

2014-12-01

Atomistic molecular dynamics simulation of an aqueous solution of the small protein HP-36 has been carried out with explicit solvent at room temperature. Efforts have been made to explore the influence of the protein on the relative packing and ordering of water molecules around its secondary structures, namely, three α-helices. The calculations reveal that the inhomogeneous water ordering and density distributions around the helices are correlated with their relative hydrophobicity. Importantly, we have identified the existence of a narrow relatively dehydrated region containing randomly organized "quasi-free" water molecules beyond the first layer of "bound" waters at the protein surface. These water molecules with relatively weaker binding energies form the transition state separating the "bound" and "free" water molecules at the interface. Further, increased contribution of solid-like caging motions of water molecules around the protein is found to be responsible for reduced fluidity of the hydration layer. Interestingly, we notice that the hydration layer of helix-3 is more fluidic with relatively higher entropy as compared to the hydration layers of the other two helical segments. Such characteristics of helix-3 hydration layer correlate well with the activity of HP-36, as helix-3 contains the active site of the protein.

Effect of Carbon in the Dielectric Fluid and Workpieces on the Characteristics of Recast Layers Machined by Electrical Discharge Machining

NASA Astrophysics Data System (ADS)

Muttamara, Apiwat; Kanchanomai, Chaosuan

2016-06-01

Electrical discharge machining (EDM) is a popular non-traditional machining technique that is usually performed in kerosene. Carbon from the kerosene is mixed into the recast layer during EDM, increasing its hardness. EDM can be performed in deionized water, which causes decarburization. We studied the effects of carbon in the dielectric fluid and workpiece on the characteristics of recast layers. Experiments were conducted using gray cast iron and mild steel workpieces in deionized water or kerosene under identical operating conditions. Scanning electron microscopy revealed that the recast layer formed on gray iron was rougher than that produced on mild steel. Moreover, the dispersion of graphite flakes in the gray iron seemed to cause subsurface cracks, even when EDM was performed in deionized water. Dendritic structures and iron carbides were found in the recast layer of gray iron treated in deionized water. Kerosene caused more microcracks to form and increased surface roughness compared with deionized water. The microcrack length per unit area of mild steel treated in deionized water was greater than that treated in kerosene, but the cracks formed in kerosene were wider. The effect of the diffusion of carbon during cooling on the characteristics of the recast layer was discussed.

Unlocking the relationship of biotic integrity of impaired waters to anthropogenic stresses.

PubMed

Novotny, Vladimir; Bartosová, Alena; O'Reilly, Neal; Ehlinger, Timothy

2005-01-01

The Clean Water Act expressed its goals in terms of restoring and preserving the physical, chemical and biological integrity of the Nation's waters. Integrity has been defined as the ability of the water body's ecological system to support and maintain a balanced integrated, adaptive community of organisms comparable to that of a natural biota of the region. Several indices of biotic integrity (IBIs) have been developed to measure quantitatively the biotic composition and, hence, the integrity. Integrity can be impaired by discharges of pollutants from point and nonpoint sources and by other pollution-related to watershed/landscape and channel stresses, including channel and riparian zone modifications and habitat impairment. Various models that link the stressors to the biotic assessment endpoints, i.e., the IBIs, have been presented and discussed. Simple models that link IBIs directly to single or multiple surrogate stressors such as percent imperviousness are inadequate because they may not represent a true cause-effect proximate relationship. Furthermore, some surrogate landscape parameters are irreversible and the relationships cannot be used for development of plans for restoration of the water body integrity. A concept of a layered hierarchical model that will link the watershed, landscape and stream morphology pollution stressors to the biotic assessment endpoints (IBIs) is described. The key groups of structural components of the model are: IBIs and their metrics in the top layer, chemical water and sediment risks and a habitat quality index in the layer below, in-stream concentrations in water and sediments and channel/habitat impairment parameters in the third layer, and watershed/landscaper pollution generating stressors, land use change rates, and hydrology in the lowest layer of stressors. A modified and expanded Maximum Species Richness concept is developed and used to reveal quantitatively the functional relationships between the top two layers of the structural components and parameters of the model.

A new type of artificial structure to achieve broadband omnidirectional acoustic absorption

NASA Astrophysics Data System (ADS)

Zheng, Li-Yang; Wu, Ying; Zhang, Xiao-Liu; Ni, Xu; Chen, Ze-Guo; Lu, Ming-Hui; Chen, Yan-Feng

2013-10-01

We present a design for a two-dimensional omnidirectional acoustic absorber that can achieve 98.6% absorption of acoustic waves in water, forming an effective acoustic black hole. This artificial black hole consists of an absorptive core coated with layers of periodically distributed polymer cylinders embedded in water. Effective medium theory describes the response of the coating layers to the acoustic waves. The polymer parameters can be adjusted, allowing practical fabrication of the absorber. Since the proposed structure does not rely on resonances, it is applicable to broad bandwidths. The design might be extended to a variety of applications.

Ice-like water supports hydration forces and eases sliding friction

PubMed Central

Dhopatkar, Nishad; Defante, Adrian P.; Dhinojwala, Ali

2016-01-01

The nature of interfacial water is critical in several natural processes, including the aggregation of lipids into the bilayer, protein folding, lubrication of synovial joints, and underwater gecko adhesion. The nanometer-thin water layer trapped between two surfaces has been identified to have properties that are very different from those of bulk water, but the molecular cause of such discrepancy is often undetermined. Using surface-sensitive sum frequency generation (SFG) spectroscopy, we discover a strongly coordinated water layer confined between two charged surfaces, formed by the adsorption of a cationic surfactant on the hydrophobic surfaces. By varying the adsorbed surfactant coverage and hence the surface charge density, we observe a progressively evolving water structure that minimizes the sliding friction only beyond the surfactant concentration needed for monolayer formation. At complete surfactant coverage, the strongly coordinated confined water results in hydration forces, sustains confinement and sliding pressures, and reduces dynamic friction. Observing SFG signals requires breakdown in centrosymmetry, and the SFG signal from two oppositely oriented surfactant monolayers cancels out due to symmetry. Surprisingly, we observe the SFG signal for the water confined between the two charged surfactant monolayers, suggesting that this interfacial water layer is noncentrosymmetric. The structure of molecules under confinement and its macroscopic manifestation on adhesion and friction have significance in many complicated interfacial processes prevalent in biology, chemistry, and engineering. PMID:27574706

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.

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

Corrosion behavior of oxide dispersion strengthened ferritic steels in supercritical water

NASA Astrophysics Data System (ADS)

Gao, Wenhua; Guo, Xianglong; Shen, Zhao; Zhang, Lefu

2017-04-01

The corrosion resistance of three different Cr content oxide dispersion strengthened (ODS) ferritic steels in supercritical water (SCW) and their passive films formed on the surface have been investigated. The results show that the dissolved oxygen (DO) and chemical composition have significant influence on the corrosion behavior of the ODS ferritic steels. In 2000 ppb DO SCW at 650 °C, the 14Cr-4Al ODS steel forms a tri-layer oxide film and the surface morphologies have experienced four structures. For the tri-layer oxide film, the middle layer is mainly Fe-Cr spinel and the Al is gradually enriched in the inner layer.

A unique form of light reflector and the evolution of signalling in Ovalipes (Crustacea: Decapoda: Portunidae)

PubMed Central

Parker, A. R.; Mckenzie, D. R.; Ahyong, S. T.

1998-01-01

The first demonstration, to our knowledge, of an evolutionary shift in communication mode in animals is presented. Some species of Ovalipes display spectacular iridescence resulting from multilayer reflectors in the cuticle. This reflector is unique in animals because each layer is corrugated and slightly out of phase with adjacent layers. Solid layers are separated from fluid layers in the reflector by side branches acting as support struts. An effect of this reflector is that blue light is reflected over a 'broad' angle around a plane parallel to the sea floor when the host crab is resting. Species of Ovalipes all possess stridulatory structures. The shallow-water species with the best developed stridulatory structures are non-iridescent and use sound as a signal. Deep-water species possess poorly developed stridulatory structures and display iridescence from most regions of the body. In deep water, where incident light is blue, light display is highly directional in contrast to sound produced via stridulation. Sound and light display probably perform the same function of sexual signalling in Ovalipes, although the directional signal is less likely to attract predators. Deep-water species of Ovalipes appear to have evolved towards using light in conspecific signalling. This change from using sound to using light reflects the change in habitat light properties, perhaps the hunting mechanisms of cohabitees, and its progression is an indicator of phylogeny. The changes in sexual signalling mechanisms, following spatial–geographical isolation, may have promoted speciation in Ovalipes.

Origin of the 'dike-like' structure and transitions in eruptive styles at Colton Crater, northern Arizona: San Francisco Volcanic Field REU

NASA Astrophysics Data System (ADS)

Witter, M. R.; Ort, M. H.; Leudemann, L. A.

2013-12-01

Colton Crater, located within the San Francisco Volcanic Field (SFVF) in northern Arizona, is one of over 600 scoria cones in the field. Unlike most other volcanoes in the SFVF, Colton Crater is characterized as a hybrid volcano that had Strombolian, Hawaiian, and Surtseyan explosions. Surtseyan explosions led to the excavation of the center of the volcano, creating a large 1.3-km-diameter crater with a 30-m post-phreatomagmatic scoria cone at its center. A vertical erosion-resistant feature along the northern rim of the crater, originally mapped as a dike, provides valuable information about the sequence and timing of the transition to phreatomagmatic eruptions because it disrupts the otherwise continuous spatter layers deposited just prior to that change. Stratigraphic sections and paleomagnetic analysis of Colton Crater reveal the origin and timing of emplacement of this vertical structure and its place in the transitional eruptive history. The prominent upper layers in the crater walls show some variation throughout the crater, but generally are composed of agglutinated spatter, welded scoria and bombs, and rootless lava flows. The uppermost portion of the outward-dipping spatter layers that lie between the two saddles on the northern rim closely match the layers observed in the vertical structure, revealing that the structure is a section of rotated spatter. The characteristic remanent magnetization (ChRM), identified using alternating field (AF) demagnetization, shows the timing of the displacement of sections of the agglutinated spatter and welded cinder. Sites along the vertical structure yield ChRMs statistically identical to non-rotated sites, which indicates that rotation of the vertical structure occurred before the ChRM had been set, i.e., the layers were above the Curie temperature during rotation. The eruption started as Strombolian and Hawaiian perhaps because the flux of magma overpowered the influx of water from local aquifer formations, creating a stable and sealed conduit. Lava flows associated with the Strombolian and Hawaiian activity breached the northern flank and destabilized the walls of the crater. Water may have been introduced to the magmatic system through conduit collapse beneath the water table or vent migration to a conduit location with greater water flux, leading to the Surtseyan explosions. As space was created on the northern rim, the destabilized spatter layers detached and rotated, creating the vertical structure. The eruption ended with a small Strombolian phase, forming the 30-m-high scoria cone in the bottom of the crater. The sequence of these events must have happened within a short time period because the rotated spatter layers of the vertical structure remained above 580 oC.

Evaluating the importance of characterizing soil structure and horizons in parameterizing a hydrologic process model

USGS Publications Warehouse

Mirus, Benjamin B.

2015-01-01

Incorporating the influence of soil structure and horizons into parameterizations of distributed surface water/groundwater models remains a challenge. Often, only a single soil unit is employed, and soil-hydraulic properties are assigned based on textural classification, without evaluating the potential impact of these simplifications. This study uses a distributed physics-based model to assess the influence of soil horizons and structure on effective parameterization. This paper tests the viability of two established and widely used hydrogeologic methods for simulating runoff and variably saturated flow through layered soils: (1) accounting for vertical heterogeneity by combining hydrostratigraphic units with contrasting hydraulic properties into homogeneous, anisotropic units and (2) use of established pedotransfer functions based on soil texture alone to estimate water retention and conductivity, without accounting for the influence of pedon structures and hysteresis. The viability of this latter method for capturing the seasonal transition from runoff-dominated to evapotranspiration-dominated regimes is also tested here. For cases tested here, event-based simulations using simplified vertical heterogeneity did not capture the state-dependent anisotropy and complex combinations of runoff generation mechanisms resulting from permeability contrasts in layered hillslopes with complex topography. Continuous simulations using pedotransfer functions that do not account for the influence of soil structure and hysteresis generally over-predicted runoff, leading to propagation of substantial water balance errors. Analysis suggests that identifying a dominant hydropedological unit provides the most acceptable simplification of subsurface layering and that modified pedotransfer functions with steeper soil-water retention curves might adequately capture the influence of soil structure and hysteresis on hydrologic response in headwater catchments.

Structure and dynamics of water inside hydrophobic and hydrophilic nanotubes

NASA Astrophysics Data System (ADS)

Köhler, Mateus Henrique; Bordin, José Rafael; da Silva, Leandro B.; Barbosa, Marcia C.

2018-01-01

We have used Molecular Dynamics simulations to investigate the structure and dynamics of TIP4P/2005 water confined inside nanotubes. The nanotubes have distinct sizes and were built with hydrophilic or hydrophobic sites, and we compare the water behavior inside each nanotube. Our results shows that the structure and dynamics are strongly influenced by polarity inside narrow nanotubes, where water layers were observed, and the influence is negligible for wider nanotubes, where the water has a bulk-like density profile. As well, we show that water at low density can have a smaller diffusion inside nanotubes than water at higher densities. This result is a consequence of water diffusion anomaly.

Bifurcation structure of a wind-driven shallow water model with layer-outcropping

NASA Astrophysics Data System (ADS)

Primeau, François W.; Newman, David

The steady state bifurcation structure of the double-gyre wind-driven ocean circulation is examined in a shallow water model where the upper layer is allowed to outcrop at the sea surface. In addition to the classical jet-up and jet-down multiple equilibria, we find a new regime in which one of the equilibrium solutions has a large outcropping region in the subpolar gyre. Time dependent simulations show that the outcropping solution equilibrates to a stable periodic orbit with a period of 8 months. Co-existing with the periodic solution is a stable steady state solution without outcropping. A numerical scheme that has the unique advantage of being differentiable while still allowing layers to outcrop at the sea surface is used for the analysis. In contrast, standard schemes for solving layered models with outcropping are non-differentiable and have an ill-defined Jacobian making them unsuitable for solution using Newton's method. As such, our new scheme expands the applicability of numerical bifurcation techniques to an important class of ocean models whose bifurcation structure had hitherto remained unexplored.

Lyotropic chromonic liquid crystals as materials for optical and biosensing applications

NASA Astrophysics Data System (ADS)

Tortora, L.; Park, H.-S.; Antion, K.; Finotello, D.; Lavrentovich, O. D.

2007-02-01

Lyotropic chromonic liquid crystals (LCLCs) are formed by molecules with rigid polyaromatic cores and ionic groups at the periphery that form aggregates while in water. Most of the LCLCs are not toxic to the biological cells and can be used as an amplifying medium in real-time biosensors. The detector is based on the principle that the immune aggregates growing in the LCLC bulk trigger the director distortions. Self-assembly of LCLC molecules into oriented structures allows one to use them in various structured films. For example, layer-by-layer electrostatic deposition produces monomolecular layers and stacks of layers of LCLC with long-range in-plane orientational order which sets them apart from the standard Langmuir-Blodgett films. We demonstrate that divalent and multivalent salts as well as acidic and basic materials that alter pH of the LCLC water solutions, are drastically modifying the phase diagrams of LCLC, from shifting the phase transition temperatures by tens of degrees, to causing condensation of the LCLC aggregates into more compact structures, such as birefringent bundles or formation of a columnar hexagonal phase from the nematic phase.

The Density and Refractive Index of Adsorbing Protein Layers

PubMed Central

Vörös, Janos

2004-01-01

The structure of the adsorbing layers of native and denatured proteins (fibrinogen, γ-immunoglobulin, albumin, and lysozyme) was studied on hydrophilic TiO2 and hydrophobic Teflon-AF surfaces using the quartz crystal microbalance with dissipation and optical waveguide lightmode spectroscopy techniques. The density and the refractive index of the adsorbing protein layers could be determined from the complementary information provided by the two in situ instruments. The observed density and refractive index changes during the protein-adsorption process indicated the presence of conformational changes (e.g., partial unfolding) in general, especially upon contact with the hydrophobic surface. The structure of the formed layers was found to depend on the size of the proteins and on the experimental conditions. On the TiO2 surface smaller proteins formed a denser layer than larger ones and the layer of unfolded proteins was less dense than that adsorbed from the native conformation. The hydrophobic surface induced denaturation and resulted in the formation of thin compact protein films of albumin and lysozyme. A linear correlation was found between the quartz crystal microbalance measured dissipation factor and the total water content of the layer, suggesting the existence of a dissipative process that is related to the solvent molecules present inside the adsorbed protein layer. Our measurements indicated that water and solvent molecules not only influence the 3D structure of proteins in solution but also play a crucial role in their adsorption onto surfaces. PMID:15240488

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.

Impact origin of sediments at the Opportunity landing site on Mars.

PubMed

Knauth, L Paul; Burt, Donald M; Wohletz, Kenneth H

2005-12-22

Mars Exploration Rover Opportunity discovered sediments with layered structures thought to be unique to aqueous deposition and with minerals attributed to evaporation of an acidic salty sea. Remarkable iron-rich spherules were ascribed to later groundwater alteration, and the inferred abundance of water reinforced optimism that Mars was once habitable. The layered structures, however, are not unique to water deposition, and the scenario encounters difficulties in accounting for highly soluble salts admixed with less soluble salts, the lack of clay minerals from acid-rock reactions, high sphericity and near-uniform sizes of the spherules and the absence of a basin boundary. Here we present a simple alternative explanation involving deposition from a ground-hugging turbulent flow of rock fragments, salts, sulphides, brines and ice produced by meteorite impact. Subsequent weathering by intergranular water films can account for all of the features observed without invoking shallow seas, lakes or near-surface aquifers. Layered sequences observed elsewhere on heavily cratered Mars and attributed to wind, water or volcanism may well have formed similarly. If so, the search for past life on Mars should be reassessed accordingly.

Molecular dynamics study of structure and vibrational spectra at zwitterionoic lipid/aqueous KCl, NaCl, and CaCl2 solution interfaces

NASA Astrophysics Data System (ADS)

Ishiyama, Tatsuya; Shirai, Shinnosuke; Okumura, Tomoaki; Morita, Akihiro

2018-06-01

Molecular dynamics (MD) simulations of KCl, NaCl, and CaCl2 solution/dipalmytoylphosphatidylcholine lipid interfaces were performed to analyze heterodyne-detected vibrational sum frequency generation (HD-VSFG) spectra in relation to the interfacial water structure. The present MD simulation well reproduces the experimental spectra and elucidates a specific cation effect on the interfacial structure. The K+, Na+, and Ca2+ cation species penetrate in the lipid layer more than the anions in this order, due to the electrostatic interaction with negative polar groups of lipid, and the electric double layer between the cations and anions cancels the intrinsic orientation of water at the water/lipid interface. These mechanisms explain the HD-VSFG spectrum of the water/lipid interface and its spectral perturbation by adding the ions. The lipid monolayer reverses the order of surface preference of the cations at the solution/lipid interface from that at the solution/air interface.

Influences of layer thickness on the compatibility and physical properties of polycarbonate/polystyrene multilayered film via nanolayer coextrusion

NASA Astrophysics Data System (ADS)

Cheng, Junfeng; Chen, Zhiru; Zhou, Jiaqi; Cao, Zheng; Wu, Dun; Liu, Chunlin; Pu, Hongting

2018-05-01

The effects of layer thickness on the compatibility between polycarbonate (PC) and polystyrene (PS) and physical properties of PC/PS multilayered film via nanolayer coextrusion are studied. The morphology of multilayered structure is observed using a scanning electron microscope. This multilayered structure may have a negative impact on the transparency, but it can improve the water resistance and heat resistance of film. To characterize the compatibility between PC and PS, differential scanning calorimetry is used to measure the glass transition temperature. The compatibility is found to be improved with the decrease of layer thickness. Therefore, the viscosity of multilayered film is also reduced with the decrease of layer thickness. In addition, the multilayered structure can improve the tensile strength with the increase of layer numbers. Because of the complete and continuous layer structure of PC, the PC/PS multilayered film can retain its mechanical strength at the temperature above Tg of PS.

Driving force behind adsorption-induced protein unfolding: a time-resolved X-ray reflectivity study on lysozyme adsorbed at an air/water interface.

PubMed

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

2009-01-06

Time-resolved X-ray reflectivity measurements for lysozyme (LSZ) adsorbed at an air/water interface were performed to study the mechanism of adsorption-induced protein unfolding. The time dependence of the density profile at the air/water interface revealed that the molecular conformation changed significantly during adsorption. Taking into account previous work using Fourier transform infrared (FTIR) spectroscopy, we propose that the LSZ molecules initially adsorbed on the air/water interface have a flat unfolded structure, forming antiparallel beta-sheets as a result of hydrophobic interactions with the gas phase. In contrast, as adsorption continues, a second layer forms in which the molecules have a very loose structure having random coils as a result of hydrophilic interactions with the hydrophilic groups that protrude from the first layer.

Water types and their relaxation behavior in partially rehydrated CaFe-mixed binary oxide obtained from CaFe-layered double hydroxide in the 155-298 K temperature range.

PubMed

Bugris, Valéria; Haspel, Henrik; Kukovecz, Ákos; Kónya, Zoltán; Sipiczki, Mónika; Sipos, Pál; Pálinkó, István

2013-10-29

Heat-treated CaFe-layered double hydroxide samples were equilibrated under conditions of various relative humidities (11%, 43% and 75%). Measurements by FT-IR and dielectric relaxation spectroscopies revealed that partial to full reconstruction of the layered structure took place. Water types taking part in the reconstruction process were identified via dielectric relaxation measurements either at 298 K or on the flash-cooled (to 155 K) samples. The dynamics of water molecules at the various positions was also studied by this method, allowing the flash-cooled samples to warm up to 298 K.

Highly stable thin film transistors using multilayer channel structure

NASA Astrophysics Data System (ADS)

Nayak, Pradipta K.; Wang, Zhenwei; Anjum, D. H.; Hedhili, M. N.; Alshareef, H. N.

2015-03-01

We report highly stable gate-bias stress performance of thin film transistors (TFTs) using zinc oxide (ZnO)/hafnium oxide (HfO2) multilayer structure as the channel layer. Positive and negative gate-bias stress stability of the TFTs was measured at room temperature and at 60 °C. A tremendous improvement in gate-bias stress stability was obtained in case of the TFT with multiple layers of ZnO embedded between HfO2 layers compared to the TFT with a single layer of ZnO as the semiconductor. The ultra-thin HfO2 layers act as passivation layers, which prevent the adsorption of oxygen and water molecules in the ZnO layer and hence significantly improve the gate-bias stress stability of ZnO TFTs.

An Assessment of Southern Ocean Water Masses and Sea Ice During 1988-2007 in a Suite of Interannual CORE-II Simulations

NASA Technical Reports Server (NTRS)

Downes, Stephanie M.; Farneti, Riccardo; Uotila, Petteri; Griffies, Stephen M.; Marsland, Simon J.; Bailey, David; Behrens, Erik; Bentsen, Mats; Bi, Daohua; Biastoch, Arne;

Connecting Interface Structure to Energy Level Alignment at Aqueous Semiconductor Interfaces

NASA Astrophysics Data System (ADS)

Hybertsen, Mark

Understanding structure-function relationships at aqueous semiconductor interfaces presents fundamental challenges, including the discovery of the key interface structure motifs themselves. Important examples include the alignment of electrochemical redox levels with the semiconductor band edges and the identification of catalytic active sites. We have developed a multistep approach, initially demonstrated for GaN, ZnO and their alloys, motivated by measured high efficiency for photocatalytic water oxidation. The interface structure is simulated using ab initio molecular dynamics (AIMD). The calculated, average interface dipole is combined with the GW approach from many-body perturbation theory to calculate the energy level alignment between the semiconductor band edges and the centroid of the occupied 1b1 energy level of water and thus, the electrochemical levels. Cluster models are used to study reaction pathways. The emergent interface motif is the full (GaN) or partial (ZnO) dissociated interface water layer. Here I will focus on the aqueous interfaces to the stable TiO2 anatase (101) and rutile (110) facets. The AIMD calculations reveal interface water dissociation and reassociation processes through distinct pathways: one direct at the interface and the other via a spectator water molecule from the hydration layer. Comparisons between the two interfaces shows that the energy landscape for these pathways depends on the local hydrogen bonding patterns and the interplay with the interface template. Combined results from different initial conditions and AIMD temperatures demonstrate a partially dissociated interface water layer in both cases. Specifically for rutile, structure and the GW-based analysis of the interface energy level alignment agree with experiment. Finally, hole localization at different interface structure motifs will be discussed. Work performed in collaboration with J. Lyons, N. Kharche, M. Ertem and J. Muckerman, done in part at the CFN, which is a U.S. DOE Office of Science Facility, at BNL under Contract No. DE-SC0012704 and with resources from NERSC under Contract No. DE-AC02-05CH11231.

Mesozoic Compressional Folds of the Nansha Waters, Southern South China Sea

NASA Astrophysics Data System (ADS)

Zhu, R.; Liu, H.; Yao, Y.; Wang, Y.

2017-12-01

As an important part of the South China Sea, the southern margin of the South China Sea is fundamental to understand the interaction of the Eurasian, Pacific and Indian-Australian plates and the evolution of the South China Sea. Some multi-channel seismic profiles of the Nansha waters together with published drillings and dredge data were correlated for interpretation. The strata of the study region can be divided into the upper, middle and lower structural layers. The upper and middle structural layers with extensional tectonics are Cenozoic; the lower structural layer suffered compression is Mesozoic. Further structural restoration was done to remove the Cenozoic tectonic influence and to calculate the Mesozoic tectonic compression ratios. The results indicate that two diametrically opposite orientations of compressive stress, S(S)E towards N(N)W orientation and N(N)W towards S(S)E orientation respectively, once existed in the lower structural layer of the study area and shared the same variation trend. The compression ratio values gradually decrease both from the north to the south and from the west to the east in each stress orientation. The phenomena may be related to the opening of the proto-South China Sea (then located in south of the Nansha block) and the rate of the Nansha block drifted northward in Late Jurassic to Late Cretaceous, which had pushed the Nansha block drifted northward until it collided and sutured with the Southern China Margin. Thus the opening of the present-day South China Sea may be related to this suture zone, which was tectonically weakness zone.Key words: Mesozoic compression; structural restoration; proto-South China Sea; Nansha waters; Southern South China Sea; Acknowledgements: The work was granted by the National Natural Science Foundation of China (Grant Nos. 41476039, 91328205, 41576068 and 41606080).

The electrochemistry of "solid/water" interfaces involved in PEM-H2O reactors: part I. The "Pt/water" interfaces.

PubMed

Wang, Qiang; Cha, Chuan-Sin; Lu, Juntao; Zhuang, Lin

2009-01-28

The nature and properties of Pt surfaces in contact with pure water in PEM-H2O reactors were mimetically studied by employing CV measurements with microelectrode techniques. These "Pt/water" interfaces were found to be electrochemically polarizable, and the local interfacial potential relative to reversible hydrogen electrode (RHE) potential in pure water is numerically the same as the potential value measured against a RHE in contact with PEM as the reference electrode. However, the structural parameters of the electric double layer at the "Pt/water" interfaces can be quite different from those at the "Pt/PEM" interfaces, and the kinetics of electrode processes could be seriously affected by the structure of electric double layer in pure water media. Besides, there is active diffusional flow of intermediates of electrode reactions between the "Pt/water" and the "Pt/PEM" interfaces, thus facilitating the active involvement of the "Pt/water" interfaces in the current-generation mechanism of PEM fuel cells and other types of PEM-H2O reactors.

Direct Imaging of Individual Intrinsic Hydration Layers on Lipid Bilayers at Ångstrom Resolution

PubMed Central

Fukuma, Takeshi; Higgins, Michael J.; Jarvis, Suzanne P.

2007-01-01

The interactions between water and biological molecules have the potential to influence the structure, dynamics, and function of biological systems, hence the importance of revealing the nature of these interactions in relation to the local biochemical environment. We have investigated the structuring of water at the interface of supported dipalmitoylphosphatidylcholine bilayers in the gel phase in phosphate buffer solution using frequency modulation atomic force microscopy (FM-AFM). We present experimental results supporting the existence of intrinsic (i.e., surface-induced) hydration layers adjacent to the bilayer. The force versus distance curves measured between the bilayer and the AFM tip show oscillatory force profiles with a peak spacing of 0.28 nm, indicative of the existence of up to two hydration layers next to the membrane surface. These oscillatory force profiles reveal the molecular-scale origin of the hydration force that has been observed between two apposing lipid bilayers. Furthermore, FM-AFM imaging at the water/lipid interface visualizes individual hydration layers in three dimensions, with molecular-scale corrugations corresponding to the lipid headgroups. The results demonstrate that the intrinsic hydration layers are stable enough to present multiple energy barriers to approaching nanoscale objects, such as proteins and solvated ions, and are expected to affect membrane permeability and transport. PMID:17325013

Al{sub 2}O{sub 3} multi-density layer structure as a moisture permeation barrier deposited by radio frequency remote plasma atomic layer deposition

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

Jung, Hyunsoo; Samsung Display Co. Ltd., Tangjeong, Chungcheongnam-Do 336-741; Jeon, Heeyoung

2014-02-21

Al{sub 2}O{sub 3} films deposited by remote plasma atomic layer deposition have been used for thin film encapsulation of organic light emitting diode. In this study, a multi-density layer structure consisting of two Al{sub 2}O{sub 3} layers with different densities are deposited with different deposition conditions of O{sub 2} plasma reactant time. This structure improves moisture permeation barrier characteristics, as confirmed by a water vapor transmission rate (WVTR) test. The lowest WVTR of the multi-density layer structure was 4.7 × 10{sup −5} gm{sup −2} day{sup −1}, which is one order of magnitude less than WVTR for the reference single-density Al{submore » 2}O{sub 3} layer. This improvement is attributed to the location mismatch of paths for atmospheric gases, such as O{sub 2} and H{sub 2}O, in the film due to different densities in the layers. This mechanism is analyzed by high resolution transmission electron microscopy, elastic recoil detection, and angle resolved X-ray photoelectron spectroscopy. These results confirmed that the multi-density layer structure exhibits very good characteristics as an encapsulation layer via location mismatch of paths for H{sub 2}O and O{sub 2} between the two layers.« less

Sensitivity of polarization fluctuations to the nature of protein-water interactions: Study of biological water in four different protein-water systems

NASA Astrophysics Data System (ADS)

Ghosh, Rikhia; Banerjee, Saikat; Hazra, Milan; Roy, Susmita; Bagchi, Biman

2014-12-01

Since the time of Kirkwood, observed deviations in magnitude of the dielectric constant of aqueous protein solution from that of neat water (˜80) and slower decay of polarization have been subjects of enormous interest, controversy, and debate. Most of the common proteins have large permanent dipole moments (often more than 100 D) that can influence structure and dynamics of even distant water molecules, thereby affecting collective polarization fluctuation of the solution, which in turn can significantly alter solution's dielectric constant. Therefore, distance dependence of polarization fluctuation can provide important insight into the nature of biological water. We explore these aspects by studying aqueous solutions of four different proteins of different characteristics and varying sizes, chicken villin headpiece subdomain (HP-36), immunoglobulin binding domain protein G (GB1), hen-egg white lysozyme (LYS), and Myoglobin (MYO). We simulate fairly large systems consisting of single protein molecule and 20000-30000 water molecules (varied according to the protein size), providing a concentration in the range of ˜2-3 mM. We find that the calculated dielectric constant of the system shows a noticeable increment in all the cases compared to that of neat water. Total dipole moment auto time correlation function of water ⟨δMW(0)δMW(t)⟩ is found to be sensitive to the nature of the protein. Surprisingly, dipole moment of the protein and total dipole moment of the water molecules are found to be only weakly coupled. Shellwise decomposition of water molecules around protein reveals higher density of first layer compared to the succeeding ones. We also calculate heuristic effective dielectric constant of successive layers and find that the layer adjacent to protein has much lower value (˜50). However, progressive layers exhibit successive increment of dielectric constant, finally reaching a value close to that of bulk 4-5 layers away. We also calculate shellwise orientational correlation function and tetrahedral order parameter to understand the local dynamics and structural re-arrangement of water. Theoretical analysis providing simple method for calculation of shellwise local dielectric constant and implication of these findings are elaborately discussed in the present work.

Growth history of cultured pearl oysters based on stable oxygen isotope analysis

NASA Astrophysics Data System (ADS)

Nakashima, R.; Furuta, N.; Suzuki, A.; Kawahata, H.; Shikazono, N.

2007-12-01

We investigated the oxygen isotopic ratio in shells of the pearl oyster Pinctada martensii cultivated in embayments in Mie Prefecture, central Japan, to evaluate the biomineralization of shell structures of the species and its pearls in response to environmental change. Microsamples for oxygen isotope analysis were collected from the surfaces of shells (outer, middle, and inner shell layers) and pearls. Water temperature variations were estimated from the oxygen isotope values of the carbonate. Oxygen isotope profiles of the prismatic calcite of the outer shell layer reflected seasonal variations of water temperature, whereas those of nacreous aragonites of the middle and inner shell layers and pearls recorded temperatures from April to November, June to September, and July to September, respectively. Lower temperatures in autumn and winter might slow the growth of nacreous aragonites. The oxygen isotope values are controlled by both variations of water temperature and shell structures; the prismatic calcite of this species is useful for reconstructing seasonal changes of calcification temperature.

Effect of phase inversion on microporous structure development of Al 2O 3/poly(vinylidene fluoride-hexafluoropropylene)-based ceramic composite separators for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Jeong, Hyun-Seok; Kim, Dong-Won; Jeong, Yeon Uk; Lee, Sang-Young

To improve the thermal shrinkage of the separators that are essential to securing the electrical isolation between electrodes in lithium-ion batteries, we develop a new separator based on a ceramic composite membrane. Introduction of microporous, ceramic coating layers onto both sides of a polyethylene (PE) separator allows such a progress. The ceramic coating layers consist of nano-sized alumina (Al 2O 3) powders and polymeric binders (PVdF-HFP). The microporous structure of the ceramic coating layers is observed to be crucial to governing the thermal shrinkage as well as the ionic transport of the ceramic composite separators. This microporous structure is determined by controlling the phase inversion, more specifically, nonsolvent (water) contents in the coating solutions. To provide a theoretical basis for this approach, a pre-investigation on the phase diagram for a ternary mixture comprising PVdF-HFP, acetone, and water is conducted. On the basis of this observation, the effect of phase inversion on the morphology and air permeability (i.e. Gurley value) of ceramic coating layers is systematically discussed. In addition, to explore the application of ceramic composite separators to lithium-ion batteries, the influence of the structural change in the coating layers on the thermal shrinkage and electrochemical performance of the separators is quantitatively identified.

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.

Stable Ordering in Langmuir-Blodgett Films

NASA Astrophysics Data System (ADS)

Takamoto, Dawn Y.; Aydil, Eray; Zasadzinski, Joseph A.; Ivanova, Ani T.; Schwartz, Daniel K.; Yang, Tinglu; Cremer, Paul S.

2001-08-01

Defects in the layering of Langmuir-Blodgett (LB) films can be eliminated by depositing from the appropriate monolayer phase at the air-water interface. LB films deposited from the hexagonal phase of cadmium arachidate (CdA2) at pH 7 spontaneously transform into the bulk soap structure, a centrosymmetric bilayer with an orthorhombic herringbone packing. A large wavelength folding mechanism accelerates the conversion between the two structures, leading to a disruption of the desired layering. At pH > 8.5, though it is more difficult to draw LB films, almost perfect layering is obtained due to the inability to convert from the as-deposited structure to the equilibrium one.

New potentional of high-speed water jet technology for renovating concrete structures

NASA Astrophysics Data System (ADS)

Bodnárová, L.; Sitek, L.; Hela, R.; Foldyna, J.

2011-06-01

The paper discusses the background and results of research focused on the action of a high-speed water jet on concrete with different qualities. The sufficient and careful removal of degraded concrete layers is very important for the renovation of concrete structures. High-speed water jet technology is one of the most common methods used for removing degraded concrete layers. Different types of high-speed water jets were tested in the experimental part. The classical technology of a single continuous water jet generated with one nozzle was tested as well as the technology of revolving water jets generated by multiple nozzles (used mainly for the renovation of larger areas). A continuous flat water jet and pulsating flat water jet were tested the first time, because the connection of a water jet with the acoustic generator of a pulsating jet offers new possibilities for the use of a water jet (see [1] and [2]). A water jet with such a modification is capable of efficient action and can even be used for cutting solid concrete with a relatively low consumption of energy. A flat pulsating water jet which can be newly used for renovation seems to be a promising technology.

The Structure of Microbial Community and Degradation of Diatoms in the Deep Near-Bottom Layer of Lake Baikal

PubMed Central

Zakharova, Yulia R.; Galachyants, Yuri P.; Kurilkina, Maria I.; Likhoshvay, Alexander V.; Petrova, Darya P.; Shishlyannikov, Sergey M.; Ravin, Nikolai V.; Mardanov, Andrey V.; Beletsky, Alexey V.; Likhoshway, Yelena V.

2013-01-01

Insight into the role of bacteria in degradation of diatoms is important for understanding the factors and components of silica turnover in aquatic ecosystems. Using microscopic methods, it has been shown that the degree of diatom preservation and the numbers of diatom-associated bacteria in the surface layer of bottom sediments decrease with depth; in the near-bottom water layer, the majority of bacteria are associated with diatom cells, being located either on the cell surface or within the cell. The structure of microbial community in the near-bottom water layer has been characterized by pyrosequencing of the 16S rRNA gene, which has revealed 149 208 unique sequences. According to the results of metagenomic analysis, the community is dominated by representatives of Proteobacteria (41.9%), Actinobacteria (16%); then follow Acidobacteria (6.9%), Cyanobacteria (5%), Bacteroidetes (4.7%), Firmicutes (2.8%), Nitrospira (1.6%), and Verrucomicrobia (1%); other phylotypes account for less than 1% each. For 18.7% of the sequences, taxonomic identification has been possible only to the Bacteria domain level. Many bacteria identified to the genus level have close relatives occurring in other aquatic ecosystems and soils. The metagenome of the bacterial community from the near-bottom water layer also contains 16S rRNA gene sequences found in previously isolated bacterial strains possessing hydrolytic enzyme activity. These data show that potential degraders of diatoms occur among the vast variety of microorganisms in the near-bottom water of Lake Baikal. PMID:23560063

Large-eddy simulations of unidirectional water flow over dunes

NASA Astrophysics Data System (ADS)

Grigoriadis, D. G. E.; Balaras, E.; Dimas, A. A.

2009-06-01

The unidirectional, subcritical flow over fixed dunes is studied numerically using large-eddy simulation, while the immersed boundary method is implemented to incorporate the bed geometry. Results are presented for a typical dune shape and two Reynolds numbers, Re = 17,500 and Re = 93,500, on the basis of bulk velocity and water depth. The numerical predictions of velocity statistics at the low Reynolds number are in very good agreement with available experimental data. A primary recirculation region develops downstream of the dune crest at both Reynolds numbers, while a secondary region develops at the toe of the dune crest only for the low Reynolds number. Downstream of the reattachment point, on the dune stoss, the turbulence intensity in the developing boundary layer is weaker than in comparable equilibrium boundary layers. Coherent vortical structures are identified using the fluctuating pressure field and the second invariant of the velocity gradient tensor. Vorticity is primarily generated at the dune crest in the form of spanwise "roller" structures. Roller structures dominate the flow dynamics near the crest, and are responsible for perturbing the boundary layer downstream of the reattachment point, which leads to the formation of "horseshoe" structures. Horseshoe structures dominate the near-wall dynamics after the reattachment point, do not rise to the free surface, and are distorted by the shear layer of the next crest. The occasional interaction between roller and horseshoe structures generates tube-like "kolk" structures, which rise to the free surface and persist for a long time before attenuating.

4-D Model of CO2 Deposition at North and South of Mars from HEND/Odyssey and MOLA/MGS

NASA Technical Reports Server (NTRS)

Litvak, M. L.; Mitrofanov, I. G.; Kozyrev, A. S.; Sanin, A. B.; Tretyakov, V.; Smith, D. E.; Zuber, M. T.; Boynton, W. V.; Hamara, D. K.; Shinohara, C.

2003-01-01

The first 1.5 year of neutron mapping measurements onboard Mars Odyssey spacecraft are presented based on High Energy Neutron Detector (HEND) observations. HEND instrument is a part of GRS suite responsible for registration of epithermal and fast neutrons originating in Mars subsurface layer. The scattering of fast neutrons in Mars surface caused by primary cosmic rays is strongly sensitive to presence of hydrogen atoms. Even several percents of subsurface water significantly depress epithermal and fast neutron flux. It turns orbit neutron spectroscopy into one of most efficient methods for finding distribution of subsurface water. The Mars Odyssey observations revealed huge water- ice regions above 60N and 60S latitudes. It was founded that distribution of subsurface water has layered structure at these regions. It is thought that more than 50% wt water ice covered by relatively dry layer with different thickness.

Decrease in osmotically driven water flux and transport through mangrove roots after oil spills in the presence and absence of dispersants.

PubMed

Tansel, Berrin; Arreaza, Ariadna; Tansel, Derya Z; Lee, Mengshan

2015-09-15

The objective of this study was to evaluate the effect of crude oil on water transport through mangroves roots in the presence and absence of dispersants. Water transport through the roots were evaluated experimentally using red mangrove root segments exposed to salt water contaminated with Louisiana crude oil for seven days in the presence and absence of Corexit 9500A (dispersant). Experimental observations were interpreted in view of the structural integrity and fouling phenomena observed on the epidermis and endodermis layers of the roots. The effects of oil on the radial water flux through the epidermis and endodermis were analyzed using a dual layer filtration model. Progression of fouling due to accumulation and penetration of the contaminants through the root layers were interpreted in relation to observed mangrove health (long and short term effects) reported in the literature. Copyright © 2015 Elsevier Ltd. All rights reserved.

Formation and Restacking of Disordered Smectite Osmotic Hydrates

DOE PAGES

Gilbert, Benjamin; Comolli, Luis R.; Tinnacher, Ruth M.; ...

2015-12-01

Clay swelling, an important phenomenon in natural systems, can dramatically affect the properties of soils and sediments. Something of particular interest in low-salinity, saturated systems are osmotic hydrates, forms of smectite in which the layer separation greatly exceeds the thickness of a single smectite layer due to the intercalation of water. In situ X-ray diffraction (XRD) studies have shown a strong link between ionic strength and average interlayer spacing in osmotic hydrates but also indicate the presence of structural disorder that has not been fully described. In the present study the structural state of expanded smectite in sodium chloride solutionsmore » was investigated by combining very low electron dose, high-resolution cryogenic-transmission electron microscopy observations with XRD experiments. Wyoming smectite (SWy-2) was embedded in vitreous ice to evaluate clay structure in aqua. Lattice-fringe images showed that smectite equilibrated in aqueous, low-ionic-strength solutions, exists as individual smectite layers, osmotic hydrates composed of parallel layers, as well as disordered layer conformations. There was no evidence found here for edge-to-sheet attractions, but significant variability in interlayer spacing was observed. Whether this variation could be explained by a dependence of the magnitude of long-range cohesive (van der Waals) forces on the number of layers in a smectite particle was investigated here. Calculations of the Hamaker constant for layer-layer interactions showed that van der Waals forces may span at least five layers plus the intervening water and confirmed that forces vary with layer number. The drying of the disordered osmotic hydrates induced re-aggregation of the smectite to form particles that exhibited coherent scattering domains. Clay disaggregation and restacking may be considered as an example of oriented attachment, with the unusual distinction that it may be cycled repeatedly by changing solution conditions.« less

Formation and Restacking of Disordered Smectite Osmotic Hydrates

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

Gilbert, Benjamin; Comolli, Luis R.; Tinnacher, Ruth M.

Clay swelling, an important phenomenon in natural systems, can dramatically affect the properties of soils and sediments. Something of particular interest in low-salinity, saturated systems are osmotic hydrates, forms of smectite in which the layer separation greatly exceeds the thickness of a single smectite layer due to the intercalation of water. In situ X-ray diffraction (XRD) studies have shown a strong link between ionic strength and average interlayer spacing in osmotic hydrates but also indicate the presence of structural disorder that has not been fully described. In the present study the structural state of expanded smectite in sodium chloride solutionsmore » was investigated by combining very low electron dose, high-resolution cryogenic-transmission electron microscopy observations with XRD experiments. Wyoming smectite (SWy-2) was embedded in vitreous ice to evaluate clay structure in aqua. Lattice-fringe images showed that smectite equilibrated in aqueous, low-ionic-strength solutions, exists as individual smectite layers, osmotic hydrates composed of parallel layers, as well as disordered layer conformations. There was no evidence found here for edge-to-sheet attractions, but significant variability in interlayer spacing was observed. Whether this variation could be explained by a dependence of the magnitude of long-range cohesive (van der Waals) forces on the number of layers in a smectite particle was investigated here. Calculations of the Hamaker constant for layer-layer interactions showed that van der Waals forces may span at least five layers plus the intervening water and confirmed that forces vary with layer number. The drying of the disordered osmotic hydrates induced re-aggregation of the smectite to form particles that exhibited coherent scattering domains. Clay disaggregation and restacking may be considered as an example of oriented attachment, with the unusual distinction that it may be cycled repeatedly by changing solution conditions.« less

Double Layer Structure and Electrode Kinetics.

DTIC Science & Technology

1980-09-30

Extensive double layer studies were made at the water- membrane and water-mercury interfaces. The effect of the neu- tral compound phloretin , which can...used to determine the nature of the phloretin adsorption isotherm. A boxcar integration method was developed which allows us to measure short-lived...235-252. 5. R. de Levie, S. K. Rangarajan, P. F. Seelig and 0. S. Andersen, On the adsorption of phloretin onto a black lipid membrane, Biophys. J. 25

Calculation of effective transport properties of partially saturated gas diffusion layers

NASA Astrophysics Data System (ADS)

Bednarek, Tomasz; Tsotridis, Georgios

2017-02-01

A large number of currently available Computational Fluid Dynamics numerical models of Polymer Electrolyte Membrane Fuel Cells (PEMFC) are based on the assumption that porous structures are mainly considered as thin and homogenous layers, hence the mass transport equations in structures such as Gas Diffusion Layers (GDL) are usually modelled according to the Darcy assumptions. Application of homogenous models implies that the effects of porous structures are taken into consideration via the effective transport properties of porosity, tortuosity, permeability (or flow resistance), diffusivity, electric and thermal conductivity. Therefore, reliable values of those effective properties of GDL play a significant role for PEMFC modelling when employing Computational Fluid Dynamics, since these parameters are required as input values for performing the numerical calculations. The objective of the current study is to calculate the effective transport properties of GDL, namely gas permeability, diffusivity and thermal conductivity, as a function of liquid water saturation by using the Lattice-Boltzmann approach. The study proposes a method of uniform water impregnation of the GDL based on the "Fine-Mist" assumption by taking into account the surface tension of water droplets and the actual shape of GDL pores.

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.

Interior Structure of Ceres Artist Concept

NASA Image and Video Library

2016-08-03

This artist's concept shows a diagram of how the inside of Ceres could be structured, based on data about the dwarf planet's gravity field from NASA's Dawn mission. Using information about Ceres' gravity and topography, scientists found that Ceres is "differentiated," which means that it has compositionally distinct layers at different depths. The densest layer is at the core, which scientists suspect is made of hydrated silicates. Above that is a volatile-rich shell, topped with a crust of mixed materials. This research teaches scientists about what internal processes could have occurred during the early history of Ceres. It appears that, during a heating phase early in the history of Ceres, water and other light materials partially separated from rock. These light materials and water then rose to the outer layer of Ceres. http://photojournal.jpl.nasa.gov/catalog/PIA20867

Water Ice Clouds and Dust in the Martian Atmosphere Observed by Mars Climate Sounder

NASA Technical Reports Server (NTRS)

Benson, Jennifer L.; Kass, David; Heavens, Nicholas; Kleinbohl, Armin

2011-01-01

The water ice clouds are primarily controlled by the temperature structure and form at the water condensation level. Clouds in all regions presented show day/night differences. Cloud altitude varies between night and day in the SPH and tropics: (1) NPH water ice opacity is greater at night than day at some seasons (2) The diurnal thermal tide controls the daily variability. (3) Strong day/night changes indicate that the amount of gas in the atmosphere varies significantly. See significant mixtures of dust and ice at the same altitude planet-wide (1) Points to a complex radiative and thermal balance between dust heating (in the visible) and ice heating or cooling in the infrared. Aerosol layering: (1) Early seasons reveal a zonally banded spatial distribution (2) Some localized longitudinal structure of aerosol layers (3) Later seasons show no consistent large scale organization

Understanding the role of pore size homogeneity in the water transport through graphene layers.

PubMed

Su, Jiaye; Zhao, Yunzhen; Fang, Chang

2018-06-01

Graphene is a versatile 2D material and attracts an increasing amount of attention from a broad scientific community, including novel nanofluidic devices. In this work, we use molecular dynamics simulations to study the pressure driven water transport through graphene layers, focusing on the pore size homogeneity, realized by the arrangement of two pore sizes. For a given layer number, we find that water flux exhibits an excellent linear behavior with pressure, in agreement with the prediction of the Hagen-Poiseuille equation. Interestingly, the flux for concentrated pore size distribution is around two times larger than that of a uniform distribution. More surprisingly, under a given pressure, the water flux changes in an opposite way for these two distributions, where the flux ratio almost increases linearly with the layer number. For the largest layer number, more distributions suggest the same conclusion that higher water flux can be attained for more concentrated pore size distributions. Similar differences for the water translocation time and occupancy are also identified. The major reason for these results should clearly be due to the hydrogen bond and density profile distributions. Our results are helpful to delineate the exquisite role of pore size homogeneity, and should have great implications for the design of high flux nanofluidic devices and inversely the detection of pore structures.

Understanding the role of pore size homogeneity in the water transport through graphene layers

NASA Astrophysics Data System (ADS)

Su, Jiaye; Zhao, Yunzhen; Fang, Chang

2018-06-01

Graphene is a versatile 2D material and attracts an increasing amount of attention from a broad scientific community, including novel nanofluidic devices. In this work, we use molecular dynamics simulations to study the pressure driven water transport through graphene layers, focusing on the pore size homogeneity, realized by the arrangement of two pore sizes. For a given layer number, we find that water flux exhibits an excellent linear behavior with pressure, in agreement with the prediction of the Hagen–Poiseuille equation. Interestingly, the flux for concentrated pore size distribution is around two times larger than that of a uniform distribution. More surprisingly, under a given pressure, the water flux changes in an opposite way for these two distributions, where the flux ratio almost increases linearly with the layer number. For the largest layer number, more distributions suggest the same conclusion that higher water flux can be attained for more concentrated pore size distributions. Similar differences for the water translocation time and occupancy are also identified. The major reason for these results should clearly be due to the hydrogen bond and density profile distributions. Our results are helpful to delineate the exquisite role of pore size homogeneity, and should have great implications for the design of high flux nanofluidic devices and inversely the detection of pore structures.

Water Density in the Electric Double Layer at the Insulator/Electrolyte Solution Interface

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

Tikhonov,A.

I studied the spatial structure of the thick transition region between n-hexane and a colloidal solution of 7-nm silica particles by X-ray reflectivity and grazing incidence small-angle scattering. The interfacial structure is discussed in terms of a semiquantitative interface model wherein the potential gradient at the n-hexane/sol interface reflects the difference in the potentials of 'image forces' between the cationic Na{sup +} and anions (nanoparticles) and the specific adsorption of surface charge at the interface between the adsorbed layer and the solution, as well as at the interface between the adsorbed layer and n-hexane. The X-ray scattering data revealed thatmore » the average density of water in the field {approx}10{sup 9}-10{sup 10} V/m of the electrical double layer at the hexane/silica sol interface is the same as, or only few percent higher (1-7%) than, its density under normal conditions.« less

Chemical and morphological modifications of single layer graphene submitted to annealing in water vapor

NASA Astrophysics Data System (ADS)

Rolim, Guilherme Koszeniewski; Corrêa, Silma Alberton; Galves, Lauren Aranha; Lopes, João Marcelo J.; Soares, Gabriel Vieira; Radtke, Cláudio

2018-01-01

Modifications of single layer graphene transferred to SiO2/Si substrates resulting from annealing in water vapor were investigated. Near edge X-ray absorption fine structure spectroscopy evidenced graphene puckering between 400 and 500 °C. Synchrotron radiation based X-ray photoelectron spectroscopy showed variation of sp2 and sp3C bonding configurations specially in this same temperature range. Moreover, oxygen related functionalities are formed as a result of water vapor annealing. Based on these results and complementary Raman and nuclear reaction analysis, one distinguishes three different regimes of water interaction with graphene concerning modifications of the graphene layer. In the low temperature range (200-400 °C), no prominent modification of graphene itself is observed. At higher temperatures (400-500 °C), to accommodate newly formed oxygen functionalities, the flat and continuous sp2 bonding network of graphene is disrupted, giving rise to a puckered layer. For 600 °C and above, shrinking of graphene domains and a higher doping level take place.

Structural and dielectric properties of thin ZrO2 films on silicon grown by atomic layer deposition from cyclopentadienyl precursor

NASA Astrophysics Data System (ADS)

Niinistö, J.; Putkonen, M.; Niinistö, L.; Kukli, K.; Ritala, M.; Leskelä, M.

2004-01-01

ZrO2 thin films with thicknesses below 20 nm were deposited by the atomic layer deposition process on Si(100) substrates at 350 °C. An organometallic precursor, Cp2Zr(CH3)2 (Cp=cyclopentadienyl, C5H5) was used as the zirconium source and water or ozone as oxygen source. The influence of oxygen source and substrate pretreatment on the dielectric properties of ZrO2 films was investigated. Structural characterization with high-resolution transmission electron microscopy was performed to films grown onto HF-etched or native oxide covered silicon. Strong inhibition of ZrO2 film growth was observed with the water process on HF-etched Si. Ozone process on HF-etched Si resulted in interfacial SiO2 formation between the dense and uniform film and the substrate while water process produced interfacial layer with intermixing of SiO2 and ZrO2. The effective permittivity of ZrO2 in Al/ZrO2/Si/Al capacitor structures was dependent on the ZrO2 layer thickness and oxygen source used. The interfacial layer formation increased the capacitance equivalent oxide thickness (CET). CET of 2.0 nm was achieved with 5.9 nm ZrO2 film deposited with the H2O process on HF-stripped Si. The ozone-processed films showed good dielectric properties such as low hysteresis and nearly ideal flatband voltage. The leakage current density was lower and breakdown field higher for the ozone-processed ZrO2 films.

Oxidation of Alloy 600 and Alloy 690: Experimentally Accelerated Study in Hydrogenated Supercritical Water

NASA Astrophysics Data System (ADS)

Moss, Tyler; Cao, Guoping; Was, Gary S.

2017-04-01

The objective of this study is to determine whether the oxidation of Alloys 600 and 690 in supercritical water occurs by the same mechanism in subcritical water. Coupons of Alloys 690 and 600 were exposed to hydrogenated subcritical and supercritical water from 633 K to 673 K (360 °C to 400 °C) and the oxidation behavior was observed. By all measures of oxide character and behavior, the oxidation process is the same above and below the supercritical line. Similar oxide morphologies, structures, and chemistries were observed for each alloy across the critical point, indicating that the oxidation mechanism is the same in both subcritical and supercritical water. Oxidation results in a multi-layer oxide structure composed of particles of NiO and NiFe2O4 formed by precipitation on the outer surface and a chromium-rich inner oxide layer formed by diffusion of oxygen to the metal-oxide interface. The inner oxide on Alloy 600 is less chromium rich than that observed on Alloy 690 and is accompanied by preferential oxidation of grain boundaries. The inner oxide on Alloy 690 initially forms by internal oxidation before a protective layer of chromium-rich MO is formed with Cr2O3 at the metal-oxide interface. Grain boundaries in Alloy 690 act as fast diffusion paths for chromium that forms a protective Cr2O3 layer at the surface, preventing grain boundary oxidation from occurring.

Influence of Excessive Moisture in the Subgrade on the Durability and Load-Bearing Capacity of Road Pavements

NASA Astrophysics Data System (ADS)

Mieczkowski, P.; Budziński, B.

2018-05-01

When well performed, pavement renewal or alteration shall ensure the desired properties of the road during the assumed period of operation. Presence of water in the subgrade can be one of the main factors affecting the structural capacity of pavement and can result in cracking of the bituminous layers, even after a very short period of trafficking. Reconstruction of one of regional roads in Poland has been chosen to serve as an example of inappropriate approach to the problem of the presence of water in the road structure. The project included construction of new layers of pavement and increasing the design life of the whole pavement structure to 4.06 million ESAL of 100 kN (as per the Standard Catalogue of Typical Flexible and Semi-rigid Road Pavement Structures, issue of 1997). After a relatively short period of trafficking (3-5 years) localised alligator cracking appeared on the surface along with structural deformations. The pavement condition assessment including FWD tests was carried out to reveal excessive deflections (over 500 μm) which classify the road for renewal. The analysis of data showed that the main cause of distress was softening of the subgrade caused by an ingress of precipitation water under the pavement layers through the roadway and shoulder edges. The deficiencies of the performed reconstruction occurred both in the roadway (including small step-outs in the cement-treated layer) and partly in the shoulders where the existing soil was in places replaced with impervious material, with the existing (cohesive) material left in place on a major part of the overall length.

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.

Effect of temperature on compact layer of Pt electrode in PEMFCs by first-principles molecular dynamics calculations

NASA Astrophysics Data System (ADS)

He, Yang; Chen, Changfeng; Yu, Haobo; Lu, Guiwu

2017-01-01

Formation of the double-layer electric field and capacitance of the water-metal interface is of significant interest in physicochemical processes. In this study, we perform first- principles molecular dynamics simulations on the water/Pt(111) interface to investigate the temperature dependence of the compact layer electric field and capacitance based on the calculated charge densities. On the Pt (111) surface, water molecules form ice-like structures that exhibit more disorder along the height direction with increasing temperature. The Osbnd H bonds of more water molecules point toward the Pt surface to form Ptsbnd H covalent bonds with increasing temperature, which weaken the corresponding Osbnd H bonds. In addition, our calculated capacitance at 300 K is 15.2 mF/cm2, which is in good agreement with the experimental results. As the temperature increases from 10 to 450 K, the field strength and capacitance of the compact layer on Pt (111) first increase and then decrease slightly, which is significant for understanding the water/Pt interface from atomic level.

Spatial distribution of the phytoplankton in the White Sea during atypical domination of dinoflagellates (July 2009)

NASA Astrophysics Data System (ADS)

Ilyash, L. V.; Zhitina, L. S.; Belevich, T. A.; Shevchenko, V. P.; Kravchishina, M. D.; Pantyulin, A. N.; Tolstikov, A. V.; Chultsova, A. L.

2016-05-01

The species composition and biomass of phytoplankton, concentrations of chlorophyll a (Chl a) and nutrients, and accompanying hydrophysical conditions have been studied in the White Sea on July 6-11, 2009. The temperature of the surface water layer was lower than the multiyear average in July. Dinoflagellates dominated in the entire studied area; this was not the typical event for July. We suggest that domination of dinoflagellates was caused by low water temperature, when the nutrient regeneration rate was insufficient to support diatom growth. The abundance of microalgae and the structure of the phytoplankton community depended on the water structure. Variations in the phytoplankton community structure were caused not by substitution of specific species but rather by variability of the abundance of a single species, Heterocapsa triquetra. The highest phytoplankton biomass has been recorded in weakly stratified waters, where tidal mixing supplied the income of inorganic nutrients. The income of nutrients to the photic layer was limited in the stratified waters of Dvina Bay during the summer low-water period, so the phytoplankton abundance was low. We suggest that the lens of surface desalinated water presumably originated from the outlet of the Dvina River was registered in the central part of the White Sea.

Water adsorption on the P-rich GaP(100) surface: optical spectroscopy from first principles

NASA Astrophysics Data System (ADS)

May, Matthias M.; Sprik, Michiel

2018-03-01

The contact of water with semiconductors typically changes its surface electronic structure by oxidation or corrosion processes. A detailed knowledge—or even control of—the surface structure is highly desirable, as it impacts the performance of opto-electronic devices from gas-sensing to energy conversion applications. It is also a prerequisite for density functional theory-based modelling of the electronic structure in contact with an electrolyte. The P-rich GaP(100) surface is extraordinary with respect to its contact with gas-phase water, as it undergoes a surface reordering, but does not oxidise. We investigate the underlying changes of the surface in contact with water by means of theoretically derived reflection anisotropy spectroscopy (RAS). A comparison of our results with experiment reveals that a water-induced hydrogen-rich phase on the surface is compatible with the boundary conditions from experiment, reproducing the optical spectra. We discuss potential reaction paths that comprise a water-enhanced hydrogen mobility on the surface. Our results also show that computational RAS—required for the interpretation of experimental signatures—is feasible for GaP in contact with water double layers. Here, RAS is sensitive to surface electric fields, which are an important ingredient of the Helmholtz-layer. This paves the way for future investigations of RAS at the semiconductor–electrolyte interface.

Water-rich planets: How habitable is a water layer deeper than on Earth?

NASA Astrophysics Data System (ADS)

Noack, L.; Höning, D.; Rivoldini, A.; Heistracher, C.; Zimov, N.; Journaux, B.; Lammer, H.; Van Hoolst, T.; Bredehöft, J. H.

2016-10-01

Water is necessary for the origin and survival of life as we know it. In the search for life-friendly worlds, water-rich planets therefore are obvious candidates and have attracted increasing attention in recent years. The surface H2O layer on such planets (containing a liquid water ocean and possibly high-pressure ice below a specific depth) could potentially be hundreds of kilometres deep depending on the water content and the evolution of the proto-atmosphere. We study possible constraints for the habitability of deep water layers and introduce a new habitability classification relevant for water-rich planets (from Mars-size to super-Earth-size planets). A new ocean model has been developed that is coupled to a thermal evolution model of the mantle and core. Our interior structure model takes into account depth-dependent thermodynamic properties and the possible formation of high-pressure ice. We find that heat flowing out of the silicate mantle can melt an ice layer from below (in some cases episodically), depending mainly on the thickness of the ocean-ice shell, the mass of the planet, the surface temperature and the interior parameters (e.g. radioactive mantle heat sources). The high pressure at the bottom of deep water-ice layers could also impede volcanism at the water-mantle boundary for both stagnant lid and plate tectonics silicate shells. We conclude that water-rich planets with a deep ocean, a large planet mass, a high average density or a low surface temperature are likely less habitable than planets with an Earth-like ocean.

Geotechnical studies for evaluation and limitations of environmental and engineering hazards that affect the economic infrastructure in Abha, Saudi Arabia

NASA Astrophysics Data System (ADS)

Shaaban, Fathy; Al-Salami, Ali E.

2014-12-01

Abha is the capital of Asir province in Saudi Arabia. It is situated 2200 meters (7200 ft) above the sea level in the fertile mountains of the south-western Saudi Arabia. One of the most important structures of this region is Abha dam that acts as a barrier that impounds water or underground streams thereby retaining the ground water of the region. With the passage of time, various environmental factors such as ground movement, wind and changes in temperature may have significant effect on these various structure factors and may lead to invisible cracks and other structural defects. Because the dams and tunnels are prone to sudden collapse, there is potential great risk to lives of the people and significant economic loss in this area. The use of the ground penetrating radar (GPR) and electric resistivity techniques is a non-invasive scan and could assess the conditions of various built structures as well as the earth beneath or surrounding it. So the GPR system with appropriate types of antennas (1.5 GH, 1 GH, 400 MH and 100 MH) and electrical resistivity in one dimension (VES) and two dimensions (electrical profiling and imaging) is used in this work. This work aims to investigate the dam structure, developing cracks or areas of increased moisture. Also to study the surrounding areas to detect seepage from pond that may affect nearby buildings and the dam itself. It reveals that, the depth of water bearing layer ranges from 2 m to 10 m, where the three geoelectric layers are present. The first layer has resistivity values ranging from 44 Ω m-1200 Ω m with thickness ranging from 3 m to 18 m that is interpreted as the wadi deposits. The second layer having resistivity values from 11 Ω m to 137 Ω m is interpreted as the water saturated in the fractured basements. The third layer of resistivity values ranging from 2200 Ω m to 90,000 Ω m is interpreted as dry, massive basements. The GPR results provided internal images of the slab, showing its morphology, areas of possible damage and changes to the structure, and the situation of the steel reinforcements. It showed the presence of different shapes of fractures and voids with the growing of moisture zones.

Enhancement of the barrier performance in organic/inorganic multilayer thin-film structures by annealing of the parylene layer

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

Kim, Namsu, E-mail: nkim@keti.re.kr; Components and Materials Physics Research Center, #68 Yatop-dong, Korea Electronics Technology Institute, Bundang-gu, 463-816; Graham, Samuel

2014-10-15

Highlights: • High performance thin-film barrier structure for encapsulation was fabricated. • By annealing parylene in encapsulation structure, the barrier performance was improved. • The effective water vapor transmission rate is 7.2 ± 3.0 × 10{sup −6} g/m{sup 2}/day. - Abstract: A multilayered barrier structure was fabricated by chemical vapor deposition of parylene and subsequent plasma-enhanced chemical vapor deposition of SiO{sub x} or SiN{sub x}. The barrier performance against water vapor ingress was significantly improved by annealing the parylene layer before the deposition of either SiO{sub x} or SiN{sub x}. The mechanism of this enhancement was investigated using atomic forcemore » microscopy, Raman spectroscopy, and X-ray diffraction. The surface roughness of the parylene before the deposition of either SiO{sub x} or SiN{sub x} was found to correlate closely with the barrier performance of the multilayered structures. In addition, removing absorbed water vapor in the film by annealing results in a lower water vapor transmission rate in the transient region and a longer lag time. Annealing the parylene leads to a large decrease in the effective water vapor transmission rate, which reaches 7.2 ± 3.0 × 10{sup −6} g/m{sup 2}/day.« less

Inference of the boundary layer structure over the oceans from satellite infrared measurements

NASA Technical Reports Server (NTRS)

Prabhakara, C.; Dalu, G.; Lo, R.; Nath, N. R.

1980-01-01

Remote infrared spectral measurements in the 8-13 micron m window region, at a resolution about 3 cm/1, contain useful information about the water vapor and temperature stratification of the atmosphere within the first few kilometers above the water surface. Two pieces of information are retrieved from the spectral measurements: precipitable water vapor in the atmosphere, from the depth of the line structure between 8 and 9 micron m due to water vapor lines; and sea surface temperature, from the variation of brightness temperature between 11 and 13 micron m. Together, these two pieces of information can signify either the presence of a deep moist convective layer or the prevalence of stable conditions, such as caused by temperature inversions, which inhibit moist convection. A simple infrared radiative transfer model of the 9 micron m water vapor lines was developed to validate the method. With the help of this model and the Nimbus 4 infrared interferometer spectrometer data, a gross picture of the planetary boundary layer for different seasons over the global oceans is deduced. The important regions of the trade wind inversion and the intertropical convergence zones over all the oceans are clearly identified with this method. The derived information is in reasonable agreement with some observed climatological patterns over the oceans.

Teleseismic Earthquake Signals Observed on an Ice Shelf

NASA Astrophysics Data System (ADS)

Baker, M. G.; Aster, R. C.; Anthony, R. E.; Wiens, D.; Nyblade, A.; Bromirski, P. D.; Stephen, R. A.; Gerstoft, P.

2015-12-01

The West Antarctic Rift System (WARS) is one of Earth's largest continental extension zones. Study of the WARS is complicated by the presence of the West Antarctic Ice Sheet, the Ross Ice Shelf, and the Ross Sea. Recent deployments of broadband seismographs in the POLENET project have allowed passive seismic techniques, such as receiver function analysis and surface wave dispersion, to be widely utilized to infer crustal and mantle velocity structure across much of the WARS and West Antarctica. However, a large sector of the WARS lies beneath the Ross Ice Shelf. In late 2014, 34 broadband seismographs were deployed atop the ice shelf to jointly study deep Earth structure and the dynamics of the ice shelf. Ice shelf conditions present strong challenges to broadband teleseismic imaging: 1) The presence of complicating signals in the microseism through long-period bands due to the influence of ocean gravity waves; 2) The strong velocity contrasts at the ice-water and water-sediment interfaces on either side of the water layer give rise to large amplitude reverberations; 3) The water layer screens S-waves or P-to-S phases originating from below the water layer. We present an initial analysis of the first teleseismic earthquake arrivals collected on the ice shelf at the end of the 2014 field season from a limited subset of these stations.

Novel electrospun gas diffusion layers for polymer electrolyte membrane fuel cells: Part II. In operando synchrotron imaging for microscale liquid water transport characterization

NASA Astrophysics Data System (ADS)

Chevalier, S.; Ge, N.; Lee, J.; George, M. G.; Liu, H.; Shrestha, P.; Muirhead, D.; Lavielle, N.; Hatton, B. D.; Bazylak, A.

2017-06-01

This is the second paper in a two-part series in which we investigate the impact of the gas diffusion layer structure on the liquid water distribution in an operating polymer electrolyte membrane (PEM) fuel cell through the procedures of design, fabrication, and testing of novel hydrophobic electrospun gas diffusion layers (eGDLs). In this work, fibre diameters and alignment in eGDLs are precisely controlled, and concurrent synchrotron X-ray radiography and electrochemical impedance spectroscopy (EIS) are used to evaluate the influence of the controlled eGDL parameters on the liquid water distribution and on membrane liquid water content. For eGDLs with small fibre diameters (150-200 nm) and correspondingly smaller pore sizes, reduced liquid water accumulation under the flow field ribs is observed. However, more liquid water is pinned onto the eGDL - at the interface with flow field channels. Orienting fibre alignment perpendicular to the flow field channel direction leads to improved eGDL-catalyst layer contact and prevents rib-channel membrane deformation. On the other hand, eGDLs facilitate significant membrane dry-out, even under highly humidified operating conditions at high current densities.

Structural analysis and characterization of layer perovskite oxynitrides made from Dion Jacobson oxide precursors

NASA Astrophysics Data System (ADS)

Schottenfeld, Joshua A.; Benesi, Alan J.; Stephens, Peter W.; Chen, Gugang; Eklund, Peter C.; Mallouk, Thomas E.

2005-07-01

A three-layer oxynitride Ruddlesden-Popper phase Rb 1+xCa 2Nb 3O 10-xN x· yH 2O ( x=0.7-0.8, y=0.4-0.6) was synthesized by ammonialysis at 800 °C from the Dion-Jacobson phase RbCa 2Nb 3O 10 in the presence of Rb 2CO 3. Incorporation of nitrogen into the layer perovskite structure was confirmed by XPS, combustion analysis, and MAS NMR. The water content was determined by thermal gravimetric analysis and the rubidium content by ICP-MS. A similar layered perovskite interconversion occurred in the two-layer Dion-Jacobson oxide RbLaNb 2O 7 to yield Rb 1+xLaNb 2O 7-xN x· yH 2O ( x=0.7-0.8, y=0.5-1.0). Both compounds were air- and moisture-sensitive, with rapid loss of nitrogen by oxidation and hydrolysis reactions. The structure of the three-layer oxynitride Rb 1.7Ca 2Nb 3O 9.3N 0.7·0.5H 2O was solved in space group P4 /mmm with a=3.887(3) and c=18.65(1) Å, by Rietveld refinement of X-ray powder diffraction data. The two-layer oxynitride structure Rb 1.8LaNb 2O 6.3N 0.7·1.0H 2O was also determined in space group P4 /mmm with a=3.934(2) and c=14.697(2) Å. GSAS refinement of synchrotron X-ray powder diffraction data showed that the water molecules were intercalated between a double layer of Rb+ ions in both the two- and three-layer Ruddlesden-Popper structures. Optical band gaps were measured by diffuse reflectance UV-vis for both materials. An indirect band gap of 2.51 eV and a direct band gap of 2.99 eV were found for the three-layer compound, while an indirect band gap of 2.29 eV and a direct band gap of 2.84 eV were measured for the two-layer compound. Photocatalytic activity tests of the three-layer compound under 380 nm pass filtered light with AgNO 3 as a sacrificial electron acceptor gave a quantum yield of 0.025% for oxygen evolution.

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.

Lagrangian mixed layer modeling of the western equatorial Pacific

NASA Technical Reports Server (NTRS)

Shinoda, Toshiaki; Lukas, Roger

1995-01-01

Processes that control the upper ocean thermohaline structure in the western equatorial Pacific are examined using a Lagrangian mixed layer model. The one-dimensional bulk mixed layer model of Garwood (1977) is integrated along the trajectories derived from a nonlinear 1 1/2 layer reduced gravity model forced with actual wind fields. The Global Precipitation Climatology Project (GPCP) data are used to estimate surface freshwater fluxes for the mixed layer model. The wind stress data which forced the 1 1/2 layer model are used for the mixed layer model. The model was run for the period 1987-1988. This simple model is able to simulate the isothermal layer below the mixed layer in the western Pacific warm pool and its variation. The subduction mechanism hypothesized by Lukas and Lindstrom (1991) is evident in the model results. During periods of strong South Equatorial Current, the warm and salty mixed layer waters in the central Pacific are subducted below the fresh shallow mixed layer in the western Pacific. However, this subduction mechanism is not evident when upwelling Rossby waves reach the western equatorial Pacific or when a prominent deepening of the mixed layer occurs in the western equatorial Pacific or when a prominent deepening of the mixed layer occurs in the western equatorial Pacific due to episodes of strong wind and light precipitation associated with the El Nino-Southern Oscillation. Comparison of the results between the Lagrangian mixed layer model and a locally forced Eulerian mixed layer model indicated that horizontal advection of salty waters from the central Pacific strongly affects the upper ocean salinity variation in the western Pacific, and that this advection is necessary to maintain the upper ocean thermohaline structure in this region.

Transport of water and solutes in reverse osmosis and nanofiltration membranes

NASA Astrophysics Data System (ADS)

Cahill, David

2009-03-01

The polyamide active layers of reverse osmosis and nanofiltration membranes used for water purification are real-world examples of nanoscale functional materials: the active layer is only ˜100 nm thick. Because the active layer is formed by a process of interfacial polymerization, the structure and composition of the membrane is highly inhomogeneous and even such basic physical and chemical properties as the atomic density, swelling in water, the distribution of charged species between water and membrane, and the mobility of water and ions, are poorly understood. We are using Rutherford backscattering spectrometry (RBS) to determine the composition, roughness, and thickness of the membrane; reveal the surprisingly high solubility of salt ions in the polymer active layer; analyze the acid-base chemistry of charged functional groups; and determine the degree of polymer cross-linking. Measurements of mass-uptake and adsorption-induced mechanical stress of membranes in humid air enable us to determine the water solubility, specific volume of water, and the mechanical strength of the membrane. Comparisons between these equilibrium data and the permeability of the membrane to water and salts show that the mobility of water molecules in the membrane approaches the mobility of bulk water, and that the rejection of salt ions is accomplished by low mobility, not low solubility. My collaborators in this work are Xijing Zhang, Orlando Coronell, and Prof. Benito Mariñas.

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.

Anisotropic capillary barrier for waste site surface covers

DOEpatents

Stormont, J.C.

1996-08-27

Waste sites are capped or covered upon closure. The cover structure incorporates a number of different layers each having a contributory function. One such layer is the barrier layer. Traditionally the barriers have been compacted soil and geosynthetics. These types of barriers have not been successfully implemented in unsaturated ground conditions like those found in dry climates. Capillary barriers have been proposed as barrier layers in dry environments, but the divergence length of these barriers has been found to be inadequate. An alternative to the capillary barrier is a anisotropic capillary barrier. An anisotropic capillary barrier has an increased divergence length which results in more water being diverted laterally preventing the majority of water from percolating in a downward direction through the barrier. 10 figs.

Anisotropic capillary barrier for waste site surface covers

DOEpatents

Stormont, John C.

1996-01-01

Waste sites are capped or covered upon closure. The cover structure incorporates a number of different layers each having a contributory function. One such layer is the barrier layer. Traditionally the barriers have been compacted soil and geosynthetics. These types of barriers have not been successfully implemented in unsaturated ground conditions like those found in dry climates. Capillary barriers have been proposed as barrier layers in dry environments, but the divergence length of these barriers has been found to be inadequate. An alternative to the capillary barrier is a anisotropic capillary barrier. An anisotropic capillary barrier has an increased divergence length which results in more water being diverted laterally preventing the majority of water from percolating in a downward direction through the barrier.

Enhanced Evaporation Strength through Fast Water Permeation in Graphene-Oxide Deposition

PubMed Central

Li Tong, Wei; Ong, Wee-Jun; Chai, Siang-Piao; Tan, Ming K.; Mun Hung, Yew

2015-01-01

The unique characteristic of fast water permeation in laminated graphene oxide (GO) sheets has facilitated the development of ultrathin and ultrafast nanofiltration membranes. Here we report the application of fast water permeation property of immersed GO deposition for enhancing the performance of a GO/water nanofluid charged two-phase closed thermosyphon (TPCT). By benchmarking its performance against a silver oxide/water nanofluid charged TPCT, the enhancement of evaporation strength is found to be essentially attributed to the fast water permeation property of GO deposition instead of the enhanced surface wettability of the deposited layer. The expansion of interlayer distance between the graphitic planes of GO deposited layer enables intercalation of bilayer water for fast water permeation. The capillary force attributed to the frictionless interaction between the atomically smooth, hydrophobic carbon structures and the well-ordered hydrogen bonds of water molecules is sufficiently strong to overcome the gravitational force. As a result, a thin water film is formed on the GO deposited layers, inducing filmwise evaporation which is more effective than its interfacial counterpart, appreciably enhanced the overall performance of TPCT. This study paves the way for a promising start of employing the fast water permeation property of GO in thermal applications. PMID:26100977

2D and 3D Ground Penetrating Radar monitoring of a reinforced concrete asphalt plate affected by mechanical deformation.

NASA Astrophysics Data System (ADS)

Bavusi, M.; Dumoulin, J.; Loperte, A.; Rizzo, E.; Soldovieri, F.

2012-04-01

The main facility of Hydrogeosite Laboratory of the Italian National Research Council (Marsico Nuovo, CNR) is a 3m x 7m x 10m reinforced concrete pool filled by siliceous sand designed for hydrologic experiments. One of its peculiarities is the possibility to vary the water table depth by using a proper hydraulic system [1]. In the framework of the FP7 ISTIMES project (Integrated System for Transport Infrastructure surveillance and Monitoring by Electromagnetic Sensing), a 3m x 3m layered structure has been purposely built and placed in the pool of the Hydrogeosite Laboratory with the aim to carry out a long term monitoring, by using jointly several electromagnetic sensing technologies, during two different phases simulating the rising of the water table and a mechanical solicitation. Several layers composed the structure from the top to the bottom, such as: 5 cm of asphalt; 5-10 cm of reinforced concrete; 20-25 cm of conglomerate, 55 cm of sand. Moreover, in the sand layer, three (metallic and plastic) pipes of different size were buried to simulate utilities. Ground Penetrating Radar (GPR) surveys were performed by using a the GSSI SIR 3000 system equipped with 400 MHz and 1500 MHz central frequency antennas. Surveys carried out by means of 400 MHz antenna allowed to detect and localize the three pipes (one in plastic and two in metal) and to investigate the effects of the sand water content on their radar signature. Surveys carried out by using 1500 MHz antenna were focused to characterize the shallower layers of the structure. The Hydrogeosite experiment consisted in following stages: • Arising of a water table by infiltration from the bottom; • Water gravity infiltration condescendingly; • Infiltration by peristaltic pump in the very shallow layers of the structure; • Water table drawdown; • Mechanical structure deformation; • Asphalt plate restoration after mechanical solicitation. After each stage a series of GPR surveys was performed. Moreover, a zero setting acquisition was carried out before perturbing the plate. Described experience demonstrates the GPR is a reliable technique for the: • foundation soil characterization and monitoring • Reinforced structural elements monitoring • asphalt/reinforced concrete characterization and monitoring • detection of water infiltration, structural elements, defects • evaluation of restoration intervention. In fact, the GPR technique was able to investigate the layers beyond the asphalt and provides a spatial resolution complying with the needs of the technical problem at hand by use of different antennas. Moreover noticeable performances of this technique can be further improved by implementing 3D processing and MT inversion procedures in order to increase the amount of information by the survey [2]. Acknowledgements. The research leading to these results has received funding from the European Community's Seventh Framework Programme (FP7/2007-2013) under Grant Agreement n. 225663 Joint Call FP7-ICT-SEC-2007-1 [1] Lapenna, V.; Cuomo, V.; Rizzo, E.; Fiore, S.; Troisi, S.; Straface, S. (2006). A new Large Lab-scale Facility for Hydro-Geophysical Experiments: Hydrogeosite. American Geophysical Union, Fall Meeting 2006, abstract #H31B-1422 [2] Bavusi M., Soldovieri F., Di Napoli R., Loperte A., Di Cesare A., Ponzo F.C and Lapenna V. (2011). Ground penetrating radar and microwave tomography 3D applications for the deck evaluation of the Musmeci bridge in Potenza, Italy. J. Geophys. Eng. 8 S33 doi:10.1088/1742-2132/8/3/S04

Effect of urea and glycerol on the adsorption of ribonuclease A at the air-water interface.

PubMed

Hüsecken, Anne K; Evers, Florian; Czeslik, Claus; Tolan, Metin

2010-08-17

This study reports on the influence of nonionic cosolvents on the interfacial structure of ribonuclease A (RNase) adsorbed at the air-water interface. We applied X-ray reflectometry to obtain detailed volume fraction profiles of the adsorbed layers and to follow the effect of glycerol and urea on the adsorbate structure as a function of cosolvent concentration. Under all conditions studied, the adsorbed RNase layer maintains its compact shape, and the adsorbed RNase molecules adopt a flat-on orientation at the interface. Both kosmotropic glycerol and chaotropic urea exert profound effects on the adsorbate: The surface excess decreases linearly with glycerol content and is also reduced at low urea concentration. However, at high urea concentration, parts of the adsorbed layer are dehydrated and become exposed to air. The electron density and volume fraction profiles of the adsorbed protein provide clear evidence that these effects are ruled by different mechanisms.

Formation of ZnO at zinc oxidation by near- and supercritical water under the constant electric field

NASA Astrophysics Data System (ADS)

Shishkin, A. V.; Sokol, M. Ya.; Shatrova, A. V.; Fedyaeva, O. N.; Vostrikov, A. A.

2014-12-01

The work has detected an influence of a constant electric field (up to E = 300 kV/m) on the structure of a nanocrystalline layer of zinc oxide, formed on the surface of a planar zinc anode in water under supercritical (673 K and 23 MPa) and near-critical (673 K and 17. 5 MPa) conditions. The effect of an increase of zinc oxidation rate with an increase in E is observed under supercritical conditions and is absent at near-critical ones. Increase in the field strength leads to the formation of a looser structure in the inner part of the zinc oxide layer.

In situ distribution and characterization of the organic content of the oyster shell Crassostrea gigas (Mollusca, Bivalvia).

PubMed

Dauphin, Yannicke; Ball, Alexander D; Castillo-Michel, Hiram; Chevallard, Corinne; Cuif, Jean-Pierre; Farre, Bastien; Pouvreau, Stéphane; Salomé, Murielle

2013-01-01

Cultivation of commercial oysters is now facing the possible influence of global change in sea water composition, commonly referred to as "ocean acidification". In order to test the potential consequence of the predicted environmental changes, a cultivation experiment was carried out. The left and right valves of the oyster shell Crassostrea gigas differ in their structure; moreover, lenses of non compact layers are irregular. The shell layers of juvenile C. gigas are studied using a variety of highly spatially resolved techniques to establish their composition and structure. Our results confirm the presence of three different calcitic structural types. The role of the lenses of chalky layers is not yet deciplered. Despite a common mineralogy, the elemental composition of the layers differs. The sulphur aminoacids and sulphated polysaccharide contents of the intracrystalline and intercrystalline matrices differ, as well as those of the structural types. The possible different sensitivity of these structures to environmental changes is still unknown. Copyright © 2012 Elsevier Ltd. All rights reserved.

Combined effect of capillary barrier and layered slope on water, solute and nanoparticle transfer in an unsaturated soil at lysimeter scale.

PubMed

Prédélus, Dieuseul; Coutinho, Artur Paiva; Lassabatere, Laurent; Bien, Le Binh; Winiarski, Thierry; Angulo-Jaramillo, Rafael

2015-10-01

It is well recognized that colloidal nanoparticles are highly mobile in soils and can facilitate the transport of contaminants through the vadose zone. This work presents the combined effect of the capillary barrier and soil layer slope on the transport of water, bromide and nanoparticles through an unsaturated soil. Experiments were performed in a lysimeter (1×1×1.6m(3)) called LUGH (Lysimeter for Urban Groundwater Hydrology). The LUGH has 15 outputs that identify the temporal and spatial evolution of water flow, solute flux and nanoparticles in relation to the soil surface conditions and the 3D system configuration. Two different soil structures were set up in the lysimeter. The first structure comprises a layer of sand (0-0.2cm, in diameter) 35cm thick placed horizontally above a layer of bimodal mixture also 35cm thick to create a capillary barrier at the interface between the sand and bimodal material. The bimodal material is composed of a mixture 50% by weight of sand and gravel (0.4-1.1cm, in diameter). The second structure, using the same amount of sand and bimodal mixture as the first structure represents an interface with a 25% slope. A 3D numerical model based on Richards equation for flow and the convection dispersion equations coupled with a mechanical module for nanoparticle trapping was developed. The results showed that under the effect of the capillary barrier, water accumulated at the interface of the two materials. The sloped structure deflects flow in contrast to the structure with zero slope. Approximately 80% of nanoparticles are retained in the lysimeter, with a greater retention at the interface of two materials. Finally, the model makes a good reproduction of physical mechanisms observed and appears to be a useful tool for identifying key processes leading to a better understanding of the effect of capillary barrier on nanoparticle transfer in an unsaturated heterogeneous soil. Copyright © 2015 Elsevier B.V. All rights reserved.

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

Structural, Material, and Geotechnical Solutions to Levee and Floodwall Construction and Retrofitting - Physical Modeling

DTIC Science & Technology

2012-12-01

thick sand layer was placed, the excess surface water was drained off, completing the saturated loose sand layer (Figure 22). Ten pore pressure...during flight. ERDC/GSL TR-12-37 17 Figure 28. Lasers to measure top of I-wall deflection. A 1/4-in. water supply tube was installed to provide...inflow rate via the 1/4-in. tubing would not fill the basin faster than any underseepage would develop because of the relative foundation weakness

Architecture of the hydrophobic and hydrophilic layers as found from crystal structure analysis of N-benzyl-N,N-dimethylalkylammonium bromides.

PubMed

Hodorowicz, Maciej; Stadnicka, Katarzyna; Czapkiewicz, Jan

2005-10-01

The molecular and crystal structures of N-benzyl-N,N-dimethylalkylammonium bromides monohydrates with chain length n=8-10 have been determined. The crystals are isostructural with the N-benzyl-N,N-dimethyldodecylammonium bromide monohydrate. The structures consist of alternated hydrophobic and hydrophilic layers perpendicular to [001]. The attraction between N+ of the cation head-groups and Br- anions is achieved through weak C_H...Br interactions. The water molecules incorporated into ionic layers are donors for two O_H...Br hydrogen bonds and serve as the acceptors in two weak interactions of C_H...O type. The methylene chains, with the slightly curved general shape, have the extended all-trans conformation. The mutual packing of the chains in the hydrophobic layers is governed by weak C_H...pi interactions.

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.

Improving organic tandem solar cells based on water-processed nanoparticles by quantitative 3D nanoimaging.

PubMed

Pedersen, E B L; Angmo, D; Dam, H F; Thydén, K T S; Andersen, T R; Skjønsfjell, E T B; Krebs, F C; Holler, M; Diaz, A; Guizar-Sicairos, M; Breiby, D W; Andreasen, J W

2015-08-28

Organic solar cells have great potential for upscaling due to roll-to-roll processing and a low energy payback time, making them an attractive sustainable energy source for the future. Active layers coated with water-dispersible Landfester particles enable greater control of the layer formation and easier access to the printing industry, which has reduced the use of organic solvents since the 1980s. Through ptychographic X-ray computed tomography (PXCT), we image quantitatively a roll-to-roll coated photovoltaic tandem stack consisting of one bulk heterojunction active layer and one Landfester particle active layer. We extract the layered morphology with structural and density information including the porosity present in the various layers and the silver electrode with high resolution in 3D. The Landfester particle layer is found to have an undesired morphology with negatively correlated top- and bottom interfaces, wide thickness distribution and only partial surface coverage causing electric short circuits through the layer. By top coating a polymer material onto the Landfester nanoparticles we eliminate the structural defects of the layer such as porosity and roughness, and achieve the increased performance larger than 1 V expected for a tandem cell. This study highlights that quantitative imaging of weakly scattering stacked layers of organic materials has become feasible by PXCT, and that this information cannot be obtained by other methods. In the present study, this technique specifically reveals the need to improve the coatability and layer formation of Landfester nanoparticles, thus allowing improved solar cells to be produced.

Performance of a Cross-Flow Humidifier with a High Flux Water Vapor Transport Membrane

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

Ahluwalia, R. K.; Wang, X.; Johnson, W. B.

Water vapor transport (WVT) flux across a composite membrane that consists of a very thin perfluorosulfonic acid (PFSA) ionomer layer sandwiched between two expanded polytetrafluoroethylene (PTFE) microporous layers is investigated. Static and dynamic tests are conducted to measure WVT flux for different composite structures; a transport model shows that the underlying individual resistances for water diffusion in the gas phase and microporous and ionomer layers and for interfacial kinetics of water uptake at the ionomer surface are equally important under different conditions. A finite-difference model is formulated to determine water transport in a full-scale (2-m2 active membrane area) planar cross-flowmore » humidifier module assembled using pleats of the optimized composite membrane. In agreement with the experimental data, the modeled WVT flux in the module increases at higher inlet relative humidity (RH) of the wet stream and at lower pressures, but the mass transfer effectiveness is higher at higher pressures. The model indicates that the WVT flux is highest under conditions that maintain the wet stream at close to 100% RH while preventing the dry stream from becoming saturated. The overall water transport is determined by the gradient in RH of the wet and dry streams but is also affected by vapor diffusion in the gas layer and the microporous layer.« less

The use of positrons to survey alteration layers on synthetic nuclear waste glasses

NASA Astrophysics Data System (ADS)

Reiser, Joelle T.; Parruzot, Benjamin; Weber, Marc H.; Ryan, Joseph V.; McCloy, John S.; Wall, Nathalie A.

2017-07-01

In order to safeguard society and the environment, understanding radioactive waste glass alteration mechanisms in interactions with solutions and near-field materials, such as Fe, is essential to nuclear waste repository performance assessments. Alteration products are formed at the surface of glasses after reaction with solution. In this study, glass altered in the presence of Fe0 in aqueous solution formed two alteration layers: one embedded with Fe closer to the surface and one without Fe found deeper in the sample. Both layers were found to be thinner than the alteration layer found in glass altered in aqueous solution only. For the first time, Doppler Broadening Positron Annihilation Spectroscopy (DB-PAS) is used to non-destructively characterize the pore structures of glass altered in the presence of Fe0. Advantages and disadvantages of DB-PAS compared to other techniques used to analyze pore structures for altered glass samples are discussed. Ultimately, DB-PAS has shown to be an excellent choice for pore structure characterization for glasses with multiple alteration layers. Monte Carlo modeling predicted positron trajectories through the layers, and helped explain DB-PAS data, which showed that the deeper alteration layer without Fe had a similar composition and pore structure to layers on glass altered in water only.

The use of positrons to survey alteration layers on synthetic nuclear waste glasses

DOE PAGES

Reiser, Joelle T.; Parruzot, Benjamin; Weber, Marc H.; ...

2017-07-01

Here, in order to safeguard society and the environment, understanding radioactive waste glass alteration mechanisms in interactions with solutions and near-field materials, such as Fe, is essential to nuclear waste repository performance assessments. Alteration products are formed at the surface of glasses after reaction with solution. In this study, glass altered in the presence of Fe 0 in aqueous solution formed two alteration layers: one embedded with Fe closer to the surface and one without Fe found deeper in the sample. Both layers were found to be thinner than the alteration layer found in glass altered in aqueous solution only.more » For the first time, Doppler Broadening Positron Annihilation Spectroscopy (DB-PAS) is used to non-destructively characterize the pore structures of glass altered in the presence of Fe 0. Advantages and disadvantages of DB-PAS compared to other techniques used to analyze pore structures for altered glass samples are discussed. Ultimately, DB-PAS has shown to be an excellent choice for pore structure characterization for glasses with multiple alteration layers. Monte Carlo modeling predicted positron trajectories through the layers, and helped explain DB-PAS data, which showed that the deeper alteration layer without Fe had a similar composition and pore structure to layers on glass altered in water only.« less

The use of positrons to survey alteration layers on synthetic nuclear waste glasses

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

Reiser, Joelle T.; Parruzot, Benjamin; Weber, Marc H.

Here, in order to safeguard society and the environment, understanding radioactive waste glass alteration mechanisms in interactions with solutions and near-field materials, such as Fe, is essential to nuclear waste repository performance assessments. Alteration products are formed at the surface of glasses after reaction with solution. In this study, glass altered in the presence of Fe 0 in aqueous solution formed two alteration layers: one embedded with Fe closer to the surface and one without Fe found deeper in the sample. Both layers were found to be thinner than the alteration layer found in glass altered in aqueous solution only.more » For the first time, Doppler Broadening Positron Annihilation Spectroscopy (DB-PAS) is used to non-destructively characterize the pore structures of glass altered in the presence of Fe 0. Advantages and disadvantages of DB-PAS compared to other techniques used to analyze pore structures for altered glass samples are discussed. Ultimately, DB-PAS has shown to be an excellent choice for pore structure characterization for glasses with multiple alteration layers. Monte Carlo modeling predicted positron trajectories through the layers, and helped explain DB-PAS data, which showed that the deeper alteration layer without Fe had a similar composition and pore structure to layers on glass altered in water only.« less

Effect of humidity and water intercalation on the tribological behavior of graphene and graphene oxide.

PubMed

Arif, Taib; Colas, Guillaume; Filleter, Tobin

2018-06-12

In this work, the effect of humidity and water intercalation on the friction and wear behavior of few-layers of graphene and graphene oxide (GO) was studied using friction force microscopy. Thickness measurements demonstrated significant water intercalation within GO affecting its surface topography (roughness and protrusions), whereas negligible water intercalation of graphene was observed. It was found that water intercalation in GO contributed to wearing of layers at a relative humidity as low as ~30%. The influence of surface wettability and water adsorption was also studied by comparing the sliding behavior of SiO2/GO, SiO2/Graphene, and SiO2/SiO2 interfaces. Friction for the SiO2/GO interface increased with relative humidity due to water intercalation and condensation of water. In contrast, it was observed that adsorption of water molecules lubricated the SiO2/SiO2 interface due to easy shearing of water on the hydrophobic surface, particularly once the adsorbed water layers had transitioned from "ice-like water" to "liquid-like water" structures. Lastly, an opposite friction trend was observed for the graphene/SiO2 interface with water molecules failing to lubricate the interface as compared to the dry graphene/SiO2 contact.

Structural behavior and dynamics of an anomalous fluid between attractive and repulsive walls: Templating, molding, and superdiffusion

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

Leoni, Fabio; Franzese, Giancarlo

2014-11-07

Confinement can modify the dynamics, the thermodynamics, and the structural properties of liquid water, the prototypical anomalous liquid. By considering a generic model for anomalous liquids, suitable for describing solutions of globular proteins, colloids, or liquid metals, we study by molecular dynamics simulations the effect that an attractive wall with structure and a repulsive wall without structure have on the phases, the crystal nucleation, and the dynamics of the fluid. We find that at low temperatures the large density of the attractive wall induces a high-density, high-energy structure in the first layer (“templating” effect). In turn, the first layer inducesmore » a “molding” effect on the second layer determining a structure with reduced energy and density, closer to the average density of the system. This low-density, low-energy structure propagates further through the layers by templating effect and can involve all the existing layers at the lowest temperatures investigated. Therefore, although the high-density, high-energy structure does not self-reproduce further than the first layer, the structured wall can have a long-range influence thanks to a sequence of templating, molding, and templating effects through the layers. We find that the walls also have an influence on the dynamics of the liquid, with a stronger effect near the attractive wall. In particular, we observe that the dynamics is largely heterogeneous (i) among the layers, as a consequence of the sequence of structures caused by the walls presence, and (ii) within the same layer, due to superdiffusive liquid veins within a frozen matrix of particles near the walls at low temperature and high density. Hence, the partial freezing of the first layer does not correspond necessarily to an effective reduction of the channel's section in terms of transport properties, as suggested by other authors.« less

Structural behavior and dynamics of an anomalous fluid between attractive and repulsive walls: templating, molding, and superdiffusion.

PubMed

Leoni, Fabio; Franzese, Giancarlo

2014-11-07

Confinement can modify the dynamics, the thermodynamics, and the structural properties of liquid water, the prototypical anomalous liquid. By considering a generic model for anomalous liquids, suitable for describing solutions of globular proteins, colloids, or liquid metals, we study by molecular dynamics simulations the effect that an attractive wall with structure and a repulsive wall without structure have on the phases, the crystal nucleation, and the dynamics of the fluid. We find that at low temperatures the large density of the attractive wall induces a high-density, high-energy structure in the first layer ("templating" effect). In turn, the first layer induces a "molding" effect on the second layer determining a structure with reduced energy and density, closer to the average density of the system. This low-density, low-energy structure propagates further through the layers by templating effect and can involve all the existing layers at the lowest temperatures investigated. Therefore, although the high-density, high-energy structure does not self-reproduce further than the first layer, the structured wall can have a long-range influence thanks to a sequence of templating, molding, and templating effects through the layers. We find that the walls also have an influence on the dynamics of the liquid, with a stronger effect near the attractive wall. In particular, we observe that the dynamics is largely heterogeneous (i) among the layers, as a consequence of the sequence of structures caused by the walls presence, and (ii) within the same layer, due to superdiffusive liquid veins within a frozen matrix of particles near the walls at low temperature and high density. Hence, the partial freezing of the first layer does not correspond necessarily to an effective reduction of the channel's section in terms of transport properties, as suggested by other authors.

3D FTO/FTO-Nanocrystal/TiO2 Composite Inverse Opal Photoanode for Efficient Photoelectrochemical Water Splitting.

PubMed

Wang, Zhiwei; Li, Xianglin; Ling, Han; Tan, Chiew Kei; Yeo, Loo Pin; Grimsdale, Andrew Clive; Tok, Alfred Iing Yoong

2018-05-01

A 3D fluorine-doped SnO 2 (FTO)/FTO-nanocrystal (NC)/TiO 2 inverse opal (IO) structure is designed and fabricated as a new "host and guest" type of composite photoanode for efficient photoelectrochemical (PEC) water splitting. In this novel photoanode design, the highly conductive and porous FTO/FTO-NC IO acts as the "host" skeleton, which provides direct pathways for faster electron transport, while the conformally coated TiO 2 layer acts as the "guest" absorber layer. The unique composite IO structure is fabricated through self-assembly of colloidal spheres template, a hydrothermal method and atomic layer deposition (ALD). Owing to its large surface area and efficient charge collection, the FTO/FTO-NC/TiO 2 composite IO photoanode shows excellent photocatalytic properties for PEC water splitting. With optimized dimensions of the SnO 2 nanocrystals and the thickness of the ALD TiO 2 absorber layers, the 3D FTO/FTO-NC/TiO 2 composite IO photoanode yields a photocurrent density of 1.0 mA cm -2 at 1.23 V versus reversible hydrogen electrode (RHE) under AM 1.5 illumination, which is four times higher than that of the FTO/TiO 2 IO reference photoanode. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Distribution of Arctic and Pacific copepods and their habitat in the northern Bering and Chukchi seas

NASA Astrophysics Data System (ADS)

Sasaki, Hiroko; Matsuno, Kohei; Fujiwara, Amane; Onuka, Misaki; Yamaguchi, Atsushi; Ueno, Hiromichi; Watanuki, Yutaka; Kikuchi, Takashi

2016-08-01

The advection of warm Pacific water and the reduction in sea ice in the western Arctic Ocean may influence the abundance and distribution of copepods, a key component of food webs. To quantify the factors affecting the abundance of copepods in the northern Bering and Chukchi seas, we constructed habitat models explaining the spatial patterns of large and small Arctic and Pacific copepods separately. Copepods were sampled using NORPAC (North Pacific Standard) nets. The structures of water masses indexed by principle component analysis scores, satellite-derived timing of sea ice retreat, bottom depth and chlorophyll a concentration were integrated into generalized additive models as explanatory variables. The adequate models for all copepods exhibited clear continuous relationships between the abundance of copepods and the indexed water masses. Large Arctic copepods were abundant at stations where the bottom layer was saline; however they were scarce at stations where warm fresh water formed the upper layer. Small Arctic copepods were abundant at stations where the upper layer was warm and saline and the bottom layer was cold and highly saline. In contrast, Pacific copepods were abundant at stations where the Pacific-origin water mass was predominant (i.e. a warm, saline upper layer and saline and a highly saline bottom layer). All copepod groups showed a positive relationship with early sea ice retreat. Early sea ice retreat has been reported to initiate spring blooms in open water, allowing copepods to utilize more food while maintaining their high activity in warm water without sea ice and cold water. This finding indicates that early sea ice retreat has positive effects on the abundance of all copepod groups in the northern Bering and Chukchi seas, suggesting a change from a pelagic-benthic-type ecosystem to a pelagic-pelagic type.

Layered Organization in the Coastal Ocean: 4-D Assessment of Thin Layer Structure, Dynamics and Impacts

DTIC Science & Technology

2007-09-30

For example, the differences seen between the waters off of the US Pacific Northwest and the California Bight are almost certainly a reflection of the...the Pacific Northwest were favorable for thin layer development during that study. This is even more evident in those cases where thin layers...approach during the 2005 and 2006 LOCO process study combined time series data from an array of our Ocean Response Coastal Analysis System ( ORCAS ) (Donaghay

Autonomous Sensing of Layered Structures in Hawaiian Waters

DTIC Science & Technology

2008-01-01

layers in the sea. APPROACH In March of 2007 we were awarded $112,842 for the fabrication of an autonomous profiler (the SeaHorse ) for the...detection of thin layers of phytoplankton in the coastal ocean. The SeaHorse (Figures 1, 2) makes use of wave energy to power extended, high-resolution...to adaptively change the sample rate of the SeaHorse profiler itself. For example, if we observe a layer at 10 m depth, we can instruct the profiler

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

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.

Layer-by-Layer Assembly for Preparation of High-Performance Forward Osmosis Membrane

NASA Astrophysics Data System (ADS)

Yang, Libin; Zhang, Jinglong; Song, Peng; Wang, Zhan

2018-01-01

Forward osmosis (FO) membrane with high separation performance is needed to promote its practical applications. Herein, layer-by-layer (LbL) approach was used to prepare a thin and highly cross-linked polyamide layer on a polyacrylonitrile substrate surface to prepare a thin-film composite forward osmosis (TFC-FO) membrane with enhanced FO performance. The effects of monomer concentrations and assembly cycles on the performance of the TFC-FO membranes were systematically investigated. Under the optimal preparation condition, TFC-FO membrane achieved the best performance, exhibiting the water flux of 14.4/6.9 LMH and reverse salt flux of 7.7/3.8 gMH under the pressure retarded osmosis/forward osmosis (PRO/FO) mode using 1M NaCl as the draw against a DI-water feed, and a rejection of 96.1% for 2000 mg/L NaCl aqueous solution. The result indicated that layer-by-layer method was a potential method to regulate the structure and performance of the TFC-FO membrane.

Fabrication of Uniform Hydrogel Microparticles with Alternate Polyelectrolyte/Silica Shell Layers for Applications of Controlled Loading and Releasing

NASA Astrophysics Data System (ADS)

Jeong, Eun Sook; Kim, Jin Woong

2015-03-01

Hydrogel particles, also known as microgels, consist of cross-linked three-dimensional water-soluble polymer networks. They play an essential role in loading and delivering active ingredients in medicine, cosmetics, and foods. Despite their excellent biocompatibility as well as structural diversity, much wider applications are limited due mainly to their intrinsically loose network nature. This study introduces a practical and straightforward method that enables fabrication of hydrogel microparticles layered with a mechanically robust hybrid thin shell. Basically highly monodisperse hydrogel microparticles were produced in microcapillary devices. Then, their surface was coated with alternate polyelectrolyte layers through the layer-by-layer deposition. Finally a thin silica layer was again formed by reduction of silicate on the amino-functionalized polyelectrolyte layer. We have figured out that these hybrid hydrogel microparticles showed controlled loading and releasing behaviors for water-soluble probe molecules. Moreover, we have demonstrated that they can be applied for immobilization of biomacromolecules, such as bacteria and living cells, and even for targeted releasing.

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.

Potential-specific structure at the hematite-electrolyte interface

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

McBriarty, Martin E.; Stubbs, Joanne; Eng, Peter

The atomic-scale structure of interfaces between metal oxides and aqueous electrolytes controls their catalytic, geochemical, and corrosion behavior. Measurements that probe these interfaces in situ provide important details of ion and solvent arrangements, but atomically precise structural models do not exist for common oxide-electrolyte interfaces far from equilibrium. Using a novel cell, we measured the structure of the hematite (a-Fe 2O 3) (110more » $$\\bar{2}$$)-electrolyte interface under controlled electrochemical bias using synchrotron crystal truncation rod X ray scattering. At increasingly cathodic potentials, charge-compensating protonation of surface oxygen groups increases the coverage of specifically bound water while adjacent water layers displace outwardly and became disordered. Returning to open circuit potential leaves the surface in a persistent metastable protonation state. The flux of current and ions at applied potential is thus regulated by a unique interfacial electrolyte environment, suggesting that electrical double layer models should be adapted to the dynamically changing interfacial structure far from equilibrium.« less

Porous framework of T{sub 2}[Fe(CN){sub 6}].xH{sub 2}O with T=Co, Ni, Cu, Zn, and H{sub 2} storage

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

Avila, M.; Reguera, L.; Rodriguez-Hernandez, J.

2008-11-15

The materials under study were prepared from aqueous solutions of ferrocyanic acid and salts of the involved transition metals and their crystal structure solved and refined from X-ray powder diffraction data. Complementary information from thermogravimetric, infrared and Moessbauer data was also used for the structural study. Three different crystal structures were found: hexagonal (P-3) for Zn with the zinc atom coordinated to three N ends of CN groups plus a water molecule, cubic (Pm-3m) for Ni and Cu, and monoclinic (P2{sub 1}/m) for Co. For Ni and Cu the obtained solids have an open channel framework related to 50% ofmore » vacancies for the building unit, [Fe(CN){sub 6}]. In the as-synthesized material the framework free volume is occupied by coordinated and hydrogen-bonded water molecules. These of hexacyanoferrates (II) have received certain attention as prototype of materials for the hydrogen storage. In the anhydrous phase of Ni and Cu, 50% of the metal (T) coordination sites, located at the cavities surface, will be available to interact with the hydrogen molecule. However, when the crystal waters are removed the porous frameworks collapse as it is suggested by H{sub 2} and CO{sub 2} adsorption data. For Co, a structure of stacked layers was found where the cobalt atoms have both tetrahedral and octahedral coordination. The layers remain together through a network of hydrogen-bonding interactions between coordinated and weakly bonded water molecules. No H{sub 2} adsorption was observed in the anhydrous phase of Co. For Zn, the porous framework remains stable on the water removal but with a system of narrow channels and a small available volume, also inaccessible to H{sub 2}. - Graphical abstract: Structure of stacked layers for CO{sub 2}[Fe(CN){sub 6}].xH{sub 2}O.« less

[Root anatomical structure and hydraulic traits of three typical shrubs on the sandy lands of northern Shaanxi Province, China].

PubMed

Ai, Shao-shui; Li, Yang-yang; Chen, Jia-cun; Chen, Wei-yue

2015-11-01

Root xylem anatomical structure and hydraulic traits of three typical shrubs, i.e., Salix psammophila, Caragana korshinskii and Hippophae rhamnoides, within two soil layers (0-20 cm and 30-50 cm) were compared. The results showed that S. psammophila had a higher leaf water potential than C. korshinskii and H. rhamnoides, the average maximum and minimum lumen diameter (d(max) and d(min), respectively), the average lumen area of vessels (Alum) and the ratio of lumen area of all vessels to xylem area (Aves/Axyl) in S. psammophila roots were also significantly higher than those in C. korshinskii and H. rhamnoides, and the root vessel density (VD) in S. psammophila was the same as that in H. rhamnoides but significantly higher than that in C. korshinskii. Root hydraulic conductivity in S. psammophila was 5 times of C. korshinskii and 2.8 times of H. hamnoides. The vulnerability index in S. psammophila roots was similar to that in C. korshinskii but higher than that in H. hamnoides. S. psammophila belonged to a water-spending species, whereas both C. korshinskii and H. rhamnoides were water-saving species, and C. korshinskii was more drought-resistant than H. rhamnoides. There was no difference of d(max), d(min) and Alum between roots in two soil layers, but roots within in the 30-50 cm soil layer had larger VD and Aves/Axyl. The root specific hydraulic conductivity within the 30-50 cm soil layer was significantly higher than within the surface soil layer, whereas the vulnerability index within the 30-50 cm soil layer was smaller, indicating roots in deep soil layers had higher hydraulic transport efficiency and lower hydraulic vulnerability.

Emulsion Inks for 3D Printing of High Porosity Materials.

PubMed

Sears, Nicholas A; Dhavalikar, Prachi S; Cosgriff-Hernandez, Elizabeth M

2016-08-01

Photocurable emulsion inks for use with solid freeform fabrication (SFF) to generate constructs with hierarchical porosity are presented. A high internal phase emulsion (HIPE) templating technique was utilized to prepare water-in-oil emulsions from a hydrophobic photopolymer, surfactant, and water. These HIPEs displayed strong shear thinning behavior that permitted layer-by-layer deposition into complex shapes and adequately high viscosity at low shear for shape retention after extrusion. Each layer was actively polymerized with an ultraviolet cure-on-dispense (CoD) technique and compositions with sufficient viscosity were able to produce tall, complex scaffolds with an internal lattice structure and microscale porosity. Evaluation of the rheological and cure properties indicated that the viscosity and cure rate both played an important role in print fidelity. These 3D printed polyHIPE constructs benefit from the tunable pore structure of emulsion templated material and the designed architecture of 3D printing. As such, these emulsion inks can be used to create ultra high porosity constructs with complex geometries and internal lattice structures not possible with traditional manufacturing techniques. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Orbital SAR and Ground-Penetrating Radar for Mars: Complementary Tools in the Search for Water

NASA Technical Reports Server (NTRS)

Campbell, B. A.; Grant, J. A.

2000-01-01

The physical structure and compositional variability of the upper martian crust is poorly understood. Optical and infrared measurements probe at most the top few cm of the surface layer and indicate the presence of layered volcanics and sediments, but it is likely that permafrost, hydrothermal deposits, and transient liquid water pockets occur at depths of meters to kilometers within the crust. An orbital synthetic aperture radar (SAR) can provide constraints on surface roughness, the depth of fine-grained aeolian or volcanic deposits, and the presence of strongly absorbing near-surface deposits such as carbonates. This information is crucial to the successful landing and operation of any rover designed to search for subsurface water. A rover-based ground-penetrating radar (GPR) can reveal layering in the upper crust, the presence of erosional or other subsurface horizons, depth to a permafrost layer, and direct detection of near-surface transient liquid water. We detail here the radar design parameters likely to provide the best information for Mars, based on experience with SAR and GPR in analogous terrestrial or planetary environments.

Co-delivery of ibuprofen and gentamicin from nanoporous anodic titanium dioxide layers.

PubMed

Pawlik, Anna; Jarosz, Magdalena; Syrek, Karolina; Sulka, Grzegorz D

2017-04-01

Although single-drug therapy may prove insufficient in treating bacterial infections or inflammation after orthopaedic surgeries, complex therapy (using both an antibiotic and an anti-inflammatory drug) is thought to address the problem. Among drug delivery systems (DDSs) with prolonged drug release profiles, nanoporous anodic titanium dioxide (ATO) layers on Ti foil are very promising. In the discussed research, ATO samples were synthesized via a three-step anodization process in an ethylene glycol-based electrolyte with fluoride ions. The third step lasted 2, 5 and 10min in order to obtain different thicknesses of nanoporous layers. Annealing the as-prepared amorphous layers at the temperature of 400°C led to obtaining the anatase phase. In this study, water-insoluble ibuprofen and water-soluble gentamicin were used as model drugs. Three different drug loading procedures were applied. The desorption-desorption-diffusion (DDD) model of the drug release was fitted to the experimental data. The effects of crystalline structure, depth of TiO 2 nanopores and loading procedure on the drug release profiles were examined. The duration of the drug release process can be easily altered by changing the drug loading sequence. Water-soluble gentamicin is released for a long period of time if gentamicin is loaded in ATO as the first drug. Additionally, deeper nanopores and anatase phase suppress the initial burst release of drugs. These results confirm that factors such as morphological and crystalline structure of ATO layers, and the procedure of drug loading inside nanopores, allow to alter the drug release performance of nanoporous ATO layers. Copyright © 2017 Elsevier B.V. All rights reserved.

Developing a framework for integrating turbulence measurements and modeling of ecosystem-atmosphere interactions

NASA Astrophysics Data System (ADS)

Markfort, C. D.

2017-12-01

Aquatic ecosystems are integrators of nutrient and carbon from their watersheds. The effects of climate change in many cases will enhance the rate of these inputs and change the thermodynamics within aquatic environments. It is unclear the extent these changes will have on water quality and carbon assimilation, but the drivers of these processes will be determined by the complex interactions at the land-water and air-water interfaces. For example, flow over and beneath wind-driven surface waves generate turbulence that plays an important role in aquatic ecology and biogeochemistry, exchange of gases such as oxygen and carbon dioxide, and it is important for the transfer of energy and controlling evaporation. Energy transferred from the atmosphere promotes the generation and maintenance of waves. A fraction of the energy is transferred to the surface mixed layer through the generation of turbulence. Energy is also transferred back to the atmosphere by waves. There is a need to quantify the details of the coupled boundary layers of the air-water system to better understand how turbulence plays a role in the interactions. We have developed capabilities to conduct field and laboratory experiments using eddy covariance on tall-towers and rafts, UAS platforms integrated with remote sensing, and detailed wind-wave measurements with time-resolved PIV in a new boundary layer wind-wave tunnel. We will show measurements of the detailed structure of the air and water boundary layers under varying wind and wave conditions in the newly developed IIHR Boundary-Layer Wind-Wave Tunnel. The facility combines a 30-m long recirculating water channel with an open-return boundary layer wind tunnel. A thick turbulent boundary layer is developed in the 1 m high air channel, over the water surface, allowing for the study of boundary layer turbulence interacting with a wind-driven wave field. Results will help interpret remote sensing, energy budget measurements, and turbulence transport models for sheltered lakes influenced by terrain and tall trees.

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

Sankar, M. S. Ravi, E-mail: rameshg.phy@pondiuni.edu; Gangineni, Ramesh Babu, E-mail: rameshg.phy@pondiuni.edu

The present work reveals soft lithography strategy based on self assembly and replica molding for carrying out micro and nanofabrication. It provides a convenient, effective and very low cost method for the formation and manufacturing of micro and nano structures. Al-layer of compact disc (sony CD-R) used as a stamp with patterned relief structures to generate patterns and structures with pattern size of 100nm height, 1.7 μm wide. In literature, PDMS (Polydimethylsiloxane) solution is widely used to get negative copy of the Al-layer. In this work, we have used inexpensive white glue (Polyvinylacetate + water), 15gm (□5) and PVDF (Polyvinylidenemore » difluoride) spin coated films and successfully transferred the nano patterns of Al layer on to white glue and PVDF films.« less

An ellipsometric approach towards the description of inhomogeneous polymer-based Langmuir layers

PubMed Central

Rottke, Falko O; Schulz, Burkhard; Richau, Klaus; Kratz, Karl

2016-01-01

Summary The applicability of nulling-based ellipsometric mapping as a complementary method next to Brewster angle microscopy (BAM) and imaging ellipsometry (IE) is presented for the characterization of ultrathin films at the air–water interface. First, the methodology is demonstrated for a vertically nonmoving Langmuir layer of star-shaped, 4-arm poly(ω-pentadecalactone) (PPDL-D4). Using nulling-based ellipsometric mapping, PPDL-D4-based inhomogeneously structured morphologies with a vertical dimension in the lower nm range could be mapped. In addition to the identification of these structures, the differentiation between a monolayer and bare water was possible. Second, the potential and limitations of this method were verified by applying it to more versatile Langmuir layers of telechelic poly[(rac-lactide)-co-glycolide]-diol (PLGA). All ellipsometric maps were converted into thickness maps by introduction of the refractive index that was derived from independent ellipsometric experiments, and the result was additionally evaluated in terms of the root mean square roughness, R q. Thereby, a three-dimensional view into the layers was enabled and morphological inhomogeneity could be quantified. PMID:27826490

Origin of leucite-rich and sanidine-rich flow layers in the Leucite Hills Volcanic Field, Wyoming

NASA Astrophysics Data System (ADS)

Gunter, W. D.; Hoinkes, Georg; Ogden, Palmer; Pajari, G. E.

1990-09-01

Two types of orendite (sanidine-phlogopite lamproite) and wyomingite (leucite-phlogopite lamproite) intraflow layering are present in the ultrapotassic Leucite Hills Volcanic Field, Wyoming. In large-scale layering, wyomingites are confined to the base of the flow, while in centimeter-scale layering, orendite and wyomingite alternate throughout the flow. The mineralogy of the orendites and wyomingites are the same; only the relative amount of each mineral vary substantially. The chemical compositions of adjacent layers of wyomingite and orendite are almost identical except for water. The centimeter-scale flow layering probably represents fossil streamlines of the lava and therefore defines the path of circulation of the viscous melt. Toward the front of the flow, the layers are commonly folded. Structures present which are indicative that the flows may have possessed a yield strength are limb shears, boudinage, and slumping. Phlogopite phenocrysts are poorly aligned in the orendite layers, while they are often in subparallel alignment in the wyomingite layers; and they are used as a measure of shearing intensity during emplacement of the flow. Vesicle volumes are concentrated in the orendite layers. In the large-scale layering, a discontinuous base rubble zone of autobreccia is overlain by a thin platy zone followed by a massive zone which composes more than the upper 75% of the flow. Consequently, we feel that the origin of the layering may be related to shearing. Two extremes in the geometry of shearing are proposed: closely spaced, thin, densely sheared layers separated by discrete intervals throughout a lava flow as in the centimeter-scale layering and classical plug flow where all the shearing is confined to the base as in the large-scale layering. A mechanism is proposed which causes thixotropic behavior and localizes shearing: the driving force is the breakdown of molecular water to form T-OH bonds which establishes a chemical potential gradient for water in the melt. The higher activity of water in the nonsheared regions allows sandine to crystallize, whereas the lower activity of water in the areas of active shearing causes leucite to crystallize.

Synthesis, characterization and application of two-dimensional layered metal hydroxides for environmental remediation purposes

NASA Astrophysics Data System (ADS)

Machingauta, Cleopas

Two-dimensional layered nano composites, which include layered double hydroxides (LDHs), hydroxy double salts (HDSs) and layered hydroxide salts (LHSs) are able to intercalate different molecular species within their gallery space. These materials have a tunable structural composition which has made them applicable as fire retardants, adsorbents, catalysts, catalyst support materials, and ion exchangers. Thermal treatment of these materials results in destruction of the layers and formation of mixed metal oxides (MMOs) and spinels. MMOs have the ability to adsorb anions from solution and may also regenerate layered structures through a phenomenon known as memory effect. Zinc-nickel hydroxy nitrate was used for the uptake of a series of halogenated acetates (HAs). HAs are pollutants introduced into water systems as by-products of water chlorination and pesticide degradation; their sequestration from water is thus crucial. Optimization of layered materials for controlled uptake requires an understanding of their ion-exchange kinetics and thermodynamics. Exchange kinetics of these anions was monitored using ex-situ PXRD, UV-vis, HPLC and FTIR. It was revealed that exchange rates and uptake efficiencies are related to electronic spatial extents and the charge on carboxyl-oxygen atoms. In addition, acetate and nitrate-based HDSs were used to explore how altering the hydroxide layer affects uptake of acetate/nitrate ions. Changing the metal identities affects the interaction of the anions with the layers. From FTIR, we observed that nitrates coordinate in a D3h and Cs/C 2v symmetry; the nitrates in D3h symmetry were easily exchangeable. Interlayer hydrogen bonding was also revealed to be dependent on metal identity. Substituting divalent cations with trivalent cations produces materials with a higher charge density than HDSs and LHSs. A comparison of the uptake efficiency of zinc-aluminum, zinc-gallium and zinc-nickel hydroxy nitrates was performed using trichloroacetic acid as target anion. Uptake efficiency was better for LDHs than HDS, and between the LDHs, zinc-aluminum hydroxy nitrate was the best material for the uptake of tClAc. Calcined LDHs were applied for the uptake of methyl-orange, model azo-dye. The ability to regenerate the layered structures was helpful for improving adsorption efficiency. It has been reveal that calcined LDHs are also better adsorbents than calcined HDSs.

Ultrathin epitaxial barrier layer to avoid thermally induced phase transformation in oxide heterostructures

DOE PAGES

Baek, David J.; Lu, Di; Hikita, Yasuyuki; ...

2016-12-22

Incorporating oxides with radically different physical and chemical properties into heterostructures offers tantalizing possibilities to derive new functions and structures. Recently, we have fabricated freestanding 2D oxide membranes using the water-soluble perovskite Sr 3Al 2O 6 as a sacrificial buffer layer. Here, with atomic-resolution spectroscopic imaging, we observe that direct growth of oxide thin films on Sr 3Al 2O 6 can cause complete phase transformation of the buffer layer, rendering it water-insoluble. More importantly, we demonstrate that an ultrathin SrTiO 3 layer can be employed as an effective barrier to preserve Sr 3Al 2O 6 during subsequent growth, thus allowingmore » its integration in a wider range of oxide heterostructures.« less

Field data analysis of asphalt road paving damages caused by tree roots

NASA Astrophysics Data System (ADS)

Weissteiner, Clemens; Rauch, Hans Peter

2015-04-01

Tree root damages are a frequent problem along paved cycling paths and service roads of rivers and streams. Damages occur mostly on streets with thin asphalt layers and especially in the upper part of the pavement structure. The maintainers of these roads are faced with frequent and high annual repair costs in order to guarantee traffic safety and pleasant cycling conditions. The focus of this research project is to get an insight in the processes governing the growth of the tree roots in asphalt layers and to develop test methods to avoid rood penetration into the road structure. Tree vegetation has been analysed selectively along a 300 km long cycle and service path of the Danube River in the region of Austria. Tree characteristics, topographic as well as hydrologic conditions have been analysed at 119 spots with different asphalt damage intensities. On 5 spots additional investigations on the root growth characteristics where performed. First results underline a high potential damage of pioneer trees which are growing naturally along rivers. Mostly, local occurring fast growing tree species penetrated the road layer structure. In a few cases other tree species where as well responsible for road structure damages. The age respectively the size of the trees didn't seem to influence significantly the occurrence of asphalt damages. Road structure damages were found to appear unaffected by hydrologic or topographic conditions. However, results have to be interpreted with care as the investigations represent a temporally limited view of the problem situation. The investigations of the root growth characteristics proved that tree roots penetrate the road structure mostly between the gravel sublayer and the asphalt layer as the layers it selves don't allow a penetration because of their high compaction. Furthermore roots appear to be attracted by condensed water at the underside of the asphalt layer. Further steps of the research project imply testing of different compositions of gravel size mixtures as sublayer material. A coarse gravel size mixture allows the condensed water to drain in deeper layers and inhibits root growth because of mechanical impedance and air pruning of roots.

Minimalist design of water-soluble cross-[beta] architecture

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

Biancalana, Matthew; Makabe, Koki; Koide, Shohei

Demonstrated successes of protein design and engineering suggest significant potential to produce diverse protein architectures and assemblies beyond those found in nature. Here, we describe a new class of synthetic protein architecture through the successful design and atomic structures of water-soluble cross-{beta} proteins. The cross-{beta} motif is formed from the lamination of successive {beta}-sheet layers, and it is abundantly observed in the core of insoluble amyloid fibrils associated with protein-misfolding diseases. Despite its prominence, cross-{beta} has been designed only in the context of insoluble aggregates of peptides or proteins. Cross-{beta}'s recalcitrance to protein engineering and conspicuous absence among the knownmore » atomic structures of natural proteins thus makes it a challenging target for design in a water-soluble form. Through comparative analysis of the cross-{beta} structures of fibril-forming peptides, we identified rows of hydrophobic residues ('ladders') running across {beta}-strands of each {beta}-sheet layer as a minimal component of the cross-{beta} motif. Grafting a single ladder of hydrophobic residues designed from the Alzheimer's amyloid-{beta} peptide onto a large {beta}-sheet protein formed a dimeric protein with a cross-{beta} architecture that remained water-soluble, as revealed by solution analysis and x-ray crystal structures. These results demonstrate that the cross-{beta} motif is a stable architecture in water-soluble polypeptides and can be readily designed. Our results provide a new route for accessing the cross-{beta} structure and expanding the scope of protein design.« less

Minimalist design of water-soluble cross-beta architecture.

PubMed

Biancalana, Matthew; Makabe, Koki; Koide, Shohei

2010-02-23

Demonstrated successes of protein design and engineering suggest significant potential to produce diverse protein architectures and assemblies beyond those found in nature. Here, we describe a new class of synthetic protein architecture through the successful design and atomic structures of water-soluble cross-beta proteins. The cross-beta motif is formed from the lamination of successive beta-sheet layers, and it is abundantly observed in the core of insoluble amyloid fibrils associated with protein-misfolding diseases. Despite its prominence, cross-beta has been designed only in the context of insoluble aggregates of peptides or proteins. Cross-beta's recalcitrance to protein engineering and conspicuous absence among the known atomic structures of natural proteins thus makes it a challenging target for design in a water-soluble form. Through comparative analysis of the cross-beta structures of fibril-forming peptides, we identified rows of hydrophobic residues ("ladders") running across beta-strands of each beta-sheet layer as a minimal component of the cross-beta motif. Grafting a single ladder of hydrophobic residues designed from the Alzheimer's amyloid-beta peptide onto a large beta-sheet protein formed a dimeric protein with a cross-beta architecture that remained water-soluble, as revealed by solution analysis and x-ray crystal structures. These results demonstrate that the cross-beta motif is a stable architecture in water-soluble polypeptides and can be readily designed. Our results provide a new route for accessing the cross-beta structure and expanding the scope of protein design.

Simulation of Surface Energy Fluxes and Snow Interception Using a Higher Order Closure Multi-Layer Soil-Vegetation-Atmospheric Model: The Effect of Canopy Shape and Structure

NASA Astrophysics Data System (ADS)

McGowan, L. E.; Dahlke, H. E.; Paw U, K. T.

2015-12-01

Snow cover is a critical driver of the Earth's surface energy budget, climate change, and water resources. Variations in snow cover not only affect the energy budget of the land surface but also represent a major water supply source. In California, US estimates of snow depth, extent, and melt in the Sierra Nevada are critical to estimating the amount of water available for both California agriculture and urban users. However, accurate estimates of snow cover and snow melt processes in forested area still remain a challenge. Canopy structure influences the vertical and spatiotemporal distribution of snow, and therefore ultimately determines the degree and extent by which snow alters both the surface energy balance and water availability in forested regions. In this study we use the Advanced Canopy-Atmosphere-Soil algorithm (ACASA), a multi-layer soil-vegetation-atmosphere numerical model, to simulate the effect of different snow-covered canopy structures on the energy budget, and temperature and other scalar profiles within different forest types in the Sierra Nevada, California. ACASA incorporates a higher order turbulence closure scheme which allows the detailed simulation of turbulent fluxes of heat and water vapor as well as the CO2 exchange of several layers within the canopy. As such ACASA can capture the counter gradient fluxes within canopies that may occur frequently, but are typically unaccounted for, in most snow hydrology models. Six different canopy types were modeled ranging from coniferous forests (e.g. most biomass near the ground) to top-heavy (e.g. most biomass near the top of the crown) deciduous forests to multi-layered forest canopies (e.g. mixture of young and mature trees). Preliminary results indicate that the canopy shape and structure associated with different canopy types fundamentally influence the vertical scalar profiles (including those of temperature, moisture, and wind speed) in the canopy and thus alter the interception and snow melt dynamics in forested land surfaces. The turbulent transport dynamics, including counter-gradient fluxes, and radiation features including land surface albedo, are discussed in the context of the snow energy balance.

Performance of pervious pavement parking bays storing rainwater in the north of Spain.

PubMed

Gomez-Ullate, E; Bayon, J R; Coupe, S; Castro-Fresno, D

2010-01-01

Pervious pavements are drainage techniques that improve urban water management in a sustainable manner. An experimental pervious pavement parking area has been constructed in the north of Spain (Santander), with the aim of harvesting good quality rainwater. Forty-five pervious pavement structures have been designed and constructed to measure stored water quantity and quality simultaneously. Ten of these structures are specifically constructed with different geotextile layers for improving water storage within the pavements. Following the confirmation in previous laboratory experiments that the geotextile influenced on water storage, two different geosynthetics (Inbitex and a One Way evaporation control membrane) and control pervious pavements with no geotextile layers were tested in the field. Weather conditions were monitored in order to find correlations with the water storage within the pervious pavement models tested. During one year of monitoring the three different pervious pavement types tested remained at their maximum storage capacity. The heavy rain events which occurred during the experimental period caused evaporation rates within the pervious pavements to be not significant, but allowed the researchers to observe certain trends in the water storage. Temperature was the most closely correlated weather factor with the level of the water stored within the pervious pavements tested.

Freezing, melting and structure of ice in a hydrophilic nanopore.

PubMed

Moore, Emily B; de la Llave, Ezequiel; Welke, Kai; Scherlis, Damian A; Molinero, Valeria

2010-04-28

The nucleation, growth, structure and melting of ice in 3 nm diameter hydrophilic nanopores are studied through molecular dynamics simulations with the mW water model. The melting temperature of water in the pore was T(m)(pore) = 223 K, 51 K lower than the melting point of bulk water in the model and in excellent agreement with experimental determinations for 3 nm silica pores. Liquid and ice coexist in equilibrium at the melting point and down to temperatures as low as 180 K. Liquid water is located at the interface of the pore wall, increasing from one monolayer at the freezing temperature, T(f)(pore) = 195 K, to two monolayers a few degrees below T(m)(pore). Crystallization of ice in the pore occurs through homogeneous nucleation. At the freezing temperature, the critical nucleus contains approximately 75 to 100 molecules, with a radius of gyration similar to the radius of the pore. The critical nuclei contain features of both cubic and hexagonal ice, although stacking of hexagonal and cubic layers is not defined until the nuclei reach approximately 150 molecules. The structure of the confined ice is rich in stacking faults, in agreement with the interpretation of X-ray and neutron diffraction experiments. Though the presence of cubic layers is twice as prevalent as hexagonal ones, the crystals should not be considered defective Ic as sequences with more than three adjacent cubic (or hexagonal) layers are extremely rare in the confined ice.

First oceanographic observations on the Wandel Sea shelf in Northeast Greenland: Tracing the Arctic Ocean outflow through the western Fram Strait

NASA Astrophysics Data System (ADS)

Dmitrenko, Igor A.; Kirillov, Sergei A.; Rudels, Bert; Babb, David G.; Pedersen, Leif T.; Rysgaard, Soeren; Kristoffersen, Yngve; Barber, David G.

2016-04-01

The first-ever conductivity-temperature-depth (CTD) observations on the Wandel Sea shelf in North Eastern Greenland were collected from the land-fast ice in April-May 2015 as a part of the Arctic Science Partnership collaboration during the first research campaign at the Villum Research Station. They were complemented by (i) the ice-tethered profiler (ITP) and Acoustic Dopler Current Profiler (ADCP) mooring observations in ~300 m of the tidewater glacier outlet from the Flade Isblink Ice Cap and (ii) CTDs taken in June-July 2015 along the Wandel Sea continental slope during the Norwegian FRAM 2014-15 sea ice drift. The CTD profiles deeper than 100 m are used to reveal the origin of water masses and determine the extent to which these water masses have interacted with ambient water from the continental slope. The subsurface water layer from ~20-70 m depth is comprised of freshened water (30-32 psu) that is likely associated with the Pacific Water outflow from the Arctic Ocean through the western Fram Strait. The underlying halocline layer centered at ~80 m (~33 psu) separates the Pacific Water layer from a deeper (<140 m) layer of modified Polar Water that has interacted with the warm Atlantic Water outflow through Fram Strait. The Atlantic Water layer with temperature above 0°C is recorded below 140 m. Over the outer shelf, the halocline layer shows numerous cold density-compensated intrusions indicating lateral interaction with an ambient Polar Water mass across the continental slope. Mooring data shows an enhanced shelf-slope interaction responding the storm event in 23-24 April 2015 with northerly winds exceeding 10 m/s. The on-shelf transport of a cold and turbid water from the upper continental slope results in enhanced interleaving within the depth range of the halocline layer (~70-100 m). Our observations of Pacific Water in the Wandel Sea subsurface layer are set in the context of upstream observations in the Beaufort Sea for 2002-2011 and downstream observations from the Northeast Water Polynya (1992-1993), and clearly show the modification of Pacific Water during its advection across the Arctic Ocean from the Bering Strait to Fram Strait. Moreover, the Wandel Sea shelf and continental slope water shows a different water mass structure indicating the different origin and pathways of the on-shore and off-shore branches of the Arctic Ocean outflow through the Western Fram Strait.

Sandwiched gold/PNIPAm/gold microstructures for smart plasmonics application: towards the high detection limit and Raman quantitative measurements.

PubMed

Elashnikov, R; Mares, D; Podzimek, T; Švorčík, V; Lyutakov, O

2017-08-07

A smart plasmonic sensor, comprising a layer of a stimuli-responsive polymer sandwiched between two gold layers, is reported. As a stimuli-responsive material, a monolayer of poly(N-isopropylacrylamide) (PNIPAm) crosslinked globules is used. A quasi-periodic structure of the top gold layer facilitates efficient excitation and serves as a support for plasmon excitation and propagation. The intermediate layer of PNIPAm efficiently entraps targeted molecules from solutions. The sensor structure was optimized for efficient light focusing in the "active" PNIPAm layer. The optimization was based on the time-resolved finite-element simulations, which take into account the thickness of gold layers, size of PNIPAm globules and Raman excitation wavelength (780 nm). The prepared structures were characterized using SEM, AFM, UV-Vis refractometry and goniometry. Additional AFM scans were performed in water at two temperatures corresponding to the collapsed and swollen PNIPAm states. The Raman measurements demonstrate a high detection limit and perfect reproducibility of the Raman scattering signal for the prepared sensor. In addition, the use of created SERS structures for the detection of relevant molecules in the medical, biological and safety fields was demonstrated.

Hydrogeologic Framework in Three Drainage Basins in the New Jersey Pinelands, 2004-06

USGS Publications Warehouse

Walker, Richard L.; Reilly, Pamela A.; Watson, Kara M.

2008-01-01

The U.S. Geological Survey, in cooperation with the New Jersey Pinelands Commission, began a multi-phase hydrologic investigation in 2004 to characterize the hydrologic system supporting the aquatic and wetland communities of the New Jersey Pinelands area (Pinelands). The Pinelands is an ecologically diverse area in the southern New Jersey Coastal Plain underlain by the Kirkwood-Cohansey aquifer system. The demand for ground water from this aquifer system is increasing as local development increases. To assess the effects of ground-water withdrawals on Pinelands stream and wetland water levels, three drainage basins were selected for detailed hydrologic assessments, including the Albertson Brook, McDonalds Branch and the Morses Mill Stream basins. Study areas were defined surrounding the three drainage basins to provide sub-regional hydrogeologic data for the ground-water flow modeling phase of this study. In the first phase of the hydrologic assessments, a database of hydrogeologic information and a hydrogeologic framework model for each of the three study areas were produced. These framework models, which illustrate typical hydrogeologic variations among different geographic subregions of the Pinelands, are the structural foundation for predictive ground-water flow models to be used in assessing the hydrologic effects of increased ground-water withdrawals. During 2004-05, a hydrogeologic database was compiled using existing and new geophysical and lithologic data including suites of geophysical logs collected at 7 locations during the drilling of 21 wells and one deep boring within the three study areas. In addition, 27 miles of ground-penetrating radar (GPR) surface geophysical data were collected and analyzed to determine the depth and extent of shallow clays in the general vicinity of the streams. On the basis of these data, the Kirkwood-Cohansey aquifer system was divided into 7 layers to construct a hydrogeologic framework model for each study area. These layers are defined by their predominant sediment textures as aquifers and leaky confining layers. The confining layer at the base of the Kirkwood-Cohansey aquifer system, depending on location, is defined as one of two distinct clays of the Kirkwood Formation. The framework models are described using hydrogeologic sections, maps of structure tops of layers, and thickness maps showing variations of sediment textures of the various model layers. The three framework models are similar in structure but unique to their respective study areas. The hydraulic conductivity of the Kirkwood-Cohansey aquifer system in the vicinity of the three study areas was determined from analysis of 16 slug tests and 136 well-performance tests. The mean values for hydraulic conductivity in the three study areas ranged from about 84 feet per day to 130 feet per day. With the exception of the basal confining layers, the variable and discontinuous nature of clay layers within the Kirkwood-Cohansey aquifer system was confirmed by the geophysical and lithologic records. Leaky confining layers and discontinuous clays are generally more common in the upper part of the aquifer system. Although the Kirkwood-Cohansey aquifer system generally has been considered a water-table aquifer in most areas, localized clays in the aquifer layers and the effectiveness of the leaky confining layers may act to impede the flow of ground water in varying amounts depending on the degree of confinement and the location, duration, and magnitude of the hydraulic stresses applied. Considerable variability exists in the different sediment textures. The extent to which this hydrogeologic variability can be characterized is constrained by the extent of the available data. Thus, the hydraulic properties of the modeled layers were estimated on the basis of available horizontal hydraulic conductivity data and the range of sediment textures estimated from geophysical and lithologic data.

Porous structures of polymer films prepared by spin coating with mixed solvents under humid condition.

PubMed

Park, Min Soo; Joo, Wonchul; Kim, Jin Kon

2006-05-09

We investigate the effects of interfacial energy between water and solvent as well as polymer concentration on the formation of porous structures of polymer films prepared by spin coating of cellulose acetate butyrate (CAB) in mixed solvent of tetrahydrofuran (THF) and chloroform under humid condition. The interfacial energy between water and the solvent was gradually changed by the addition of chloroform to the solvent. At a high polymer concentration (0.15 g/cm3 in THF), porous structures were limited only at the top surfaces of CAB films, regardless of interfacial energies, due to the high viscosity of the solution. At a medium concentration (approximately 0.08 g/cm3 in THF), CAB film had relatively uniform pores at the top surface and very small pores inside the film because of the mixing of the water droplets with THF solution. When chloroform was added to THF, pores at the inner CAB film had a comparable size with those at the top surface because of the reduced degree of the mixing between the water droplets and the mixed solvent. A further decrease in polymer concentration (0.05 g/cm3 in THF) caused the final films to have a two-layer porous structure, and the size of pores at each layer was almost the same.

Integrated Assessment to Evaluate the Artificial Recharge in a Small Portion of the Aquifer of Puebla, Mexico

NASA Astrophysics Data System (ADS)

Arango-Galván, C.; Flores-Marquez, L. E.; Martínez-Serrano, R.

2009-12-01

New policies on the use of water resources in Mexico have led to implement some alternative measures to optimize water management. In particular, water regulation entities have recommended some tools to preserve and protect the groundwater supplies. One of these tools is the artificial recharge by injecting water directly into the aquifer. The main goal of this study is to assess if it is suitable to inject rainwater and surface water in a small portion of the aquifer of the city of Puebla, in central Mexico. Artificial aquifer recharging was evaluated using a numeric model, which simulated the physical properties of the system. The model setup was inferred from an integrated study taking into account hydraulic, geological and geophysical data. The geoelectrical model was computed using electric resistivity tomography (ERT) and time domain electromagnetic data (TDEM). The aquifer geological structure inferred from geophysics depicts the presence of a shallower layer composed of sand and clay deposits with low saturation and permeability. This layer contains silt lenses that can be controlling the persistence of small water bodies on surface. Some water surficial bodies seem to be isolated from the main aquifer system. The intermediate layer shows lower electrical resistivity and higher permeability. Underlying this horizon, it is a deeper layer that reaches 200 m depth, according to information obtained from borehole in the zone. This layer shows an electrical resistivity even lower than intermediate layer but low permeability, caused by the higher content of silts. Both of these layers are the shallower aquifer exploited in the area. Once the numeric model was built we proceeded to simulate scenarios that include the continued extraction and recharge of water in wells located in strategic areas of the study zone. The results suggest that the effect of infiltration is beneficial on aquifer recharge and reduces the cone of depression caused by the extraction. However, this remedial action will only have a positive effect if the extraction rate is adequate.

Structure of the shelf and slope waters of the Antarctic Seas

NASA Astrophysics Data System (ADS)

Artamonova, Ksenia; Antipov, Nikolay; Gangnus, Ivan; Maslennikov, Vyacheslav

2015-04-01

The main objective of present work is to consider characteristics of shelf and slope waters in the Commonwealth, Ross, Amundson and Bellingshausen Seas. Data of Russian surveys led during the Antarctic summer of 2006 - 2014 on RV "Academic Fedorov"and "Academic Treshnikov"was analyzed. Distribution of temperature, salinity, dissolved oxygen, silicate, phosphates and nitrates in the water masses of the Commonwealth and Amundsen seas was shown. Significant differences in the structures of the shelf and slope waters of the seas were observed. A water structure at the oceanological sections of the Commonwealth Sea was constituted by the Antarctic Surface Water (AASW) with enough high concentration of silicate, nitrate nitrogen and phosphates compare with other areas of the World Ocean; the Upper Circumpolar Deep Water (UCDW) characterized by a minimum of the oxygen content, and a maximum of nutrient concentrations; The Lower Circumpolar Deep Water (LCDW) primary characterized by a salinity maximum and a minimum of nutritive salts as well; and the Antarctic Bottom water (AABW). It was shown that the local cold, salt and dense Antarctic Shelf water (ASW) formed in the shelf area of the Commonwealth Sea. The characteristics of ASW were defined. The ASW mixed with the CDW and their mixture (The Bottom Water of the Prydz Bay (BWPB)) moved down along the slope, and reached the bottom.The characteristics of the BWPB were analyzed. The BWPB was defined by higher content of dissolved oxygen (more 5.5 ml/l) and lower contents of biogenic elements (silicon - low 120 µМ, phosphates - low 2.35 µМ and nitrates - low 29 µМ) in the bottom layer at the slope compared with the Circumpolar Deep Water (CDW) characteristics. Interannual variability of characteristics of the water masses was observed on the repeated oceanological section along 70° E in the Commonwealth Sea. It was shown that characteristics and structure of the BWPB undergo appreciable changes year by year. The coldest (-1,5°С) and less salted (34,54‰) BWPB was observed in 2005, and in 2006 the temperature and salinity of this water were increased (-0,6°С; 34,60‰ - 34,63‰), and the thickness of a layer was much less. In 2007 as capacity of the BWPB layer, and its thermohaline characteristics (-1,2°C, 34,56 ‰) have shown again active moving down near to a bottom of the Antarctic continental slope. A water structure at the oceanological sections in the eastern Ross, Amundson and Bellingshausen Seas was constituted by the two basic water masses - the AASW and the CDW. The CDW was presented by the UCDW and LCDW. The characteristics of the UCDW and the LCDW were defined. A significant difference of the structures of these seas from the Commonwealth Sea is a free entrance to the shelf area of the CDW therefore formation of the Antarctic Shelf Water here was represented impossible.

The impact of periglacial cover beds on runoff generation in a small spring catchment, Ore Mountains

NASA Astrophysics Data System (ADS)

Heller, Katja; Hübner, Rico; Kleber, Arno

2010-05-01

The knowledge of hillslope processes is essential to improve pollutant research and flood prediction. Relic periglacial covers are widespread on slopes of the central European low mountain ranges. Cover beds are assumed to be an important control factor for subcutaneous water flow paths. Periglacial cover beds originated by solifluction, kryoturbation and accumulation of loess during Pleistocene times. Differences in bulk density, sediment type, as well as structure and rate of coarse clasts in the layers result in vertical disparity in hydraulic conductivity (anisotropy), leading to interflow. This hypothesis has been testing in an ongoing study in a small spring catchment (6 ha) in the eastern Ore Mountains, south-eastern Germany, since November 2007. The study area is underlain by gneiss and is formed as a slope hollow. The cover beds consist of a 3-layer complex with upper layer, intermediate layer and basal layer. Soil water tension within the layers is measured with 76 recording tensiometers. Electrical resistivity tomography was used to monitor the spatial dispersal of soil moisture. Results of hydrometrical measurements and of electrical resistivity surveys will be described and new findings on slope water dynamics will be presented.

Extremely Black Vertically Aligned Carbon Nanotube Arrays for Solar Steam Generation.

PubMed

Yin, Zhe; Wang, Huimin; Jian, Muqiang; Li, Yanshen; Xia, Kailun; Zhang, Mingchao; Wang, Chunya; Wang, Qi; Ma, Ming; Zheng, Quan-Shui; Zhang, Yingying

2017-08-30

The unique structure of a vertically aligned carbon nanotube (VACNT) array makes it behave most similarly to a blackbody. It is reported that the optical absorptivity of an extremely black VACNT array is about 0.98-0.99 over a large spectral range of 200 nm-200 μm, inspiring us to explore the performance of VACNT arrays in solar energy harvesting. In this work, we report the highly efficient steam generation simply by laminating a layer of VACNT array on the surface of water to harvest solar energy. It is found that under solar illumination the temperature of upper water can significantly increase with obvious water steam generated, indicating the efficient solar energy harvesting and local temperature rise by the thin layer of VACNTs. We found that the evaporation rate of water assisted by VACNT arrays is 10 times that of bare water, which is the highest ratio for solar-thermal-steam generation ever reported. Remarkably, the solar thermal conversion efficiency reached 90%. The excellent performance could be ascribed to the strong optical absorption and local temperature rise induced by the VACNT layer, as well as the ultrafast water transport through the VACNT layer due to the frictionless wall of CNTs. Based on the above, we further demonstrated the application of VACNT arrays in solar-driven desalination.

Subduction and Restratification Along an Eddy Edge: The Role of Ekman Dynamics and Submesoscale Processes

NASA Astrophysics Data System (ADS)

Lucas, A.; Sengupta, D.; D'Asaro, E. A.; Nash, J. D.; Shroyer, E.; Mahadevan, A.; Tandon, A.; MacKinnon, J. A.; Pinkel, R.

2016-02-01

The exchange of heat between the atmosphere and ocean depends sensitively on the structure and extent of the oceanic boundary layer. Heat fluxes into and out of the ocean in turn influence atmospheric processes, and, in the northern Indian Ocean, impact the dominant regional weather pattern (the southwest Monsoon). In late 2015, measurements of the physical structure of the oceanic boundary layer were collected from a pair of research vessels and an array of autonomous assets in the Bay of Bengal as part of an India-U.S. scientific collaboration. Repeated CTD casts by a specialized shipboard system to 200m with a repeat rate of <3 min and a lateral spacing of < 200m, as well as near-surface sampling acoustic current profilers, showed how on the edge of an oceanic mesoscale eddy, the interaction of the mesoscale strain field, Ekman dynamics, and nonlinear submesoscale processes acted to subduct relative saline water under a very thin layer of fresher water derived from riverine sources. Our detailed surveys of the front between the overriding thin, fresh layer, and subducting adjacent more saline water demonstrated the important of small-scale physical dynamics to frontal slumping and the resulting re-stratification processes. These processes were strongly 3-dimensional and time-dependent. Such dynamics ultimately influence air-sea interactions by creating strongly stratified and very thin oceanic boundary layers in the Bay of Bengal, and allow the development of strong, persistent subsurface temperature maxima.

Composites of cationic nanofibrillated cellulose and layered silicates: water vapor barrier and mechanical properties.

PubMed

Ho, Thao T T; Zimmermann, Tanja; Ohr, Steffen; Caseri, Walter R

2012-09-26

Composites of trimethylammonium-modified nanofibrillated cellulose and layered silicates (TMA-NFC/LS) were prepared by high-shear homogenization followed by pressure filtration and vacuum hot-pressing, which gave rise to particularly homogeneous dispersion of the silicate particles. Thirteen different clays and micas were employed. Water vapor barrier and mechanical properties (tensile strength, E-modulus, strain at break) of the composite films were investigated, considering the effects of layered silicate types and their concentration (in the range of 0 to 85 wt %). Good interactions between TMA-NFC and LS were obtained due to electrostatic attraction between cationic fibrils and anionic silicate layers, and even favored by high-shear homogenization process. Furthermore, oriented TMA-NFC/LS composite structure was achieved. Layered silicates exerted a pronounced influence on the water vapor barrier and mechanical properties; however, there was no common trend reflecting their types. The transport of water molecules through TMA-NFC/LS composites was studied considering both diffusion and adsorption mechanisms. As a result, diffusion pathways were proposed based on two new and one well-known models: the "native network", "covered fiber composite", and "fiber-brick composite" models. Importantly, it was found that the insertion of layered silicate particles did not improve automatically the barrier properties as indicated by the commonly used "fiber-brick composite" model. Mica R120 at a 50 wt % loading in composites with TMA-NFC matrix showed 30-fold improved water vapor permeability and 5-fold higher E-modulus compared to commercially used base paper.

An in situ XPS study of L-cysteine co-adsorbed with water on polycrystalline copper and gold

NASA Astrophysics Data System (ADS)

Jürgensen, Astrid; Raschke, Hannes; Esser, Norbert; Hergenröder, Roland

2018-03-01

The interactions of biomolecules with metal surfaces are important because an adsorbed layer of such molecules introduces complex reactive functionality to the substrate. However, studying these interactions is challenging: they usually take place in an aqueous environment, and the structure of the first few monolayers on the surface is of particular interest, as these layers determine most interfacial properties. Ideally, this requires surface sensitive analysis methods that are operated under ambient conditions, for example ambient pressure x-ray photoelectron spectroscopy (AP-XPS). This paper focuses on an AP-XPS study of the interaction of water vapour and l-Cysteine on polycrystalline copper and gold surfaces. Thin films of l-Cysteine were characterized with XPS in UHV and in a water vapour atmosphere (P ≤ 1 mbar): the structure of the adsorbed l-Cysteine layer depended on substrate material and deposition method, and exposure of the surface to water vapour led to the formation of hydrogen bonds between H2O molecules and the COO- and NH2 groups of adsorbed l-Cysteine zwitterions and neutral molecules, respectively. This study also proved that it is possible to investigate monolayers of biomolecules in a gas atmosphere with AP-XPS using a conventional laboratory Al-Kα x-ray source.

Patterns in bacterial and archaeal community structure and diversity in western Beaufort Sea sediments and waters

NASA Astrophysics Data System (ADS)

Hamdan, L. J.; Sikaroodi, M.; Coffin, R. B.; Gillevet, P. M.

2010-12-01

A culture-independent phylogenetic study of microbial communities in water samples and sediment cores recovered from the Beaufort Sea slope east of Point Barrow, Alaska was conducted. The goal of the work was to describe community composition in sediment and water samples and determine the influence of local environmental conditions on microbial populations. Archaeal and bacterial community composition was studied using length heterogeneity-polymerase chain reaction (LH-PCR) and multitag pyrosequencing (MTPS). Sediment samples were obtained from three piston cores on the slope (~1000m depth) arrayed along an east-west transect and one core from a depth of approximately 2000m. Discrete water samples were obtained using a CTD-rosette from three locations adjacent to piston core sites. Water sample were selected at three discrete depths within a vertically stratified (density) water column. The microbial community in near surface waters was distinct from the community observed in deeper stratified layers of the water column. Multidimensional scaling analysis (MDS) revealed that water samples from mid and deep stratified layers bore high similarity to communities in cores collected in close proximity. Overall, the highest diversity (bacteria and archaea) was observed in a core which had elevated methane concentration relative to other locations. Geochemical (e.g., bulk organic and inorganic carbon pools, nutrients, metabolites) and physical data (e.g. depth, water content) were used to reveal the abiotic factors structuring microbial communities. The analysis indicates that sediment water content (porosity) and inorganic carbon concentration are the most significant structuring elements on Beaufort shelf sedimentary microbial communities.

Re-initiation of bottom water formation in the East Sea (Japan Sea) in a warming world.

PubMed

Yoon, Seung-Tae; Chang, Kyung-Il; Nam, SungHyun; Rho, TaeKeun; Kang, Dong-Jin; Lee, Tongsup; Park, Kyung-Ae; Lobanov, Vyacheslav; Kaplunenko, Dmitry; Tishchenko, Pavel; Kim, Kyung-Ryul

2018-01-25

The East Sea (Japan Sea), a small marginal sea in the northwestern Pacific, is ventilated deeply down to the bottom and sensitive to changing surface conditions. Addressing the response of this marginal sea to the hydrological cycle and atmospheric forcing would be helpful for better understanding present and future environmental changes in oceans at the global and regional scales. Here, we present an analysis of observations revealing a slowdown of the long-term deepening in water boundaries associated with changes of water formation rate. Our results indicate that bottom (central) water formation has been enhanced (reduced) with more (less) oxygen supply to the bottom (central) layer since the 2000s. This paper presents a new projection that allows a three-layered deep structure, which retains bottom water, at least until 2040, contrasting previous results. This projection considers recent increase of slope convections mainly due to the salt supply via air-sea freshwater exchange and sea ice formation and decrease of open-ocean convections evidenced by reduced mixed layer depth in the northern East Sea, resulting in more bottom water and less central water formations. Such vigorous changes in water formation and ventilation provide certain implications on future climate changes.

Durable underwater superoleophobic PDDA/halloysite nanotubes decorated stainless steel mesh for efficient oil-water separation

NASA Astrophysics Data System (ADS)

Hou, Kun; Zeng, Yicheng; Zhou, Cailong; Chen, Jiahui; Wen, Xiufang; Xu, Shouping; Cheng, Jiang; Lin, Yingguang; Pi, Pihui

2017-09-01

A durable underwater superoleophobic mesh was conveniently prepared by layer-by-layer (LBL) assembly of poly (diallyldimethylammonium chloride) (PDDA) and halloysite nanotubes (HNTs) on a stainless steel mesh. The hierarchical structure and roughness of the PDDA/HNTs coating surface were controlled by adjusting the number of layer deposition cycles. When the PDDA/HNTs coating with 10 deposition cycles was decorated on the mesh with pore size of about 54 μm, the underwater superoleophobic mesh was obtained. The as-prepared underwater superoleophobic PDDA/HNTs decorated mesh exhibits outstanding oil-water separation performance with a separation efficiency of over 97% for various oil/water mixtures, which allowed water to pass through while repelled oil completely. In addition, the as-prepared decorated mesh still maintained high separation efficiency above 97% after repeated 20 separation times for hexane/water mixture or chloroform/water mixture. More importantly, the as-prepared decorated mesh is durable enough to resist chemical and mechanical challenges, such as strong alkaline, salt aqueous and sand abrasion. Therefore, the as-prepared decorated mesh has practical utility in oil-water separation due to its stable oil-water performance, remarkable chemical and mechanical durability and the facile and eco-friendly preparation process.

Remote sensing and GIS approach for water-well site selection, southwest Iran

USGS Publications Warehouse

Rangzan, K.; Charchi, A.; Abshirini, E.; Dinger, J.

2008-01-01

The Pabdeh-Lali Anticline of northern Khuzestan province is located in southwestern Iran and occupies 790 km2. This structure is situated in the Zagros folded belt. As a result of well-developed karst systems in the anticlinal axis, the water supply potential is high and is drained by many peripheral springs. However, there is a scarcity of water for agriculture and population centers on the anticlinal flanks, which imposes a severe problem in terms of area development. This study combines remotely sensed (RS) data and a geographical information system (GIS) into a RSGIS technique to delineate new areas for groundwater development and specific sites for drilling productive water wells. Toward these goals, RS data were used to develop GIS layers for lithology, structural geology, topographic slope, elevation, and drainage density. Field measurements were made to create spring-location and groundwater-quality GIS layers. Subsequently, expert choice and relational methods were used in a GIS environment to conjunctively analyze all layers to delineate preferable regions and 43 individual sites in which to drill water wells. Results indicate that the most preferred areas are, in preferential order, within recent alluvial deposits, the Bakhtiyari Conglomerates, and the Aghajari Sandstone. The Asmari Limestone and other units have much lower potential for groundwater supplies. Potential usefulness of the RSGIS method was indicated when six out of nine producing wells recently drilled by the Khozestan Water and Power Authority (which had no knowledge of this study) were located in areas preferentially selected by this technique.

Is Ceres' deep interior ice-rich? Constraints from crater morphology

NASA Astrophysics Data System (ADS)

Bland, M. T.; Raymond, C. A.; Fu, R.; Marchi, S.; Castillo, J. C.; King, S. D.; Schenk, P.; Preusker, F.; Park, R. S.; Russell, C. T.

2016-12-01

Determining the composition and internal structure of Ceres is critical to understanding its origin and evolution. Analysis of the depths of Ceres' largest impact craters [Bland et al. 2016] and global shape [Fu et al. 2016] using data returned by NASA's Dawn spacecraft indicate that the dwarf planet's subsurface contains no more than 30% water ice by volume, with the other 70% consisting of salts (hydrated and/or anhydrous), clathrates, and phyllosilicates. Despite these findings, Ceres is unlikely to be ice-free. The GRaND instrument has detected probable water ice at decimeter depths (with strong latitudinal variations) [Prettyman et al. 2016], water ice has been detected in fresh [Combe et al. 2016] and permanently shadowed craters [Schorghofer et al. 2016], and the simple-complex morphologic transition diameter is consistent with a weak (icy) surface layer [Schenk et al. 2016]. Furthermore, a cryovolcanic origin for Ahuna Mons requires a source of water-rich material [Ruesch et al. 2016]. Here we use numerical simulations of the viscous relaxation of impact craters to provide new constraints on the water ice content of Ceres as a function of depth that enable a more complete understanding of the thickness and composition of its outer layer. These new simulations include three rheological layers: a high-viscosity near-surface layer, a weaker (possibly ice-rich layer), and an essentially immobile rocky layer at depth. Results are latitude (temperature) dependent; however, we generally find that retaining crater topography requires a high-viscosity (ice-poor) layer with a thickness of 50% the crater radius. For example, retaining a 100-km diameter crater at latitudes below 50o requires a high-viscosity (103x water ice) layer at least 30 km thick, if the underlying layer is pure ice. Deep, low-latitude craters 150 km in diameter are observed on Ceres [Bland et al. 2016], so the high-viscosity layer is likely >40 km thick. However, our results do not exclude the existence of a reservoir enriched in water ice at the base of Ceres' outer layer. We also find that the unique morphology of Ceres' largest crater, Kerwan, may result from viscous relaxation in a thin outer layer, potentially providing a constraint on the local thickness of Ceres outer shell.

Heat transfer of molten metal layers in severe accidents

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

Wong, Seung Kai; Walton, A.; Yang, Zhilin

1997-12-01

In some scenarios of severe accidents of light water reactors, a layer of molten metal from internal structural components of the pressure vessel is predicted to occur on top of a ceramic core debris in the lower head. The layer transfers the heat generated in the ceramic pool to the side wall of the vessel, causing the latter to melt. This problem has been investigated by Theofanous et al. for the advanced light water reactor AP600 in the context of the accident management strategy of ex-vessel cooling, and the conclusion was drawn that the melting does not seriously compromise themore » integrity of the pressure vessel.« less

Indirect diagnosis of pavement structural damages using surface GPR reflection techniques

NASA Astrophysics Data System (ADS)

Benedetto, A.; Pensa, S.

2007-06-01

The safety and operability of road networks is, in part, dependent on the quality of the pavement. It is known that pavements suffer from many different structural problems which can lead to damage to the pavement surface. To minimize the effect of these problems programmed policies for pavement management are required. Additionally a given local anomaly on the road surface can affect the safety of the road to various degrees according to the category of the road, so it is possible to set up different programmes of repair according to the different standards of road. Programmed policies for pavement management are required because of the wide structural damage which occurs to pavements during their normal operating life. This has consequences for the safety and operability of road networks. During the last decade, road networks suffered from great structural damage. The damage occurs for different reasons, such as the increasing traffic or the lack of means for routine maintenance. Many forms of damage, originating in the bottom layers are invisible until the pavement cracks. They depend on the infiltration of water and the presence of cohesive soil greatly reduces the bearing capacity of the sub-asphalt layers and underlying soils. On the basis of an in-depth literature review, an experimental survey with Ground Penetrating Radar (GPR) was carried out to calibrate the geophysical parameters and to validate the reliability of an indirect diagnostic method of pavement damage. The experiments were set on a pavement under which water was injected over a period of several hours. GPR travel time data were used to estimate the dielectric constant and the water content in the unbound aggregate layer, the variations in water content with time and particular areas where rate of infiltration decreases. A new methodology has been proposed to extract the hydraulic permittivity fields in sub-asphalt structural layers and soils from the moisture maps observed with GPR. It is effective at diagnosing the presence of clay or cohesive soil that compromises the bearing capacity of sub-base and induces damage.

Layer-by-Layer Molecular Assemblies for Dye-Sensitized Photoelectrosynthesis Cells Prepared by Atomic Layer Deposition

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

Wang, Degao; Sheridan, Matthew V.; Shan, Bing

2017-08-30

In a Dye Sensitized Photoelectrosynthesis Cell (DSPEC) the relative orientation of catalyst and chromophore play important roles. Here we introduce a new, robust, Atomic Layer Deposition (ALD) procedure for the preparation of assemblies on wide bandgap semiconductors. In the procedure, phosphonated metal complex precursors react with metal ion bridging to an external chromophore or catalyst to give assemblies bridged by Al(III), Sn(IV), Ti(IV), or Zr(IV) metal oxide units as bridges. The procedure has been extended to chromophore-catalyst assemblies for water oxidation catalysis. A SnO2 bridged assembly on SnO2/TiO2 core/shell electrodes undergoes water splitting with an incident photon conversion efficiency (IPCE)more » of 17.1% at 440 nm. Reduction of water at a Ni(II)-based catalyst on NiO films has been shown to give H2. Compared to conventional solution-based procedures, the ALD approach offers significant advantages in scope and flexibility for the preparation of stable surface structures.« less

Synthesis, Crystal Structure, and Luminescent Properties of Ag(I) Coordination Polymer with Tricarboxylic Acid and Flexible N-donor Ligand

NASA Astrophysics Data System (ADS)

Lu, J. F.; Xu, Y. H.; Li, P. A.; Jin, L. X.; Zhao, C. B.; Guoand, X. H.; Ge, H. G.

2017-12-01

The reaction of AgNO3 with combinations of 1,3-bis(4-pyridyl)propane ( bpp) and 1,3,5-benzenetricarboxylic acid (H3btc) in aqueous alcohol/ammonia at room temperature produces crystals of {[Ag6(H2O)2( bpp)6] · ( btc)2 · 25H2O} n (Ι). Single crystal X-ray diffraction analysis reveals that the complex Ι consists of 1D infinite cationic chains of [Ag( bpp)] n n+ and [Ag(H2O)( bpp)] n n+ which are further linked into the cation layer of [Ag( bpp)] n n+ by Ag···π interactions. The noncoordinated btc 3- serves as template driving surrounding water molecules to aggregate into the anionic water layer. The neighboring anionic water layer and cationic layer were further alternately joined into a 3D sandwich-like framework by hydrogen bonding. In addition, the luminescent properties of Ι were investigated.

Enhancing stability and efficiency of perovskite solar cells with crosslinkable silane-functionalized and doped fullerene

DOE PAGES

Bai, Yang; Dong, Qingfeng; Shao, Yuchuan; ...

2016-10-05

The instability of hybrid perovskite materials due to water and moisture arises as one major challenge to be addressed before any practical application of the demonstrated high efficiency perovskite solar cells. Here we report a facile strategy that can simultaneously enhance the stability and efficiency of p-i-n planar heterojunction-structure perovskite devices. Crosslinkable silane molecules with hydrophobic functional groups are bonded onto fullerene to make the fullerene layer highly water-resistant. Methylammonium iodide is introduced in the fullerene layer for n-doping via anion-induced electron transfer, resulting in dramatically increased conductivity over 100-fold. With crosslinkable silane-functionalized and doped fullerene electron transport layer, themore » perovskite devices deliver an efficiency of 19.5% with a high fill factor of 80.6%. Furthermore, a crosslinked silane-modified fullerene layer also enhances the water and moisture stability of the non-sealed perovskite devices by retaining nearly 90% of their original efficiencies after 30 days’ exposure in an ambient environment.« less

Enhancing stability and efficiency of perovskite solar cells with crosslinkable silane-functionalized and doped fullerene

PubMed Central

Bai, Yang; Dong, Qingfeng; Shao, Yuchuan; Deng, Yehao; Wang, Qi; Shen, Liang; Wang, Dong; Wei, Wei; Huang, Jinsong

2016-01-01

The instability of hybrid perovskite materials due to water and moisture arises as one major challenge to be addressed before any practical application of the demonstrated high efficiency perovskite solar cells. Here we report a facile strategy that can simultaneously enhance the stability and efficiency of p–i–n planar heterojunction-structure perovskite devices. Crosslinkable silane molecules with hydrophobic functional groups are bonded onto fullerene to make the fullerene layer highly water-resistant. Methylammonium iodide is introduced in the fullerene layer for n-doping via anion-induced electron transfer, resulting in dramatically increased conductivity over 100-fold. With crosslinkable silane-functionalized and doped fullerene electron transport layer, the perovskite devices deliver an efficiency of 19.5% with a high fill factor of 80.6%. A crosslinked silane-modified fullerene layer also enhances the water and moisture stability of the non-sealed perovskite devices by retaining nearly 90% of their original efficiencies after 30 days' exposure in an ambient environment. PMID:27703136

Double layer mixed matrix membrane adsorbers improving capacity and safety hemodialysis

NASA Astrophysics Data System (ADS)

Saiful; Borneman, Z.; Wessling, M.

2018-05-01

Double layer mixed matrix membranes adsorbers have been developed for blood toxin removal by embedding activated carbon into cellulose acetate macroporous membranes. The membranes are prepared by phase inversion method via water vapor induced phase separation followed by an immersion precipitation step. Double layer MMM consisting of an active support and a separating layer. The active support layer consists of activated carbon particles embedded in macroporous cellulose acetate; the separating layer consists of particle free cellulose acetate. The double layer membrane possess an open and interconnected macroporous structure with a high loading of activated carbon available for blood toxins removal. The MMM AC has a swelling degree of 6.5 %, porosity of 53 % and clean water flux of 800 Lm-2h-1bar-1. The prepared membranes show a high dynamic Creatinine (Crt) removal during hemodilysis process. The Crt removal by adsorption contributes to amore than 83 % of the total removal. The double layer adsorptive membrane proves hemodialysis membrane can integrated with adsorption, in which blood toxins are removed in one step.

Nanoscale structure of the oil-water interface

DOE PAGES

Fukuto, M.; Ocko, B. M.; Bonthuis, D. J.; ...

2016-12-15

X-ray reflectivity (XR) and atomistic molecular dynamics (MD) simulations, carried out to determine the structure of the oil-water interface, provide new insight into the simplest liquid-liquid interface. For several oils (hexane, dodecane, and hexadecane) the XR shows very good agreement with a monotonic interface-normal electron density profile (EDP) broadened only by capillary waves. Similar agreement is also found for an EDP including a sub-Å thick electron depletion layer separating the oil and the water. As a result, the XR and MD derived depletions are much smaller than reported for the interface between solid-supported hydrophobic monolayers and water.

Microscopic structure and properties of discrete water layer in Na-exchanged montmorillonite.

PubMed

Emmerich, Katja; Koeniger, Franz; Kaden, Heike; Thissen, Peter

2015-06-15

In this work, we focus on the atomic structure of the water interlayer of Na-exchanged montmorillonite. For two different surface charge densities, namely -0.086 and -0.172 C/m(2), the adsorption process in the presence of water is described by first principles calculations. We describe the interactions and forces for every water molecule entering the interlayer during the swelling process. In particular, the dielectric permittivity of the water interlayer is calculated. Finally, we confirm our results performing ab initio thermodynamics calculations leading to a wide range of realistic experimental scenarios. Copyright © 2015 Elsevier Inc. All rights reserved.

AFM investigation of effect of absorbed water layer structure on growth mechanism of octadecyltrichlorosilane self-assembled monolayer on oxidized silicon

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

Li, Shaowei; Zheng, Yanjun, E-mail: zhengyj@cup.edu.cn; Chen, Changfeng

2016-06-28

The growth mechanism of an octadecyltrichlorosilane (OTS) self-assembled monolayer on a silicon oxide surface at various relative humidities has been investigated. Atomic force microscopy images show that excess water may actually hinder the nucleation and growth of OTS islands. A moderate amount of water is favorable for the nucleation and growth of OTS islands in the initial stage; however, the completion of the monolayer is very slow in the final stage. The growth of OTS islands on a low-water-content surface maintains a relatively constant speed and requires the least amount of time. The mobility of water molecules is thought tomore » play an important role in the OTS monolayers, and a low-mobility water layer provides a steady condition for OTS monolayer growth.« less

AFM investigation of effect of absorbed water layer structure on growth mechanism of octadecyltrichlorosilane self-assembled monolayer on oxidized silicon

NASA Astrophysics Data System (ADS)

Li, Shaowei; Zheng, Yanjun; Chen, Changfeng

2016-06-01

The growth mechanism of an octadecyltrichlorosilane (OTS) self-assembled monolayer on a silicon oxide surface at various relative humidities has been investigated. Atomic force microscopy images show that excess water may actually hinder the nucleation and growth of OTS islands. A moderate amount of water is favorable for the nucleation and growth of OTS islands in the initial stage; however, the completion of the monolayer is very slow in the final stage. The growth of OTS islands on a low-water-content surface maintains a relatively constant speed and requires the least amount of time. The mobility of water molecules is thought to play an important role in the OTS monolayers, and a low-mobility water layer provides a steady condition for OTS monolayer growth.

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).

Steam and air co-injection in removing residual TCE in unsaturated layered sandy porous media.

PubMed

Peng, Sheng; Wang, Ning; Chen, Jiajun

2013-10-01

Steam and air co-injection is a promising technique for volatile and semi-volatile organic contaminant remediation in heterogeneous porous media. In this study, removal of trichloroethene (TCE) with steam-air co-injection was investigated through a series of 2D sandbox experiments with different layered sand structures, and through numerical simulations. The results show that a layered structure with coarse sand, in which steam and air convection are relatively rapid, resulted in a higher removal rate and a larger removal ratio than those observed in an experiment using finer sand; however, the difference was not significant, and the removal ratios from three experiments ranged from 85% to 94%. Slight downward movement of TCE was observed for Experiment 1 (TCE initially in a fine sand zone encased in a coarse sand), while no such movement was observed for Experiment 2 (TCE initially in two fine sand layers encased in a coarse sand) or 3 (TCE initially in a silty sand zone encased in a coarse sand). Simulations show accumulation of TCE at the interface of the layered sands, which indicates a capillary barrier effect in restraining the downward movement of TCE. This effect is illustrated further by a numerical experiment with homogeneous coarse sand, in which continuous downward TCE movement to the bottom of the sandbox was simulated. Another numerical experiment with higher water saturation was also conducted. The results illustrate a complicated influence of water saturation on TCE removal in a layered sand structure. Published by Elsevier B.V.

Lidar Measurements of Wind, Moisture and Boundary Layer Evolution in a Dryline During IHOP2002

NASA Technical Reports Server (NTRS)

Demoz, Belay; Evans, Keith; DiGirolamo, Paolo; Wang, Zhien; Whiteman, David; Schwemmer, Geary; Gentry, Bruce; Miller, David

2003-01-01

Variability in the convective boundary layer moisture, wind and temperature fields and their importance in the forecasting and understanding of storms have been discussed in the literature. These variations have been reported in relation to frontal zones, stationary boundaries and during horizontal convective rolls. While all three vary substantially in the convective boundary layer, moisture poses a particular challenge. Moisture or water vapor concentration (expressed as a mass mixing ratio, g/kg), is conserved in all meteorological processes except condensation and evaporation. The water vapor mixing ratio often remains distinct across an air -mass boundary even when the temperature difference is indistinct. These properties make it an ideal choice in visualizing and understanding many of the atmosphere's dynamic features. However, it also presents a unique measurement challenge because water vapor content can vary by more than three orders of magnitude in the troposphere. Characterization of the 3D-distribution of water vapor is also difficult as water vapor observations can suffer from large sampling errors and substantial variability both in the vertical and horizontal. This study presents groundbased measurements of wind, boundary layer structure and water vapor mixing ratio measurements observed by three co-located lidars. This presentation will focus on the evolution and variability of moisture and wind in the boundary layer during a dry line event that occurred on 22 May 2002. These data sets and analyses are unique in that they combine simultaneous measurements of wind, moisture and CBL structure to study the detailed thermal variability in and around clear air updrafts during a dryline event. It will quantify the variation caused by, in and around buoyant plumes and across a dryline. The data presented here were collected in the panhandle of Oklahoma as part of the International BO Project (IHOP-2002), a field experiment that took place over the Southern Great Plains (SGP) of the United States from 13 May to 30 June 2002. The chief goal of IHOP-2002 is to improve characterization of the four-dimensional (4-D) distribution of water vapor and its application to improving the understanding and prediction of convection

Lidar Measurements of Wind, Moisture, and Boundary Layer Evolution in a Dry Line during 1HOP 2002

NASA Technical Reports Server (NTRS)

Demoz, Belay; Evans, Keith; DiGirolamo, Paolo; Wang, Zhe-In; Whiteman, David; Schwemmer, Geary; Gentry, Bruce; Miller, David; Palm, Stephen

2002-01-01

Variability in the convective boundary layer moisture, wind and temperature fields and their importance in the forecasting and understanding of storms have been discussed in the literature. These . variations have been reported in relation to frontal zones, stationary boundaries and during horizontal convective rolls. While all three vary substantially in the convective boundary layer, moisture poses a particular challenge. Moisture or water vapor concentration (expressed as a mass mixing ratio, g/kg), is conserved in all meteorological processes except condensation and evaporation. The water vapor mixing ratio often remains distinct across an air-mass boundary even when the temperature difference is indistinct. These properties make it an ideal choice in visualizing and understanding many of the atmosphere's dynamic features. However, it also presents a unique measurement challenge because water vapor content can vary by more than three orders of magnitude in the troposphere. Characterization of the 3D-distribution of water vapor is also difficult as water vapor observations can suffer from large sampling errors and substantial variability both in the vertical and horizontal. This study presents ground-based measurements of wind, boundary layer structure and water vapor mixing ratio measurements observed by three co-located lidars. This presentation will focus on the evolution and variability of moisture and wind in the boundary layer during a dry line event that occurred on 22 May 2002. These data sets and analyses are unique in that they combine simultaneous measurements of wind, moisture and CBL structure to study the detailed thermal variability in and around clear air updrafts during a dryline event. It will quantify the variation caused by, in and around buoyant plumes and across a dryline. The data presented here were collected in the panhandle of Oklahoma as part of the International H2O Project (MOP-2002), a field experiment that took place over the Southern Great Plains (SGP) of the United States from 13 May to 30 June 2002. The chief goal of MOP-2002 is to improve characterization of the four-dimensional (4-D) distribution of water vapor and its application to improving the understanding and prediction of convection

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.

Weakly bound water structure, bond valence saturation and water dynamics at the goethite (100) surface/aqueous interface: ab initio dynamical simulations

DOE PAGES

Chen, Ying; Bylaska, Eric J.; Weare, John H.

2017-03-31

Many important geochemical and biogeochemical reactions occur in the mineral/formation water interface of the highly abundant mineral, goethite (α-Fe(OOH). Ab-initio molecular dynamics (AIMD) simulations of the goethite α-FeOOH (100) surface and the structure, water bond formation and dynamics of water molecules in the mineral/aqueous interface are presented. Here, several exchange correlation functionals were employed (PBE96, PBE96+Grimme, and PBE0) in the simulations of a (3 x 2) goethite surface with 65 absorbed water molecules in a 3D-periodic supercell (a=30 Å, FeOOH slab ~12 Å thick, solvation layer ~18 Å thick).

Weakly bound water structure, bond valence saturation and water dynamics at the goethite (100) surface/aqueous interface: ab initio dynamical simulations

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

Chen, Ying; Bylaska, Eric J.; Weare, John H.

Many important geochemical and biogeochemical reactions occur in the mineral/formation water interface of the highly abundant mineral, goethite (α-Fe(OOH). Ab-initio molecular dynamics (AIMD) simulations of the goethite α-FeOOH (100) surface and the structure, water bond formation and dynamics of water molecules in the mineral/aqueous interface are presented. Here, several exchange correlation functionals were employed (PBE96, PBE96+Grimme, and PBE0) in the simulations of a (3 x 2) goethite surface with 65 absorbed water molecules in a 3D-periodic supercell (a=30 Å, FeOOH slab ~12 Å thick, solvation layer ~18 Å thick).

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.

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

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

Synthesising methods of layered double hydroxides and its use in the fabrication of dye Sensitised solar cell (DSSC): A short review

NASA Astrophysics Data System (ADS)

George, Giphin; Saravanakumar, M. P.

2017-11-01

The layered double hydroxides (LDH) which are anionic clay substances comprising of stacked cationic layers and interlayer anions. The cationic sheets contain octahedral structure consisting the divalent and trivalent ions in the center and hydroxyl bunches in the corners, gathered by three bonding with the neighbouring octahedra on every side of the layer. The ratio between the quantity of cations and OH- ions is 2:1, so a positive charge shows up on the layer because of the presence of trivalent cations. The interlayer space gives the compensation anions and water molecules, assuring a balanced out layered structure. The LDH materials were successfully synthesised from magnesium, aluminium, zinc and chromium chloride salts utilizing the co-precipitation technique. A Zn-Al LDH was researched as a potential sorbent material. This article reviews the recent advances in the preparation and intercalation of layered double hydroxides and its application in the fabrication of Dye Sensitized Solar Cell (DSSC).

Remote sensing of Earth terrain

NASA Technical Reports Server (NTRS)

Kong, Jin AU

1987-01-01

Earth terrain covers were modeled as random media characterized by different dielectric constants and correlation functions. In order to model sea ice with brine inclusions and vegetation with row structures, the random medium is assumed to be anisotropic. A three layer model is used to simulate a vegetation field or a snow covered ice field with the top layer being snow or leaves, the middle layer being ice or trunks, and the bottom layer being sea water or ground. The strong fluctuation theory with the distorted Born approximation is applied to the solution of the radar backscattering coefficients.

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.

Investigating buried polymer interfaces using sum frequency generation vibrational spectroscopy

PubMed Central

Chen, Zhan

2010-01-01

This paper reviews recent progress in the studies of buried polymer interfaces using sum frequency generation (SFG) vibrational spectroscopy. Both buried solid/liquid and solid/solid interfaces involving polymeric materials are discussed. SFG studies of polymer/water interfaces show that different polymers exhibit varied surface restructuring behavior in water, indicating the importance of probing polymer/water interfaces in situ. SFG has also been applied to the investigation of interfaces between polymers and other liquids. It has been found that molecular interactions at such polymer/liquid interfaces dictate interfacial polymer structures. The molecular structures of silane molecules, which are widely used as adhesion promoters, have been investigated using SFG at buried polymer/silane and polymer/polymer interfaces, providing molecular-level understanding of polymer adhesion promotion. The molecular structures of polymer/solid interfaces have been examined using SFG with several different experimental geometries. These results have provided molecular-level information about polymer friction, adhesion, interfacial chemical reactions, interfacial electronic properties, and the structure of layer-by-layer deposited polymers. Such research has demonstrated that SFG is a powerful tool to probe buried interfaces involving polymeric materials, which are difficult to study by conventional surface sensitive analytical techniques. PMID:21113334

Modifying the anti-wetting property of butterfly wings and water strider legs by atomic layer deposition coating: surface materials versus geometry.

PubMed

Ding, Yong; Xu, Sheng; Zhang, Yue; Wang, Aurelia C; Wang, Melissa H; Xiu, Yonghao; Wong, Ching Ping; Wang, Zhong Lin

2008-09-03

Although butterfly wings and water strider legs have an anti-wetting property, their working conditions are quite different. Water striders, for example, live in a wet environment and their legs need to support their weight and bear the high pressure during motion. In this work, we have focused on the importance of the surface geometrical structures in determining their performance. We have applied an atomic layer deposition technique to coat the surfaces of both butterfly wings and water strider legs with a uniform 30 nm thick hydrophilic Al(2)O(3) film. By keeping the surface material the same, we have studied the effect of different surface roughness/structure on their hydrophobic property. After the surface coating, the butterfly wings changed to become hydrophilic, while the water strider legs still remained super-hydrophobic. We suggest that the super-hydrophobic property of the water strider is due to the special shape of the long inclining spindly cone-shaped setae at the surface. The roughness in the surface can enhance the natural tendency to be hydrophobic or hydrophilic, while the roughness in the normal direction of the surface is favorable for forming a composite interface.

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.

Model for the interpretation of nuclear magnetic resonance relaxometry of hydrated porous silicate materials

NASA Astrophysics Data System (ADS)

Faux, D. A.; Cachia, S.-H. P.; McDonald, P. J.; Bhatt, J. S.; Howlett, N. C.; Churakov, S. V.

2015-03-01

Nuclear magnetic resonance (NMR) relaxation experimentation is an effective technique for probing the dynamics of proton spins in porous media, but interpretation requires the application of appropriate spin-diffusion models. Molecular dynamics (MD) simulations of porous silicate-based systems containing a quasi-two-dimensional water-filled pore are presented. The MD simulations suggest that the residency time of the water on the pore surface is in the range 0.03-12 ns, typically 2-5 orders of magnitude less than values determined from fits to experimental NMR measurements using the established surface-layer (SL) diffusion models of Korb and co-workers [Phys. Rev. E 56, 1934 (1997), 10.1103/PhysRevE.56.1934]. Instead, MD identifies four distinct water layers in a tobermorite-based pore containing surface Ca2 + ions. Three highly structured water layers exist within 1 nm of the surface and the central region of the pore contains a homogeneous region of bulklike water. These regions are referred to as layer 1 and 2 (L1, L2), transition layer (TL), and bulk (B), respectively. Guided by the MD simulations, a two-layer (2L) spin-diffusion NMR relaxation model is proposed comprising two two-dimensional layers of slow- and fast-moving water associated with L2 and layers TL+B, respectively. The 2L model provides an improved fit to NMR relaxation times obtained from cementitious material compared to the SL model, yields diffusion correlation times in the range 18-75 ns and 28-40 ps in good agreement with MD, and resolves the surface residency time discrepancy. The 2L model, coupled with NMR relaxation experimentation, provides a simple yet powerful method of characterizing the dynamical properties of proton-bearing porous silicate-based systems such as porous glasses, cementitious materials, and oil-bearing rocks.

Effects of cell wall components on the functionality of wheat gluten.

PubMed

Autio, K

2006-01-01

Normal white wheat flours and especially whole meal flour contain solids from the inner endosperm cell walls, from germ, aleurone layer and the outer layers of cereal grains. These solids can prevent either gluten formation or gas cell structure. The addition of small amounts of pericarp layers (1-2%) to wheat flour had a marked detrimental effect on loaf volume. Microstructural studies indicated that in particular the epicarp hairs appeared to disturb the gas cell structure. The detrimental effects of insoluble cell walls can be prevented by using endoxylanases. It has been shown that some oxidative enzymes, naturally present in flour or added to the dough, will oxidise water-extractable arabinoxylans via ferulic acid bridges, and the resulting arabinoxylan gel will hinder gluten formation. The negative effects of water-unextractable arabinoxylans on gluten yield and rheological properties can be compensated by the addition of ferulic acid. Free ferulic acid can probably prevent arabinoxylan cross-linking via ferulic acid.

Ice shelf structure derived from dispersion curve analysis of ambient seismic noise, Ross Ice Shelf, Antarctica

NASA Astrophysics Data System (ADS)

Diez, A.; Bromirski, P. D.; Gerstoft, P.; Stephen, R. A.; Anthony, R. E.; Aster, R. C.; Cai, C.; Nyblade, A.; Wiens, D. A.

2016-05-01

An L-configured, three-component short period seismic array was deployed on the Ross Ice Shelf, Antarctica during November 2014. Polarization analysis of ambient noise data from these stations shows linearly polarized waves for frequency bands between 0.2 and 2 Hz. A spectral peak at about 1.6 Hz is interpreted as the resonance frequency of the water column and is used to estimate the water layer thickness below the ice shelf. The frequency band from 4 to 18 Hz is dominated by Rayleigh and Love waves propagating from the north that, based on daily temporal variations, we conclude were generated by field camp activity. Frequency-slowness plots were calculated using beamforming. Resulting Love and Rayleigh wave dispersion curves were inverted for the shear wave velocity profile within the firn and ice to ˜150 m depth. The derived density profile allows estimation of the pore close-off depth and the firn-air content thickness. Separate inversions of Rayleigh and Love wave dispersion curves give different shear wave velocity profiles within the firn. We attribute this difference to an effective anisotropy due to fine layering. The layered structure of firn, ice, water and the seafloor results in a characteristic dispersion curve below 7 Hz. Forward modelling the observed Rayleigh wave dispersion curves using representative firn, ice, water and sediment structures indicates that Rayleigh waves are observed when wavelengths are long enough to span the distance from the ice shelf surface to the seafloor. The forward modelling shows that analysis of seismic data from an ice shelf provides the possibility of resolving ice shelf thickness, water column thickness and the physical properties of the ice shelf and underlying seafloor using passive-source seismic data.

Reflection of processes of non-equilibrium two-phase filtration in oil-saturated hierarchical medium in data of active wave geophysical monitoring

NASA Astrophysics Data System (ADS)

Hachay, Olga; Khachay, Andrey; Khachay, Oleg

2016-04-01

The processes of oil extraction from deposit are linked with the movement of multi-phase multi-component media, which are characterized by non-equilibrium and non-linear rheological features. The real behavior of layered systems is defined by the complexity of the rheology of moving fluids and the morphology structure of the porous medium, and also by the great variety of interactions between the fluid and the porous medium [Hasanov and Bulgakova, 2003]. It is necessary to take into account these features in order to informatively describe the filtration processes due to the non-linearity, non-equilibrium and heterogeneity that are features of real systems. In this way, new synergetic events can be revealed (namely, a loss of stability when oscillations occur, and the formation of ordered structures). This allows us to suggest new methods for the control and management of complicated natural systems that are constructed on account of these phenomena. Thus the layered system, from which it is necessary to extract the oil, is a complicated dynamical hierarchical system. A comparison is provided of non-equilibrium effects of the influence of independent hydrodynamic and electromagnetic induction on an oil layer and the medium which it surrounds. It is known that by drainage and steeping the hysteresis effect on curves of the relative phase permeability in dependence on the porous medium's water saturation in some cycles of influence (drainage-steep-drainage) is observed. Using the earlier developed 3D method of induction electromagnetic frequency geometric monitoring, we showed the possibility of defining the physical and structural features of a hierarchical oil layer structure and estimating the water saturation from crack inclusions. This effect allows managing the process of drainage and steeping the oil out of the layer by water displacement. An algorithm was constructed for 2D modeling of sound diffraction on a porous fluid-saturated intrusion of a hierarchical structure located in layer number J of an N-layered elastic medium. The algorithm developed for modeling, and the method of mapping and monitoring of heterogenic highly complicated two-phase medium can be used for managing viscous oil extraction in mining conditions and light oil in sub-horizontal boreholes. The demand for effective economic parameters and fuller extraction of oil and gas from deposits dictates the necessity of developing new geotechnology based on the fundamental achievements in the area of geophysics and geomechanics

Evidence for Possible Exposed Water Ice Deposits in Martian Low Latitude Chasms and Chaos

NASA Technical Reports Server (NTRS)

Leovy, C.; Wood, S. E.; Catling, D.; Montgomery, D. R.; Moore, J.; Barnhart, C.; Ginder, E.; Louie, M.

2004-01-01

A light-toned interior layer deposit (ILD) on the floor of the deep martian depression Juventae Chasma is found to have a relatively high thermal inertia approx. 500 J m(exp -2) s(exp -1/2) K(exp -1). This could imply rock, but is also similar to the average value of thermal inertia found for north polar layered deposits. Furthermore, ILD-B is found to exhibit a bluff and terrace structure . A terrace structure arises naturally in model simulations of the sublimation of large ice deposits. Such a staircase terrain, of course, is a further characteristic of north polar layered terrain. Morphological similarity, thermal inertia in the range of thermal inertias of the north polar cap layered terrain, and relatively high albedo lead us to propose that the ILD-B may consist of residual water ice partially covered by, and perhaps mixed with, varying amounts of dust or sand. Other ILDs (A-C) are also found in Juventae Chasma. While these ILDs lack the close morphological resemblance to the north polar cap, they share many other common features and appear to be part of the same formation. Similar ILDs are found in chaotic terrain elsewhere in the martian tropics. This leads us to propose that water ice may exist in the martian tropics today and may be implicit in the formation of chaotic terrain.

3D morphological characterization of the polyamide active layer of RO and NF membranes using TEM and soft X-ray scattering

NASA Astrophysics Data System (ADS)

Culp, Tyler; Paul, Mou; Roy, Abhishek; Rosenberg, Steve; Behr, Michael; Kumar, Manish; Gomez, Enrique; Penn State Team; Dow Team

Polyamide-based thin-film composite (TFC) membranes used for reverse osmosis (RO) and nanofiltration (NF) separation processes are at the forefront of water desalination and purification technologies due to their high salt rejection, high energy efficiency, and ease of operation. Nevertheless, in spite of the benefits of RO and NF membranes, many open questions about the internal nanostructure of the membrane active layer remain, such as the dispersion and distribution of acid functional groups. We demonstrate that resonant soft X-ray scattering (RSOXS), where the X-ray energy is tuned to absorption edges of the constituent materials, is a powerful tool to examine the microstructure of the polyamide layer. In conjunction with complementary techniques such as transmission electron microscopy (TEM), where tomography is used to obtain a 3D reconstruction of the polyamide active layer, the effect of cross-linking can be quantified in 3D for a systematic series of membranes. This relationship can then be applied to a series of commercially available RO and NF membranes where the effect of polyamide cross-linking on their respective structure and water transport properties can be evaluated. The combination of RSOXS with traditional characterization tools provides a strategy for linking the chemical structure to the morphology and water transport properties of RO and NF membranes.

Bio-Inspired Aquaporinz Containing Double-Skinned Forward Osmosis Membrane Synthesized through Layer-by-Layer Assembly

PubMed Central

Wang, Shuzheng; Cai, Jin; Ding, Wande; Xu, Zhinan; Wang, Zhining

2015-01-01

We demonstrated a novel AquaporinZ (AqpZ)-incorporated double-skinned forward osmosis (FO) membrane by layer-by-layer (LbL) assembly strategy. Positively charged poly(ethyleneimine) (PEI) and negatively charged poly(sodium 4-styrenesulfonate) (PSS) were alternately deposited on both the top and bottom surfaces of a hydrolyzed polyacrylonitrile (H-PAN) substrate. Subsequently, an AqpZ-embedded 1,2-dioleloyl-sn-glycero-3-phosphocholine (DOPC)/1,2-dioleoyl-3-trimethylammonium- propane (chloride salt) (DOTAP) supported lipid bilayer (SLB) was formed on PSS-terminated (T-PSS) membrane via vesicle rupture method. The morphology and structure of the biomimetic membranes were characterized by in situ atomic force microscopy (AFM), scanning electron microscope (SEM), Fourier transform infrared spectrometer using the attenuated total reflection technique (ATR-FTIR), and contact angle. Moreover, the FO performance of the resultant membrane was measured by using 2 M MgCl2 solution as draw solution and deionized (DI) water as feed solution, respectively. The membrane with a protein-to-lipid weight ratio (P/L) of 1/50 exhibits 13.2 L/m2h water flux and 3.2 g/m2h reversed flux by using FO mode, as well as 15.6 L/m2h water flux and 3.4 L/m2h reversed flux for PRO mode (the draw solution is placed against the active layer). It was also shown that the SLB layer of the double-skinned FO membrane can increase the surface hydrophilicity and reduce the surface roughness, which leads to an improved anti-fouling performance against humic acid foulant. The current work introduced a new method of fabricating high performance biomimetic FO membrane by combining AqpZ and a double-skinned structure based on LbL assembly. PMID:26266426

Observations of transitional tidal boundary layers and their impact on sediment transport in the Great Bay, NH

NASA Astrophysics Data System (ADS)

Koetje, K. M.; Foster, D. L.; Lippmann, T. C.

2017-12-01

Observations of the vertical structure of tidal flows obtained in 2016 and 2017 in the Great Bay Estuary, NH show evidence of transitional tidal boundary layers at deployment locations on shallow mudflats. High-resolution bottom boundary layer currents, hydrography, turbidity, and bed characteristics were observed with an acoustic Doppler current profiler (ADCP), an acoustic Doppler velocimeter (ADV), conductivity-depth-temperature (CTD) sensors, optical backscatter sensors, multibeam bathymetric surveys, and sediment grab samples and cores. Over the 2.5 m tidal range and at water depths ranging from 0.3 m to 1.5 m at mean lower low water, peak flows ranged from 10 cm/s to 30 cm/s and were primarily driven by the tides. A downward-looking ADCP captured the velocity profile over the lowest 1 m of the water column. Results consistently show a dual-log layer system, with evidence of a lower layer within 15 cm of the bed, another layer above approximately 30 cm from the bed, and a transitional region where the flow field rotates between that the two layers that can be as much as 180 degrees out of phase. CTD casts collected over a complete tidal cycle suggest that the weak thermohaline stratification is not responsible for development of the two layers. On the other hand, acoustic and optical backscatter measurements show spatial and temporal variability in suspended sediments that are dependant on tidal phase. Current work includes an examination of the relationship between sediment concentrations in the water column and velocity profile characteristics, along with an effort to quantify the impact of rotation and dual-log layers on bed stress.

In-situ evaluation of internal drainage in layered soils (Tukulu, Sepane and Swartland)

NASA Astrophysics Data System (ADS)

Mavimbela, S. S. W.; van Rensburg, L. D.

2011-11-01

The soil water release (SWC) and permeability properties of layered soils following deep infiltration depends on the structural and layering composition of the profiles diagnostic horizons. Three layered soils, the Tukulu, Sepane and Swartland soil forms, from the Free State province of South Africa, were selected for internal drainage evaluation. The soil water release curves as a function of suction (h) and unsaturated hydraulic conductivity (K-coefficient) as a function of soil water content, SWC (θ), were characterised alongside the pedological properties of the profiles. The water hanging column in collaboration with the in-situ instantaneous profile method (IPM) was appropriate for this work. Independently, the saturated hydraulic conductivity (Ks) was measured using double ring infiltrometers. The three soils had a generic orthic A horizon but differed remarkable with depth. A clay rich layer was found in the Tukulu and Sepane at depths of 600 to 850 mm and 300 to 900 mm, respectively. The Swartland was weakly developed with a saprolite rock found at depth of 400-700 mm. During the 1200 h drainage period, soil water loss amounted to 21, 20 and 51 mm from the respective Tukulu, Sepane and Swartland profiles. An abrupt drop in Ks in conjunction with a steep K-coefficient gradient with depth was observed from the Tukulu and Sepane. Hydromorphic colours found on the clay-rich horizons suggested a wet soil water regime that implied restriction of internal drainage. It was therefore concluded that the clay rich horizons gave the Tukulu and Sepane soil types restricted internal drainage properties required for soil water storage under infield rainwater harvesting production technique. The coarseness of the Swartland promoted high drainage losses that proliferated a dry soil water regime.

Ries Bunte Breccia revisited: Indications for the presence of water in Itzing and Otting drill cores and implications for the emplacement process

NASA Astrophysics Data System (ADS)

Pietrek, Alexa; Kenkmann, Thomas

2016-07-01

We reassessed two drill cores of the Bunte Breccia deposits of the Ries crater, Germany. The objectives of our study were the documentation of evidence for water in the Bunte Breccia, the evaluation of how that water influenced the emplacement processes, and from which preimpact water reservoir it was derived. The Bunte Breccia in both cores can be structured into a basal layer composed mainly of local substrate material, overlain by texturally and compositionally diverse, crater-derived breccia units. The basal layer is composed of the youngest sediments (Tertiary clays and Upper Jurassic limestone) and has a razor-sharp boundary to the upper breccia units, which are composed of older rocks of Upper Jurassic to Upper Triassic age. Sparse material exchange occurred between the basal layer and the rest of the Bunte Breccia. Fluids predominantly came from the Tertiary and the Upper Triassic sandstone formation. In the basal layer, Tertiary clays were subjected to intense, ductile deformation, indicating saturation with water. This suggests that water was mixed into the matrix, creating a fluidized basal layer with a strong shear localization. In the upper units, Upper Triassic sandstones are intensely deformed by granular flow. The texture requires that the rocks were disaggregated into granular sand. Vaporization of pore water probably aided fragmentation of these rocks. In the Otting core, hot suevite (T > 600 °C) covered the Bunte Breccia shortly after its emplacement. Vertically oriented gas escape pipes in suevite partly emanate directly at the contact to the Bunte Breccia. They indicate that the Bunte Breccia contained a substantial amount of water in the upper part that was vaporized and escaped through these vents.

Metallization and Biopatterning on Ultra-Flexible Substrates via Dextran Sacrificial Layers

PubMed Central

Tseng, Peter; Pushkarsky, Ivan; Di Carlo, Dino

2014-01-01

Micro-patterning tools adopted from the semiconductor industry have mostly been optimized to pattern features onto rigid silicon and glass substrates, however, recently the need to pattern on soft substrates has been identified in simulating cellular environments or developing flexible biosensors. We present a simple method of introducing a variety of patterned materials and structures into ultra-flexible polydimethylsiloxane (PDMS) layers (elastic moduli down to 3 kPa) utilizing water-soluble dextran sacrificial thin films. Dextran films provided a stable template for photolithography, metal deposition, particle adsorption, and protein stamping. These materials and structures (including dextran itself) were then readily transferrable to an elastomer surface following PDMS (10 to 70∶1 base to crosslinker ratios) curing over the patterned dextran layer and after sacrificial etch of the dextran in water. We demonstrate that this simple and straightforward approach can controllably manipulate surface wetting and protein adsorption characteristics of PDMS, covalently link protein patterns for stable cell patterning, generate composite structures of epoxy or particles for study of cell mechanical response, and stably integrate certain metals with use of vinyl molecular adhesives. This method is compatible over the complete moduli range of PDMS, and potentially generalizable over a host of additional micro- and nano-structures and materials. PMID:25153326

Diel Vertical Dynamics of Gelatinous Zooplankton (Cnidaria, Ctenophora and Thaliacea) in a Subtropical Stratified Ecosystem (South Brazilian Bight)

PubMed Central

Nogueira Júnior, Miodeli; Brandini, Frederico Pereira; Codina, Juan Carlos Ugaz

2015-01-01

The diel vertical dynamics of gelatinous zooplankton in physically stratified conditions over the 100-m isobath (~110 km offshore) in the South Brazilian Bight (26°45’S; 47°33’W) and the relationship to hydrography and food availability were analyzed by sampling every six hours over two consecutive days. Zooplankton samples were taken in three depth strata, following the vertical structure of the water column, with cold waters between 17 and 13.1°C, influenced by the South Atlantic Central Water (SACW) in the lower layer (>70 m); warm (>20°C) Tropical Water in the upper 40 m; and an intermediate thermocline with a deep chlorophyll-a maximum layer (0.3–0.6 mg m-3). Two distinct general patterns were observed, emphasizing the role of (i) physical and (ii) biological processes: (i) a strong influence of the vertical stratification, with most zooplankton absent or little abundant in the lower layer. The influence of the cold SACW on the bottom layer apparently restricted the vertical occupation of most species, which typically inhabit epipelagic warm waters. Even among migratory species, only a few (Aglaura hemistoma, Abylopsis tetragona eudoxids, Beroe sp., Thalia democratica, Salpa fusiformis) crossed the thermocline and reached the bottom layer. (ii) A general tendency of partial migrations, with variable intensity depending on the different species and developmental stages; populations tended to be more widely distributed through the water column during daylight, and to become more aggregated in the upper layer during the night, which can be explained based on the idea of the “hunger-satiation hypothesis”, maximizing feeding and minimizing the chances of being predated. PMID:26637179

Diel Vertical Dynamics of Gelatinous Zooplankton (Cnidaria, Ctenophora and Thaliacea) in a Subtropical Stratified Ecosystem (South Brazilian Bight).

PubMed

Nogueira Júnior, Miodeli; Brandini, Frederico Pereira; Codina, Juan Carlos Ugaz

2015-01-01

The diel vertical dynamics of gelatinous zooplankton in physically stratified conditions over the 100-m isobath (~110 km offshore) in the South Brazilian Bight (26°45'S; 47°33'W) and the relationship to hydrography and food availability were analyzed by sampling every six hours over two consecutive days. Zooplankton samples were taken in three depth strata, following the vertical structure of the water column, with cold waters between 17 and 13.1°C, influenced by the South Atlantic Central Water (SACW) in the lower layer (>70 m); warm (>20°C) Tropical Water in the upper 40 m; and an intermediate thermocline with a deep chlorophyll-a maximum layer (0.3-0.6 mg m-3). Two distinct general patterns were observed, emphasizing the role of (i) physical and (ii) biological processes: (i) a strong influence of the vertical stratification, with most zooplankton absent or little abundant in the lower layer. The influence of the cold SACW on the bottom layer apparently restricted the vertical occupation of most species, which typically inhabit epipelagic warm waters. Even among migratory species, only a few (Aglaura hemistoma, Abylopsis tetragona eudoxids, Beroe sp., Thalia democratica, Salpa fusiformis) crossed the thermocline and reached the bottom layer. (ii) A general tendency of partial migrations, with variable intensity depending on the different species and developmental stages; populations tended to be more widely distributed through the water column during daylight, and to become more aggregated in the upper layer during the night, which can be explained based on the idea of the "hunger-satiation hypothesis", maximizing feeding and minimizing the chances of being predated.

Citrate bridges between mineral platelets in bone

PubMed Central

Davies, Erika; Müller, Karin H.; Wong, Wai Ching; Pickard, Chris J.; Reid, David G.; Skepper, Jeremy N.; Duer, Melinda J.

2014-01-01

We provide evidence that citrate anions bridge between mineral platelets in bone and hypothesize that their presence acts to maintain separate platelets with disordered regions between them rather than gradual transformations into larger, more ordered blocks of mineral. To assess this hypothesis, we take as a model for a citrate bridging between layers of calcium phosphate mineral a double salt octacalcium phosphate citrate (OCP-citrate). We use a combination of multinuclear solid-state NMR spectroscopy, powder X-ray diffraction, and first principles electronic structure calculations to propose a quantitative structure for this material, in which citrate anions reside in a hydrated layer, bridging between apatitic layers. To assess the relevance of such a structure in native bone mineral, we present for the first time, to our knowledge, 17O NMR data on bone and compare them with 17O NMR data for OCP-citrate and other calcium phosphate minerals relevant to bone. The proposed structural model that we deduce from this work for bone mineral is a layered structure with thin apatitic platelets sandwiched between OCP-citrate–like hydrated layers. Such a structure can explain a number of known structural features of bone mineral: the thin, plate-like morphology of mature bone mineral crystals, the presence of significant quantities of strongly bound water molecules, and the relatively high concentration of hydrogen phosphate as well as the maintenance of a disordered region between mineral platelets. PMID:24706850

Electrospun superhydrophobic membranes with unique structures for membrane distillation.

PubMed

Liao, Yuan; Loh, Chun-Heng; Wang, Rong; Fane, Anthony G

2014-09-24

With modest temperature demand, low operating pressure, and high solute rejection, membrane distillation (MD) is an attractive option for desalination, waste treatment, and food and pharmaceutical processing. However, large-scale practical applications of MD are still hindered by the absence of effective membranes with high hydrophobicity, high porosity, and adequate mechanical strength, which are important properties for MD permeation fluxes, stable long-term performance, and effective packing in modules without damage. This study describes novel design strategies for highly robust superhydrophobic dual-layer membranes for MD via electrospinning. One of the newly developed membranes comprises a durable and ultrathin 3-dimensional (3D) superhydrophobic skin and porous nanofibrous support whereas another was fabricated by electrospinning 3D superhydrophobic layers on a nonwoven support. These membranes exhibit superhydrophobicity toward distilled water, salty water, oil-in-water emulsion, and beverages, which enables them to be used not only for desalination but also for other processes. The superhydrophobic dual-layer membrane #3S-N with nanofibrous support has a competitive permeation flux of 24.6 ± 1.2 kg m(-2) h(-1) in MD (feed and permeate temperate were set as 333 and 293 K, respectively) due to the higher porosity of the nanofibrous scaffold. Meanwhile, the membranes with the nonwoven support exhibit greater mechanical strength due to this support combined with better long-term performance because of the thicker 3D superhydrophobic layers. The morphology, pore size, porosity, mechanical properties, and liquid enter pressure of water of these superhydrophobic composite membranes with two different structures are reported and compared with commercial polyvinylidene fluoride membranes.

Passive seismic monitoring of the Bering Glacier during its last surge event

NASA Astrophysics Data System (ADS)

Zhan, Z.

2017-12-01

The physical causes behind glacier surges are still unclear. Numerous evidences suggest that they probably involve changes in glacier basal conditions, such as switch of basal water system from concentrated large tunnels to a distributed "layer" as "connected cavities". However, most remote sensing approaches can not penetrate to the base to monitor such changes continuously. Here we apply seismic interferometry using ambient noise to monitor glacier seismic structures, especially to detect possible signatures of the hypothesized high-pressure water "layer". As an example, we derive an 11-year long history of seismic structure of the Bering Glacier, Alaska, covering its latest surge event. We observe substantial drops of Rayleigh and Love wavespeeds across the glacier during the surge event, potentially caused by changes in crevasse density, glacier thickness, and basal conditions.

Poly[[tetra-μ3-acetato-hexa-μ2-acetato­diaqua-μ2-oxalato-tetra­lanthanum(III)] dihydrate

PubMed Central

Di, Wen-Jing; Lan, Shao-Min; Zhang, Qun; Liang, Yun-Xiao

2011-01-01

The title compound, {[La4(CH3CO2)10(C2O4)(H2O)2]·2H2O}n, exhibits a two-dimensional layered structure with the oxalate and acetate ligands acting as bridges. The asymmetric unit contains two crystallographically independent lanthanum(III) ions, half of an oxalate ligand, five acetate ligands, one coordinated water mol­ecule and one uncoordinated water mol­ecule. The coordination numbers of the two La ions are 9 and 10. Adjacent layers of the structure, which extend parallel to (100), are linked by O–H⋯O hydrogen bonds and are also held together by van der Waals inter­actions between the CH3 groups of the acetate anions. PMID:22064832

Mn0.95I0.02[PO3(OH)] · 2H2O phosphate-iodate, an inorganic analogue of phosphonates

NASA Astrophysics Data System (ADS)

Belokoneva, E. L.; Dimitrova, O. V.; Volkov, A. S.

2015-09-01

The new Mn0.95I0.02[PO3(OH)] · 2H2O phosphate-iodate (space group Pnam = Pnma, D {2/h 16}) is obtained under hydrothermal conditions. The crystal structure is determined without preliminary knowledge of the chemical formula. The structure consists of layers of MnО6 octahedra connected with PO4 tetrahedra. Water molecules are located between the layers. [IO3]- groups having a typical umbrella-like coordination are statistically implanted in layers of MnО6 octahedra at a distance of 1.2 Å from Mn atoms. Their content in the crystal is minor. The structures of the phosphate-iodate coincides with the structures of phosphonates with consideration for the replacement of one (OH) vertex of the РО4 tetrahedron by the organic methyl radical СН3. In the structures of phosphonates and earlier studied phosphates, identical layers are distinguished and the cause of the existence of two MDO varieties is established based on the analysis within the OD theory. Possible hybrid structures derived from the prototypes under consideration are predicted.

Effect of CaCl2 on the property of an anionic surfactant monolayer formed at the air/water interface: a molecular dynamics study

NASA Astrophysics Data System (ADS)

Zhang, Tiantian; You, Jing; Yu, Jiliang; Fan, Chengcheng; Ma, Yunfei; Cui, Yanjie; Gao, Shanshan; Li, Yongbin; Hu, Songqing; Liu, Huiqin

2017-12-01

Molecular dynamics simulation had been carried out to investigate the influence of CaCl2 on the aggregation behaviour of sodium dodecyl polyoxyethylene sulfonate (A12E2SO3) at the air/water interface. First, structure properties of A12E2SO3 monolayer was studied by analyzing the snapshots of the configuration and density profiles of different components in A12E2SO3 systems. Results showed that Ca2+ could replace some Na+ to combine with the hydrophilic headgroups. Besides, the addition of CaCl2 could reduce the thickness of water layer at the interface. Second, the interactions between A12E2SO3 headgroups and water molecules were studied through calculating radial distribution functions (RDFs) between water molecules and the sulfonate group, as well as the oxyethyl group. Results revealed that Ca2+ could penetrate the hydration layer of the sulfonate group, but could not enter the first hydration layer of the oxygen ethyl group close to the sulfonate group. The addition of CaCl2 could make the degree of hydration more orderly and the thickness of hydration layer in the headgroups of A12E2SO3 molecules increase. Third, the property of interface double layer was studied through analyzing RDFs of the headgroups and counterions. Results showed that the addition of CaCl2 could not only reduce the interaction between the headgroups and the counterions, but also compress the thickness of the electric double layer in A12E2SO3 system.

Surface modification of paper on a continuous atmospheric-pressure-plasma system

NASA Astrophysics Data System (ADS)

Cruz-Barba, Luis Emilio

Plasma technologies for the continuous modification of materials in atmospheric-pressure-plasma conditions were used to evaluate the surface modification of paper under different plasma conditions. The generation of hydrophobic layers was used to characterize the efficiency of the originally designed system for future application in the paper industry. Generation of hydrophobic layers was carried out by deposition of thin layers from fluorine containing gases, as well as cross-linking of pre-deposited thin layers of hydrophobic materials, such as fluoropolymers and silicones, in a continuous system plasma reactor (CSPR). Physical and chemical characterization of these layers was carried out by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), scanning electron microscopy (SEM), contact angle goniometry, and water absorption evaluations. Pure gaseous CF4 and a CF4/CH4 mixture were used to deposit fluorinated layers, rendering paper surfaces with low to moderate relative surface atomic contents of fluorine (2.5 to 16.3%). Morphological characterization revealed that the deposition consists of small clusters of fluorinated species scattered on the surface. Contact angle evaluations (50°--70°) indicated a reduction in the water affinity of the paper. Thin layers of fluoropolymer pre-deposited on paper surfaces were cross-linked in the presence of CF4, CF4/CH4, and NH 3 plasmas. All of the gases proved to be effective for the cross-linking under different conditions. These cross-linked layers were determined to maintain the original polymer structure, consisting mainly of CF2-CF 2 and small quantities of CFx. Surface characterization by AFM indicated lower roughness values compared to the untreated additive-free paper (45.1 vs 67.1 nm). Paper samples treated by this approach showed a highly hydrophobic character with up to 160° contact angles, and water absorption was reduced by as much as 61.6%. Silicone layers were cross-linked in the presence of argon and oxygen plasmas. Characterization of the silicone-coated paper indicated, as in the case of fluoropolymers, the retention of the original chemical structure. Surface roughness values (AFM) were in the range of 11.8 to 18.2 nm, evidence of a very smooth surface. High hydrophobicity levels were reached, as shown by contact angles of up to 126°, and water absorption showed a maximum reduction of 76.8%.

Modelling and simulation of high-frequency (100 MHz) ultrasonic linear arrays based on single crystal LiNbO3.

PubMed

Zhang, J Y; Xu, W J; Carlier, J; Ji, X M; Nongaillard, B; Queste, S; Huang, Y P

2012-01-01

High-frequency ultrasonic transducer arrays are essential for high resolution imaging in clinical analysis and Non-Destructive Evaluation (NDE). However, the fabrication of conventional backing-layer structure, which requires a pitch (distance between the centers of two adjacent elements) of half wavelength in medium, is really a great challenge. Here we present an alternative buffer-layer structure with a silicon lens for volumetric imaging. The requirement for the size of the pitch is less critical for this structure, making it possible to fabricate high-frequency (100MHz) ultrasonic linear array transducers. Using silicon substrate also makes it possible to integrate the arrays with IC (Integrated Circuit). To compare with the conventional backing-layer structure, a finite element tool, COMSOL, is employed to investigate the performances of acoustic beam focusing, the influence of pitch size for the buffer-layer configuration, and to calculate the electrical properties of the arrays, including crosstalk effect and electrical impedance. For a 100MHz 10-element array of buffer-layer structure, the ultrasound beam in azimuth plane in water could be electronically focused to obtain a spatial resolution (a half-amplitude width) of 86μm at the focal depth. When decreasing from half wavelength in silicon (42μm) to half wavelength in water (7.5μm), the pitch sizes weakly affect the focal resolution. The lateral spatial resolution is increased by 4.65% when the pitch size decreases from 42μm to 7.5μm. The crosstalk between adjacent elements at the central frequency is, respectively, -95dB, -39.4dB, and -60.5dB for the 10-element buffer, 49-element buffer and 49-element backing arrays. Additionally, the electrical impedance magnitudes for each structure are, respectively, 4kΩ, 26.4kΩ, and 24.2kΩ, which is consistent with calculation results using Krimholtz, Leedom, and Matthaei (KLM) model. These results show that the buffer-layer configuration is a promising alternative for the fabrication of high-frequency ultrasonic linear arrays dedicated to volumetric imaging. Copyright © 2011 Elsevier B.V. All rights reserved.

Acoustic measurements of the spatial and temporal structure of the near-bottom boundary layer in the 1990-1991 STRESS experiment

NASA Astrophysics Data System (ADS)

Lynch, James F.; Irish, James D.; Gross, Thomas F.; Wiberg, Patricia L.; Newhall, Arthur E.; Traykovski, Peter A.; Warren, Joseph D.

1997-08-01

As part of the 1990-1991 Sediment TRansport Events on Shelves and Slopes (STRESS) experiment, a 5 MHz Acoustic BackScatter System (ABSS) was deployed in 90 m of water to measure vertical profiles of near-bottom suspended sediment concentration. By looking at the vertical profile of concentration from 0 to 50 cm above bottom (cmab) with 1 cm vertical resolution, the ABSS was able to examine the detailed structure of the bottom boundary layer created by combined wave and current stresses. The acoustic profiles clearly showed the wave-current boundary layer, which extends to (order) 10 cmab. The profiles also showed evidence of an "intermediate" boundary layer, also influenced by combined wave and current stresses, just above the wave-current boundary layer. This paper examines the boundary-layer structure by comparing acoustic data obtained by the authors to a 1-D eddy viscosity model formulation. Specifically, these data are compared to a simple extension of the Grant-Glenn-Madsen model formulation. Also of interest is the appearance of apparently 3-D "advective plume" structures in these data. This is an interesting feature in a site which was initially chosen to be a good example of (temporally averaged) 1-D bottom boundary-layer dynamics. Computer modeling and sector-scanning sonar images are presented to justify the plausibility of observing 3-D structure at the STRESS site. 1997 Elsevier Science Ltd

X-ray Study of the Electric Double Layer at the n-Hexane/Nanocolloidal Silica Interface

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

Tikhonov,A.

The spatial structure of the transition region between an insulator and an electrolyte solution was studied with x-ray scattering. The electron-density profile across the n-hexane/silica sol interface (solutions with 5, 7, and 12 nm colloidal particles) agrees with the theory of the electrical double layer and shows separation of positive and negative charges. The interface consists of three layers, i.e., a compact layer of Na{sup +}, a loose monolayer of nanocolloidal particles as part of a thick diffuse layer, and a low-density layer sandwiched between them. Its structure is described by a model in which the potential gradient at themore » interface reflects the difference in the potentials of 'image forces' between the cationic Na{sup +} and anionic nanoparticles and the specific adsorption of surface charge. The density of water in the large electric field ({approx}10{sup 9}-10{sup 10} V/m) of the transition region and the layering of silica in the diffuse layer is discussed.« less

Controllable synthesizing DLC nano structures as a super hydrophobic layer on cotton fabric using a low-cost ethanol electrospray-assisted atmospheric plasma jet.

PubMed

Sohbatzadeh, F; Eshghabadi, M; Mohsenpour, T

2018-06-29

The surface modification of cotton samples was carried out using a liquid (ethanol) electrospray-assisted atmospheric pressure plasma jet. X-ray photoelectron spectroscopy (XPS) and Raman analysis confirmed the successful deposition of diamond like carbon (DLC) nano structures on the cotton surface. The super hydrophobic state of the samples was probed by contact angle measurements. The water repellency of the layers was tuned by controlling the voltage applied to the electrospray electrode. An investigation of the morphological and chemical structures of the samples by field emission scanning microscopy, atomic force microscopy (AFM) and XPS indicated that the physical shape, distribution and amorphization of the DLC structures were successfully adjusted and improved by applying a voltage to the electrospray electrode. Finally wash durability of the best sample was tested for 35 cycles. In this work, the use of a well-developed atmospheric pressure plasma jet for DLC nano structures deposition can enable a promising environmentally friendly and low-cost approach for modifying cotton fabrics for super water-repellent fabric applications.

Controllable synthesizing DLC nano structures as a super hydrophobic layer on cotton fabric using a low-cost ethanol electrospray-assisted atmospheric plasma jet

NASA Astrophysics Data System (ADS)

Sohbatzadeh, F.; Eshghabadi, M.; Mohsenpour, T.

2018-06-01

The surface modification of cotton samples was carried out using a liquid (ethanol) electrospray-assisted atmospheric pressure plasma jet. X-ray photoelectron spectroscopy (XPS) and Raman analysis confirmed the successful deposition of diamond like carbon (DLC) nano structures on the cotton surface. The super hydrophobic state of the samples was probed by contact angle measurements. The water repellency of the layers was tuned by controlling the voltage applied to the electrospray electrode. An investigation of the morphological and chemical structures of the samples by field emission scanning microscopy, atomic force microscopy (AFM) and XPS indicated that the physical shape, distribution and amorphization of the DLC structures were successfully adjusted and improved by applying a voltage to the electrospray electrode. Finally wash durability of the best sample was tested for 35 cycles. In this work, the use of a well-developed atmospheric pressure plasma jet for DLC nano structures deposition can enable a promising environmentally friendly and low-cost approach for modifying cotton fabrics for super water-repellent fabric applications.

Subsurface chlorophyll maximum layers: enduring enigma or mystery solved?

PubMed

Cullen, John J

2015-01-01

The phenomenon of subsurface chlorophyll maximum layers (SCMLs) is not a unique ecological response to environmental conditions; rather, a broad range of interacting processes can contribute to the formation of persistent layers of elevated chlorophyll a concentration (Chl) that are nearly ubiquitous in stratified surface waters. Mechanisms that contribute to the formation and maintenance of the SCMLs include a local maximum in phytoplankton growth rate near the nutricline, photoacclimation of pigment content that leads to elevated Chl relative to phytoplankton biomass at depth, and a range of physiologically influenced swimming behaviors in motile phytoplankton and buoyancy control in diatoms and cyanobacteria that can lead to aggregations of phytoplankton in layers, subject to grazing and physical control. A postulated typical stable water structure characterizes consistent patterns in vertical profiles of Chl, phytoplankton biomass, nutrients, and light across a trophic gradient structured by the vertical flux of nutrients and characterized by the average daily irradiance at the nutricline. Hypothetical predictions can be tested using a nascent biogeochemical global ocean observing system. Partial results to date are generally consistent with predictions based on current knowledge, which has strong roots in research from the twentieth century.

Infrared and Raman spectroscopic characterization of the silicate-carbonate mineral carletonite - KNa4Ca4Si8O18(CO3)4(OH,F)·H2O

NASA Astrophysics Data System (ADS)

Frost, Ray L.; Xi, Yunfei; Scholz, Ricardo; López, Andrés; Belotti, Fernanda Maria

2013-06-01

An assessment of the molecular structure of carletonite a rare phyllosilicate mineral with general chemical formula given as KNa4Ca4Si8O18(CO3)4(OH,F)·H2O has been undertaken using vibrational spectroscopy. Carletonite has a complex layered structure. Within one period of c, it contains a silicate layer of composition NaKSi8O18·H2O, a carbonate layer of composition NaCO3·0.5H2O and two carbonate layers of composition NaCa2CO3(F,OH)0.5. Raman bands are observed at 1066, 1075 and 1086 cm-1. Whether these bands are due to the CO32- ν1 symmetric stretching mode or to an SiO stretching vibration is open to question. Multiple bands are observed in the 300-800 cm-1 spectral region, making the attribution of these bands difficult. Multiple water stretching and bending modes are observed showing that there is much variation in hydrogen bonding between water and the silicate and carbonate surfaces.

Stable aqueous dispersions of functionalized multi-layer graphene by pulsed underwater plasma exfoliation of graphite

NASA Astrophysics Data System (ADS)

Meyer-Plath, Asmus; Beckert, Fabian; Tölle, Folke J.; Sturm, Heinz; Mülhaupt, Rolf

2016-02-01

A process was developed for graphite particle exfoliation in water to stably dispersed multi-layer graphene. It uses electrohydraulic shockwaves and the functionalizing effect of solution plasma discharges in water. The discharges were excited by 100 ns high voltage pulsing of graphite particle chains that bridge an electrode gap. The underwater discharges allow simultaneous exfoliation and chemical functionalization of graphite particles to partially oxidized multi-layer graphene. Exfoliation is caused by shockwaves that result from rapid evaporation of carbon and water to plasma-excited gas species. Depending on discharge energy and locus of ignition, the shockwaves cause stirring, erosion, exfoliation and/or expansion of graphite flakes. The process was optimized to produce long-term stable aqueous dispersions of multi-layer graphene from graphite in a single process step without requiring addition of intercalants, surfactants, binders or special solvents. A setup was developed that allows continuous production of aqueous dispersions of flake size-selected multi-layer graphenes. Due to the well-preserved sp2-carbon structure, thin films made from the dispersed graphene exhibited high electrical conductivity. Underwater plasma discharge processing exhibits high innovation potential for morphological and chemical modifications of carbonaceous materials and surfaces, especially for the generation of stable dispersions of two-dimensional, layered materials.

Contrasting sea-ice and open-water boundary layers during melt and freeze-up seasons: Some result from the Arctic Clouds in Summer Experiment.

NASA Astrophysics Data System (ADS)

Tjernström, Michael; Sotiropoulou, Georgia; Sedlar, Joseph; Achtert, Peggy; Brooks, Barbara; Brooks, Ian; Persson, Ola; Prytherch, John; Salsbury, Dominic; Shupe, Matthew; Johnston, Paul; Wolfe, Dan

2016-04-01

With more open water present in the Arctic summer, an understanding of atmospheric processes over open-water and sea-ice surfaces as summer turns into autumn and ice starts forming becomes increasingly important. The Arctic Clouds in Summer Experiment (ACSE) was conducted in a mix of open water and sea ice in the eastern Arctic along the Siberian shelf during late summer and early autumn 2014, providing detailed observations of the seasonal transition, from melt to freeze. Measurements were taken over both ice-free and ice-covered surfaces, offering an insight to the role of the surface state in shaping the lower troposphere and the boundary-layer conditions as summer turned into autumn. During summer, strong surface inversions persisted over sea ice, while well-mixed boundary layers capped by elevated inversions were frequent over open-water. The former were often associated with advection of warm air from adjacent open-water or land surfaces, whereas the latter were due to a positive buoyancy flux from the warm ocean surface. Fog and stratus clouds often persisted over the ice, whereas low-level liquid-water clouds developed over open water. These differences largely disappeared in autumn, when mixed-phase clouds capped by elevated inversions dominated in both ice-free and ice-covered conditions. Low-level-jets occurred ~20-25% of the time in both seasons. The observations indicate that these jets were typically initiated at air-mass boundaries or along the ice edge in autumn, while in summer they appeared to be inertial oscillations initiated by partial frictional decoupling as warm air was advected in over the sea ice. The start of the autumn season was related to an abrupt change in atmospheric conditions, rather than to the gradual change in solar radiation. The autumn onset appeared as a rapid cooling of the whole atmosphere and the freeze up followed as the warm surface lost heat to the atmosphere. While the surface type had a pronounced impact on boundary-layer structure in summer, the surface was often warmer than the atmosphere in autumn, regardless of surface type. Hence the autumn boundary-layer structure was more dependent on synoptic scale meteorology.

Inelastic neutron scattering and molecular simulation of the dynamics of interlayer water in smectite clay minerals

DOE PAGES

Cygan, Randall T.; Daemen, Luke L.; Ilgen, Anastasia G.; ...

2015-11-16

The study of mineral–water interfaces is of great importance to a variety of applications including oil and gas extraction, gas subsurface storage, environmental contaminant treatment, and nuclear waste repositories. Understanding the fundamentals of that interface is key to the success of those applications. Confinement of water in the interlayer of smectite clay minerals provides a unique environment to examine the interactions among water molecules, interlayer cations, and clay mineral surfaces. Smectite minerals are characterized by a relatively low layer charge that allows the clay to swell with increasing water content. Montmorillonite and beidellite varieties of smectite were investigated to comparemore » the impact of the location of layer charge on the interlayer structure and dynamics. Inelastic neutron scattering of hydrated and dehydrated cation-exchanged smectites was used to probe the dynamics of the interlayer water (200–900 cm –1 spectral region) and identify the shift in the librational edge as a function of the interlayer cation. Molecular dynamics simulations of equivalent phases and power spectra, derived from the resulting molecular trajectories, indicate a general shift in the librational behavior with interlayer cation that is generally consistent with the neutron scattering results for the monolayer hydrates. Both neutron scattering and power spectra exhibit librational structures affected by the location of layer charge and by the charge of the interlayer cation. Furthermore, divalent cations (Ba 2+ and Mg 2+) characterized by large hydration enthalpies typically exhibit multiple broad librational peaks compared to monovalent cations (Cs + and Na +), which have relatively small hydration enthalpies.« less

Dark gray soils on two-layered deposits in the north of Tambov Plain: Agroecology, properties, and diagnostics

NASA Astrophysics Data System (ADS)

Zaidelman, F. R.; Nikiforova, A. S.; Stepantsova, L. V.; Volokhina, V. P.

2012-05-01

Dark gray soils in the Tambov Plain are developed from the light-textured glaciofluvial deposits underlain by the calcareous loam. Their morphology, water regime, and productivity are determined by the depth of the slightly permeable calcareous loamy layer, relief, and the degree of gleyzation. The light texture of the upper layer is responsible for its weak structure, high density, the low content of productive moisture, and the low water-holding capacity. If the calcareous loam is at a depth of 100-130 cm, dark gray soils are formed; if it lies at a depth of 40-70 cm, temporary perched water appears in the profile, and dark gray contact-gleyed soils are formed. Their characteristic pedofeatures are skeletans in the upper layers, calcareous nodules in the loamy clay layer, and iron nodules in the podzolized humus and podzolic horizons. The appearance of Fe-Mn concretions is related to gleyzation. The high yield of winter cereals is shown to be produced on the dark gray soils; the yields of spring crops are less stable. Spring cereals should not be grown on the contact-gleyed dark gray soils.

Cloud and boundary layer structure over San Nicolas Island during FIRE

NASA Technical Reports Server (NTRS)

Albrecht, Bruce A.; Fairall, Christopher W.; Syrett, William J.; Schubert, Wayne H.; Snider, Jack B.

1990-01-01

The temporal evolution of the structure of the marine boundary layer and of the associated low-level clouds observed in the vicinity of the San Nicolas Island (SNI) is defined from data collected during the First ISCCP Regional Experiment (FIRE) Marine Stratocumulus Intense Field Observations (IFO) (July 1 to 19). Surface, radiosonde, and remote-sensing measurements are used for this analysis. Sounding from the Island and from the ship Point Sur, which was located approximately 100 km northwest of SNI, are used to define variations in the thermodynamic structure of the lower-troposphere on time scales of 12 hours and longer. Time-height sections of potential temperature and equivalent potential temperature clearly define large-scale variations in the height and the strength of the inversion and periods where the conditions for cloud-top entrainment instability (CTEI) are met. Well defined variations in the height and the strength of the inversion were associated with a Cataline Eddy that was present at various times during the experiment and with the passage of the remnants of a tropical cyclone on July 18. The large-scale variations in the mean thermodynamic structure at SNI correlate well with those observed from the Point Sur. Cloud characteristics are defined for 19 days of the experiment using data from a microwave radiometer, a cloud ceilometer, a sodar, and longwave and shortwave radiometers. The depth of the cloud layer is estimated by defining inversion heights from the sodar reflectivity and cloud-base heights from a laser ceilometer. The integrated liquid water obtained from NOAA's microwave radiometer is compared with the adiabatic liquid water content that is calculated by lifting a parcel adiabatically from cloud base. In addition, the cloud structure is characterized by the variability in cloud-base height and in the integrated liquid water.

Ciliate diversity and distribution patterns in the sediments of a seamount and adjacent abyssal plains in the tropical Western Pacific Ocean.

PubMed

Zhao, Feng; Filker, Sabine; Stoeck, Thorsten; Xu, Kuidong

2017-09-12

Benthic ciliates and the environmental factors shaping their distribution are far from being completely understood. Likewise, deep-sea systems are amongst the least understood ecosystems on Earth. In this study, using high-throughput DNA sequencing, we investigated the diversity and community composition of benthic ciliates in different sediment layers of a seamount and an adjacent abyssal plain in the tropical Western Pacific Ocean with water depths ranging between 813 m and 4566 m. Statistical analyses were used to assess shifts in ciliate communities across vertical sediment gradients and water depth. Nine out of 12 ciliate classes were detected in the different sediment samples, with Litostomatea accounting for the most diverse group, followed by Plagiopylea and Oligohymenophorea. The novelty of ciliate genetic diversity was extremely high, with a mean similarity of 93.25% to previously described sequences. On a sediment depth gradient, ciliate community structure was more similar within the upper sediment layers (0-1 and 9-10 cm) compared to the lower sediment layers (19-20 and 29-30 cm) at each site. Some unknown ciliate taxa which were absent from the surface sediments were found in deeper sediments layers. On a water depth gradient, the proportion of unique OTUs was between 42.2% and 54.3%, and that of OTUs shared by all sites around 14%. However, alpha diversity of the different ciliate communities was relatively stable in the surface layers along the water depth gradient, and about 78% of the ciliate OTUs retrieved from the surface layer of the shallowest site were shared with the surface layers of sites deeper than 3800 m. Correlation analyses did not reveal any significant effects of measured environmental factors on ciliate community composition and structure. We revealed an obvious variation in ciliate community along a sediment depth gradient in the seamount and the adjacent abyssal plain and showed that water depth is a less important factor shaping ciliate distribution in deep-sea sediments unlike observed for benthic ciliates in shallow seafloors. Additionally, an extremely high genetic novelty of ciliate diversity was found in these habitats, which points to a hot spot for the discovery of new ciliate species.

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

Qin, Ling, E-mail: qinling0924013@163.com; Wang, Yan-Qing; Ni, Gang

The title complex, ([Zn(ODIB){sub 1/2}(bpdc)]·2DMF){sub n} was prepared under hydrothermal conditions (dimethylformamide and water) based on two ligands, namely, 1,1′-oxy-bis[3,5-diimidazolyl-benzene] (ODIB) and biphenyldicarboxylic acid (H{sub 2}bpdc). ODIB ligands link Zn cations to give layers in crystal. bpdc{sup 2–} anions coordinate to Zn atoms, however, their introduction does not increase the dimension of the structure. Each layer is partially passes through the adjacent layers in the offset ABAB manner.

Mössbauer study of oxide phase distributions in rust formed on steel constructions near the Black Sea in Sochi

NASA Astrophysics Data System (ADS)

Filippov, V. P.; Lauer, Yu. A.; Goloborodko, P. G.; Polyakov, A. M.

2016-12-01

The phase composition of the intermediate oxide layers formed on elements of steel structures at different positions relative to the sea water of the Black Sea near Sochi are investigated. The differences of the phase composition of these oxide layers are shown, depending on the location of the design details in relation to the sea and the abundancies of certain types of oxides in the studied layers are discussed.

Boundary Layer Structure and Its Relation to Precipitation Over the St. Louis Area.

DTIC Science & Technology

1980-10-01

of METEORO LOGY SECTION 0i{1J ( 0I~) AT THE mp UNI VERSITY OV ILLINOIS0 SMISContract Report 241 T - BOUNDARY LAYER STRUCTURE AND ITS RELATION TO...PRECIPITATION OVER THE ST. LOUIS AREA Gary L. Achtemeier Meteorology Section Ill1inois State Water &uIvey, DTII CLeELEC T E C.> JAN 15 1981( Technical...in f r ’TNil PA&F rlhImm Does Rnteredl 𔄃. -. , .’.-..,. -.- -/" . ECumITYv CLASSFICATIOW Of TH t PAGE(Wfhn Date Entr,.e) 15529. 4-GS ?0. ABSTRACT

The effects of gas diffusion layers structure on water transportation using X-ray computed tomography based Lattice Boltzmann method

NASA Astrophysics Data System (ADS)

Jinuntuya, Fontip; Whiteley, Michael; Chen, Rui; Fly, Ashley

2018-02-01

The Gas Diffusion Layer (GDL) of a Polymer Electrolyte Membrane Fuel Cell (PEMFC) plays a crucial role in overall cell performance. It is responsible for the dissemination of reactant gasses from the gas supply channels to the reactant sites at the Catalyst Layer (CL), and the adequate removal of product water from reactant sites back to the gas channels. Existing research into water transport in GDLs has been simplified to 2D estimations of GDL structures or use virtual stochastic models. This work uses X-ray computed tomography (XCT) to reconstruct three types of GDL in a model. These models are then analysed via Lattice Boltzmann methods to understand the water transport behaviours under differing contact angles and pressure differences. In this study, the three GDL samples were tested over the contact angles of 60°, 80°, 90°, 100°, 120° and 140° under applied pressure differences of 5 kPa, 10 kPa and 15 kPa. By varying the contact angle and pressure difference, it was found that the transition between stable displacement and capillary fingering is not a gradual process. Hydrophilic contact angles in the region of 60°<θ < 90° showed stable displacement properties, whereas contact angles in the region of 100°<θ < 140° displayed capillary fingering characteristics.

Spatial and Temporal Variations of the K/T Boundary Record: Implications Concerning Possible Megaseiche in the Reworking Processes

NASA Astrophysics Data System (ADS)

Maurrasse, F. J.; Lamolda, M. A.

2004-05-01

Major physical disruptions characterize the sedimentary record of the K/T boundary (KTB) layer from different sites in the Southern Peninsula of Haiti as well as in diverse areas of the world. These disturbances are most important within the vicinity of the crater at Chicxulub, Yucatan, Mexico, and 65 million years ago that can be chronologically correlated with the bolide impact postulated by Alvarez et al (1981). At all sites the KTB layer shows spatial and temporal differences even within short distances, and the complexity of its characteristic signals includes serious micropaleontological inconsistencies with mixed biotic assemblages that perpetuate divergence of interpretations, thereby they raise doubts on the timing and real causal mechanisms of the biotic turnover that characterizes the boundary. Indeed, often the biostratigraphic signals are difficult to resolve because of hiatuses, or sediments are highly reworked, and distinct taxonomic successions are not clearly defined. Well defined as well as cryptic primary sedimentary structures within the boundary layer are constant at all outcrops, and they indicate complex, multiphase, subaqueous flow processes that affected sedimentation of the KTB layer at different times. The structures are known to characterize oscillatory wave processes that affect cohesionless sediments, and such water motion is only known to be associated with seiche as a modern analog that may have generated the amalgamation recorded at the KTB layer. We believe that "Megaseiche" associated with the KT impact event and its subsequent effects provides a plausible unifying mechanism to explain how various levels of the water column in different large basins can oscillate to develop the structures observed. Because of the magnitude of the bolide impact that generated initial tsunamis and large seismic waves worldwide, megaseiches of different frequencies and nodal modes must have developed in the oceans worldwide to leave different signatures in the mixing pattern. Most importantly, the heterogeneity must have been further intensified in subsequent times when more localized megaseiches developed in independent basins at different times during major crustal readjustment. These phenomena may explain the heterogeneity of patterns and apparent irreconcilable discrepancies observed at KTB sites worldwide, as the structures represent a record of water movement and resuspension of sediment of different intensities and at different timesat certain locations. As observed in smaller-scale modern seiche, various oscillatory modes controlled the duration and attenuation of the water movement, the magnitude of bottom traction and resuspension that led to complex sedimentary structures and reworking patterns of the sediments and microfossils.

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.

Adaptive differences in the structure and macromolecular compositions of the air and water corneas of the “four-eyed” fish (Anableps anableps)

PubMed Central

SWAMYNATHAN, SHIVALINGAPPA K.; CRAWFORD, MARY A.; ROBISON, W. GERALD; KANUNGO, JYOTSHNABALA; PIATIGORSKY, JORAM

2018-01-01

The water meniscus bisects the eyes of the “four-eyed” fish Anableps anableps, resulting in simultaneous vision in air and water. We compare the structure and macromolecular compositions of the Anableps dorsal (air) and ventral (water) corneas with the fully aquatic zebrafish cornea. The Anableps dorsal corneal epithelium is thicker (>20 cell layers), flatter (~1.94 mm radius of curvature), and contains ~15-fold more glycogen (0.16 μg/μg water-soluble protein) than the ventral corneal epithelium (5–7 cell layers; ~1.63 mm radius of curvature; 0.01 μg glycogen/μg water-soluble protein), which resembles the zebrafish corneal epithelium. Gelsolin is the major water-soluble protein in the zebrafish (~50%) and Anableps dorsal (~38%) and ventral (~21%) corneal epithelia, suggesting that gelsolin was recruited for high corneal expression before these two species diverged at least 100 million years ago and that abundant corneal gelsolin is not limited to aquatic vision. Anableps gelsolin, deduced from its cDNA, is 57% identical to zebrafish gelsolin. Paucity of Anableps corneal F-actin (consistent with high gelsolin) was confirmed by the absence of rhodaminephalloidin staining. We suggest amphibious refraction and protection from UV irradiation and desiccation in air as selective constraints for the specializations of the Anableps dorsal cornea.—Swamynathan, S. K., Craw-ford, M. A., Robison, W. G., Jr., Kanungo, J., Piatigorsky, J. Adaptive differences in the structure and macromolecular compositions of the air and water corneas of the “four-eyed” fish (Anableps anableps). PMID:14597669

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 impact of water vapor assimilation on quantitative precipitation forecast over the Washington, DC metropolitan area

NASA Astrophysics Data System (ADS)

Walford, Segayle Cereta

Forecasting subtle, small-scale convective cases in both winter and summer time is an ongoing challenge in weather forecasting. Recent studies have shown that better structure of moisture within the boundary layer is crucial for improving forecasting skills, particularly quantitative precipitation forecasting (QPF). Lidars, which take high temporal observations of moisture, are able to capture very detailed structures, especially within the boundary layer where convection often begins. This study first investigates the extent to which an aerosol and a water vapor lidar are able to capture key boundary layer processes necessary for the development of convection. The results of this preliminary study show that the water vapor lidar is best able to capture the small scale water vapor variability that is necessary for the development of convection. These results are then used to investigate impacts of assimilating moisture from the Howard University Raman Lidar (HURL) for one mesoscale convective case, July 27-28, 2006. The data for this case is from the Water Vapor Validation Experiment-Satellite and Sondes (WAVES) field campaign located at the Howard University Beltsville Site (HUBS) in Beltsville, MD. Specifically, lidar-based water vapor mixing ratio profiles are assimilated into the Weather Research and Forecasting (WRF) regional model over a 4 km grid resolution over Washington, DC. Model verification is conducted using the Meteorological Evaluation Tool (MET) and the results from the lidar run are then compared to a control (no assimilation) run. The findings indicate that quantitatively conclusions cannot be draw from this one case study. However, qualitatively, the assimilation of the lidar observations improved the equivalent potential temperature, and water vapor distribution of the region. This difference changed location, strength and spatial coverage of the convective system over the HUBS region.

Electrically Conductive Porous Membrane

NASA Technical Reports Server (NTRS)

Burke, Kenneth Alan (Inventor)

2014-01-01

The present invention relates to an electrically conductive membrane that can be configured to be used in fuel cell systems to act as a hydrophilic water separator internal to the fuel cell, or as a water separator used with water vapor fed electrolysis cells, or as a water separator used with water vapor fed electrolysis cells, or as a capillary structure in a thin head pipe evaporator, or as a hydrophobic gas diffusion layer covering the fuel cell electrode surface in a fuel cell.

Elastic Wave Propagation through Multilayered Media

DTIC Science & Technology

1980-03-01

Distilled ) 20 Water (Heavy,D^O) 19.8 o-Xylene 20 m-Xylene 20 p-Xylene 20 ■■■/ Wavespeed Long. Trans. Surf Density Ref. 10^ cm/sec gm/cm...7 3 Schematic of Three Layer Structure 15 4a Longitudinal Wave Incident on a Water /Lucite Interface 17 4b Longitudinal Wave Incident on a Lucite... Water Interface 17 5a Longitudinal Wave Incident on an Aluminum/ Water Interface 18 5b Longitudinal Wave Incident on a Steel/ Water Interface 18 6a

Designed drug-release systems having various breathable polyurethane film-backed hydrocolloid acrylated adhesive layers for moisture healing.

PubMed

Chang, Ching-Hsien; Liu, Hsia-Wei; Huang, Ching-Cheng

2014-01-01

A series of designed drug-release systems were prepared and established for clear moisture healing. These systems were designed to have an interpenetrating polymer network (IPN) structure, which contained a breathable polyurethane film, hydrocolloidlayer, and polyacrylate adhesive layer. Breathable polyurethane film (2000 g/m(2)/24 hr) with high moisture permeability was employed as a base for new drug-release systems or wound dressings. All drug-release systems having a polyurethane film-backed hydrocolloid acrylated adhesive layer showed an increase of water uptakes with increasing time. After 114 hours, high water uptakes of drug-release systems with 20% hydrocolloid components were observed in the values of 160, 1100, and 1870% for different additional hydrocolloid components of carboxymethylcellulose, sodium alginate, and carbomer U10, respectively. New drug-release systems of polyurethane film-backed hydrocolloid/adhesive layers could be designed and established for wound care managements.

Superhydrophobic alumina surface based on stearic acid modification

NASA Astrophysics Data System (ADS)

Feng, Libang; Zhang, Hongxia; Mao, Pengzhi; Wang, Yanping; Ge, Yang

2011-02-01

A novel superhydrophobic alumina surface is fabricated by grafting stearic acid layer onto the porous and roughened aluminum film. The chemical and phase structure, morphology, and the chemical state of the atoms at the superhydrophobic surface were investigated by techniques as FTIR, XRD, FE-SEM, and XPS, respectively. Results show that a super water-repellent surface with a contact angle of 154.2° is generated. The superhydrophobic alumina surface takes on an uneven flowerlike structure with many nanometer-scale hollows distribute in the nipple-shaped protrusions, and which is composed of boehmite crystal and γ-Al2O3. Furthermore, the roughened and porous alumina surface is coated with a layer of hydrophobic alkyl chains which come from stearic acid molecules. Therefore, both the roughened structure and the hydrophobic layer endue the alumina surface with the superhydrophobic behavior.

Small-scale variability in tropical tropopause layer humidity

NASA Astrophysics Data System (ADS)

Jensen, E. J.; Ueyama, R.; Pfister, L.; Karcher, B.; Podglajen, A.; Diskin, G. S.; DiGangi, J. P.; Thornberry, T. D.; Rollins, A. W.; Bui, T. V.; Woods, S.; Lawson, P.

2016-12-01

Recent advances in statistical parameterizations of cirrus cloud processes for use in global models are highlighting the need for information about small-scale fluctuations in upper tropospheric humidity and the physical processes that control the humidity variability. To address these issues, we have analyzed high-resolution airborne water vapor measurements obtained in the Airborne Tropical TRopopause EXperiment over the tropical Pacific between 14 and 20 km. Using accurate and precise 1-Hz water vapor measurements along approximately-level aircraft flight legs, we calculate structure functions spanning horizontal scales ranging from about 0.2 to 50 km, and we compare the water vapor variability in the lower (about 14 km) and upper (16-19 km) Tropical Tropopause Layer (TTL). We also compare the magnitudes and scales of variability inside TTL cirrus versus in clear-sky regions. The measurements show that in the upper TTL, water vapor concentration variance is stronger inside cirrus than in clear-sky regions. Using simulations of TTL cirrus formation, we show that small variability in clear-sky humidity is amplified by the strong sensitivity of ice nucleation rate to supersaturation, which results in highly-structured clouds that subsequently drive variability in the water vapor field. In the lower TTL, humidity variability is correlated with recent detrainment from deep convection. The structure functions indicate approximately power-law scaling with spectral slopes ranging from about -5/3 to -2.

Successful new anti-sloughing drilling fluid application, Yanchang gas field, China

NASA Astrophysics Data System (ADS)

He, Peng; Liu, Hanmei; Du, Sen; He, Chenghai

2017-10-01

Borehole collapse had always been encountered when drilling the Shiqianfeng and Shihezi formations in Yan Chang gas field. By analyzing the reasons for the collapse can be obtained, "double layer of stone" brittle strong, pore development, water sensitivity and high mineral content filling skeleton particles, water lock effect and stress sensitivity is a potential factor in inducing strong wall collapse. According to the characteristics of the geological structure developed anti-sloughing drilling fluid system "double layer of stone," "complex fluid loss - dual inhibition - materialized block" multiple cooperative mechanism to achieve the purpose of anti-collapse.

Sum frequency generation (SFG) vibrational spectroscopy of planar phosphatidylethanolamine hybrid bilayer membranes under water.

PubMed

Kett, Peter J N; Casford, Michael T L; Davies, Paul B

2010-06-15

Sum frequency generation (SFG) spectroscopy has been used to study the structure of phosphatidylethanolamine hybrid bilayer membranes (HBMs) under water at ambient temperatures. The HBMs were formed using a modified Langmuir-Schaefer technique and consisted of a layer of dipalmitoyl phosphatidylethanolamine (DPPE) physisorbed onto an octadecanethiol (ODT) self-assembled monolayer (SAM) at a series of surface pressures from 1 to 40 mN m(-1). The DPPE and ODT were selectively deuterated so that the contributions to the SFG spectra from the two layers could be determined separately. SFG spectra in both the C-H and C-D stretching regions confirmed that a monolayer of DPPE had been adsorbed to the ODT SAM and that there were gauche defects within the alkyl chains of the phospholipid. On adsorption of a layer of DPPE, methylene modes from the ODT SAM were detected, indicating that the phospholipid had partially disordered the alkanethiol monolayer. SFG spectra recorded in air indicated that removal of water from the surface of the HBM resulted in disruption of the DPPE layer and the formation of phospholipid bilayers.

Ellipsometric study of molecular orientations of Thermomyces lanuginosus lipase at the air-water interface by simultaneous determination of refractive index and thickness.

PubMed

Muth, Marco; Schmid, Reiner P; Schnitzlein, Klaus

2016-04-01

Ellipsometric studies of very thin organic films suffer from the low refractive index contrast between layer and bulk substrate. We demonstrate that null ellipsometry can not only provide detailed information about the adsorption kinetics and surface excess values, but in addition on layer thicknesses with submonolayer resolution of a lipase from Thermomyces lanuginosus at the air-water interface. While measuring very close to the Brewster angle, refractive indices and layer-thicknesses can both be determined with a precision that is sufficiently high to make conclusions on the density and orientation of the molecules at the interface. The orientation was found to be concentration- and pH value-dependent. At the isoelectric point, the lipase was almost vertically oriented with respect to the surface, while for pure distilled water and low lipase concentration a rather horizontal alignment was found. Further experiments, varying the size of the interfacial area in a Langmuir trough, confirm the different layer structures. Copyright © 2015 Elsevier B.V. All rights reserved.

Aligning nanodiscs at the air-water interface, a neutron reflectivity study.

PubMed

Wadsäter, Maria; Simonsen, Jens B; Lauridsen, Torsten; Tveten, Erlend Grytli; Naur, Peter; Bjørnholm, Thomas; Wacklin, Hanna; Mortensen, Kell; Arleth, Lise; Feidenhans'l, Robert; Cárdenas, Marité

2011-12-20

Nanodiscs are self-assembled nanostructures composed of a belt protein and a small patch of lipid bilayer, which can solubilize membrane proteins in a lipid bilayer environment. We present a method for the alignment of a well-defined two-dimensional layer of nanodiscs at the air-water interface by careful design of an insoluble surfactant monolayer at the surface. We used neutron reflectivity to demonstrate the feasibility of this approach and to elucidate the structure of the nanodisc layer. The proof of concept is hereby presented with the use of nanodiscs composed of a mixture of two different lipid (DMPC and DMPG) types to obtain a net overall negative charge of the nanodiscs. We find that the nanodisc layer has a thickness or 40.9 ± 2.6 Å with a surface coverage of 66 ± 4%. This layer is located about 15 Å below a cationic surfactant layer at the air-water interface. The high level of organization within the nanodiscs layer is reflected by a low interfacial roughness (~4.5 Å) found. The use of the nanodisc as a biomimetic model of the cell membrane allows for studies of single membrane proteins isolated in a confined lipid environment. The 2D alignment of nanodiscs could therefore enable studies of high-density layers containing membrane proteins that, in contrast to membrane proteins reconstituted in a continuous lipid bilayer, remain isolated from influences of neighboring membrane proteins within the layer. © 2011 American Chemical Society

Exploration and exploitation of homologous series of bis(acrylamido)alkanes containing pyridyl and phenyl groups: β-sheet versus two-dimensional layers in solid-state photochemical [2 + 2] reactions.

PubMed

Garai, Mousumi; Biradha, Kumar

2015-09-01

The homologous series of phenyl and pyridyl substituted bis(acrylamido)alkanes have been synthesized with the aim of systematic analysis of their crystal structures and their solid-state [2 + 2] reactivities. The changes in the crystal structures with respect to a small change in the molecular structure, that is by varying alkyl spacers between acrylamides and/or by varying the end groups (phenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl) on the C-terminal of the amide, were analyzed in terms of hydrogen-bonding interference (N-H⋯Npy versus N-H⋯O=C) and network geometries. In this series, a greater tendency towards the formation of N-H⋯O hydrogen bonds (β-sheets and two-dimensional networks) over N-H⋯N hydrogen bonds was observed. Among all the structures seven structures were found to have the required alignments of double bonds for the [2 + 2] reaction such that the formations of single dimer, double dimer and polymer are facilitated. However, only four structures were found to exhibit such a solid-state [2 + 2] reaction to form a single dimer and polymers. The two-dimensional hydrogen-bonding layer via N-H⋯O hydrogen bonds was found to promote solid-state [2 + 2] photo-polymerization in a single-crystal-to-single-crystal manner. Such two-dimensional layers were encountered only when the spacer between acryl amide moieties is butyl. Only four out of the 16 derivatives were found to form hydrates, two each from 2-pyridyl and 4-pyridyl derivatives. The water molecules in these structures govern the hydrogen-bonding networks by the formation of an octameric water cluster and one-dimensional zigzag water chains. The trends in the melting points and densities were also analyzed.

Chesapeake Bay impact structure: Morphology, crater fill, and relevance for impact structures on Mars

USGS Publications Warehouse

Horton, J. Wright; Ormo, J.; Powars, D.S.; Gohn, G.S.

2006-01-01

The late Eocene Chesapeake Bay impact structure (CBIS) on the Atlantic margin of Virginia is one of the largest and best-preserved "wet-target" craters on Earth. It provides an accessible analog for studying impact processes in layered and wet targets on volatile-rich planets. The CBIS formed in a layered target of water, weak clastic sediments, and hard crystalline rock. The buried structure consists of a deep, filled central crater, 38 km in width, surrounded by a shallower brim known as the annular trough. The annular trough formed partly by collapse of weak sediments, which expanded the structure to ???85 km in diameter. Such extensive collapse, in addition to excavation processes, can explain the "inverted sombrero" morphology observed at some craters in layered targets. The distribution of crater-fill materials i n the CBIS is related to the morphology. Suevitic breccia, including pre-resurge fallback deposits, is found in the central crater. Impact-modified sediments, formed by fluidization and collapse of water-saturated sand and silt-clay, occur in the annular trough. Allogenic sediment-clast breccia, interpreted as ocean-resurge deposits, overlies the other impactites and covers the entire crater beneath a blanket of postimpact sediments. The formation of chaotic terrains on Mars is attributed to collapse due to the release of volatiles from thick layered deposits. Some flat-floored rimless depressions with chaotic infill in these terrains are impact craters that expanded by collapse farther than expected for similar-sized complex craters in solid targets. Studies of crater materials in the CBIS provide insights into processes of crater expansion on Mars and their links to volatiles. ?? The Meteoritical Society, 2006.

Multi-scale hierarchy of Chelydra serpentina: microstructure and mechanical properties of turtle shell.

PubMed

Balani, Kantesh; Patel, Riken R; Keshri, Anup K; Lahiri, Debrupa; Agarwal, Arvind

2011-10-01

Carapace, the protective shell of a freshwater snapping turtle, Chelydra serpentina, shields them from ferocious attacks of their predators while maintaining light-weight and agility for a swim. The microstructure and mechanical properties of the turtle shell are very appealing to materials scientists and engineers for bio-mimicking, to obtain a multi-functional surface. In this study, we have elucidated the complex microstructure of a dry Chelydra serpentina's shell which is very similar to a multi-layered composite structure. The microstructure of a turtle shell's carapace elicits a sandwich structure of waxy top surface with a harder sub-surface layer serving as a shielding structure, followed by a lamellar carbonaceous layer serving as shock absorber, and the inner porous matrix serves as a load-bearing scaffold while acting as reservoir of retaining water and nutrients. The mechanical properties (elastic modulus and hardness) of various layers obtained via nanoindentation corroborate well with the functionality of each layer. Elastic modulus ranged between 0.47 and 22.15 GPa whereas hardness varied between 53.7 and 522.2 MPa depending on the microstructure of the carapace layer. Consequently, the modulus of each layer was represented into object oriented finite element (OOF2) modeling towards extracting the overall effective modulus of elasticity (~4.75 GPa) of a turtle's carapace. Stress distribution of complex layered structure was elicited with an applied strain of 1% in order to understand the load sharing of various composite layers in the turtle's carapace. Copyright © 2011 Elsevier Ltd. All rights reserved.

High mobility organic field-effect transistor based on water-soluble deoxyribonucleic acid via spray coating

NASA Astrophysics Data System (ADS)

Shi, Wei; Han, Shijiao; Huang, Wei; Yu, Junsheng

2015-01-01

High mobility organic field-effect transistors (OFETs) by inserting water-soluble deoxyribonucleic acid (DNA) buffer layer between electrodes and pentacene film through spray coating process were fabricated. Compared with the OFETs incorporated with DNA in the conventional organic solvents of ethanol and methanol: water mixture, the water-soluble DNA based OFET exhibited an over four folds enhancement of field-effect mobility from 0.035 to 0.153 cm2/Vs. By characterizing the surface morphology and the crystalline structure of pentacene active layer through atomic force microscope and X-ray diffraction, it was found that the adoption of water solvent in DNA solution, which played a key role in enhancing the field-effect mobility, was ascribed to both the elimination of the irreversible organic solvent-induced bulk-like phase transition of pentacene film and the diminution of a majority of charge trapping at interfaces in OFETs.

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.

Evaluation of the effectiveness of drainage layers.

DOT National Transportation Integrated Search

2007-12-31

Research has shown that pavement subdrainage systems can increase the life of pavements by removing : water that is detrimental to the pavement structure. The Mississippi Department of Transportation (MDOT) : began including pavement subdrainage syst...

Seasonal Overturning Circulation in the Red Sea

NASA Astrophysics Data System (ADS)

Yao, F.; Hoteit, I.; Koehl, A.

2010-12-01

The Red Sea exhibits a distinct seasonal overturning circulation. In winter, a typical two-layer exchange structure, with a fresher inflow from the Gulf of Aden on top of an outflow from the Red Sea, is established. In summer months (June to September) this circulation pattern is changed to a three-layer structure: a surface outflow from the Red Sea on top of a subsurface intrusion of the Gulf of Aden Intermediate Water and a weakened deep outflow. This seasonal variability is studied using a general circulation model, MITgcm, with 6 hourly NCEP atmospheric forcing. The model is able to reproduce the observed seasonal variability very well. The forcing mechanisms of the seasonal variability related to seasonal surface wind stress and buoyancy flux, and water mass transformation processes associated with the seasonal overturning circulation are analyzed and presented.

Bis[4-(4-pyridyl)pyridinium] (4-carboxy­pyridine-2,6-dicarboxyl­ato-κ3 O 2,N,O 6)(pyridine-2,4,6-tricarboxyl­ato-κ3 O 2,N,O 6)ferrate(III) trihydrate

PubMed Central

Zhao, Li; Dong, You-Ren; Xie, Hong-Zhen

2009-01-01

In the title salt, (C10H9N2)2[Fe(C8H2NO6)(C8H3NO6)]·3H2O, the FeIII atom is O,N,O′-chelated by dianionic and trianionic ligands in a slightly distorted octa­hedral coordination geometry. The cations and ferrate anions are linked into a layered structure; the layers are connected through the uncoordinated water mol­ecules into a hydrogen-bonded three-dimensional supra­molecular structure. One of the uncoordinated water molecules is disordered around an inversion centre and was refined with half-occupancy for each position. PMID:21582387

Variability of upper ocean thermohaline structure during a MJO event from DYNAMO aircraft observations

NASA Astrophysics Data System (ADS)

Alappattu, Denny P.; Wang, Qing; Kalogiros, John; Guy, Nick; Jorgensen, David P.

2017-02-01

This paper reports upper ocean thermohaline structure and variability observed during the life cycle of an intense Madden Julian Oscillation (MJO) event occurred in the southern tropical Indian Ocean (14°S-Eq, 70°E-81°E). Water column measurements for this study were collected using airborne expendable probes deployed from NOAA's WP-3D Orion aircraft operated as a part of Dynamics of MJO field experiment conducted during November-December 2011. Purpose of the study is twofold; (1) to provide a statistical analysis of the upper ocean properties observed during different phases of MJO and, (2) to investigate how the upper ocean thermohaline structure evolved in the study region in response to the MJO induced perturbation. During the active phase of MJO, mixed layer depth (MLD) had a characteristic bimodal distribution. Primary and secondary modes were at ˜34 m and ˜65 m, respectively. Spatial heterogeneity of the upper ocean response to the MJO forcing was the plausible reason for bimodal distribution. Thermocline and isothermal layer depth deepened, respectively, by 13 and 19 m from the suppressed through the restoring phase of MJO. Thicker (>30 m) barrier layers were found to occur more frequently in the active phase of MJO, associated with convective rainfalls. Additionally, the water mass analysis indicated that, in the active phase of this MJO event the subsurface was dominated by Indonesian throughflow, nonetheless intrusion of Arabian Sea high saline water was also noted near the equator.

Two-phase convection in the high-pressure ice layer of the large icy moons: geodynamical implications

NASA Astrophysics Data System (ADS)

Kalousova, K.; Sotin, C.; Tobie, G.; Choblet, G.; Grasset, O.

2015-12-01

The H2O layers of large icy satellites such as Ganymede, Callisto, or Titan probably include a liquid water ocean sandwiched between the deep high-pressure ice layer and the outer ice I shell [1]. It has been recently suggested that the high-pressure ice layer could be decoupled from the silicate core by a salty liquid water layer [2]. However, it is not clear whether accumulation of liquids at the bottom of the high-pressure layer is possible due to positive buoyancy of water with respect to high-pressure ice. Numerical simulation of this two-phase (i.e. ice and water) problem is challenging, which explains why very few studies have self-consistently handled the presence and transport of liquids within the solid ice [e.g. 3]. While using a simplified description of water production and transport, it was recently showed in [4] that (i) a significant fraction of the high-pressure layer reaches the melting point and (ii) the melt generation and its extraction to the overlying ocean significantly influence the global thermal evolution and interior structure of the large icy moons.Here, we treat the high-pressure ice layer as a compressible mixture of solid ice and liquid water [5]. Several aspects are investigated: (i) the effect of the water formation on the vigor of solid-state convection and its influence on the amount of heat that is transferred from the silicate mantle to the ocean; (ii) the fate of liquids within the upper thermal boundary layer - whether they freeze or reach the ocean; and (iii) the effect of salts and volatile compounds (potentially released from the rocky core) on the melting/freezing processes. Investigation of these aspects will allow us to address the thermo-chemical evolution of the internal ocean which is crucial to evaluate the astrobiological potential of large icy moons. This work has been performed at the Jet Propulsion Laboratory, California Institute of Technology, under contract to NASA. [1] Hussmann et al. (2007), Treatise of Geophysics, 10.15, 509-539. [2] Vance et al. (2014), Planet. Space Sci., 96, 62-70. [3] Kalousova et al. (2014), J. Geophys. Res. Planets, 119(3), 532-549. [4] Tobie et al. (2014), AGU, P43C-3999. [5] Soucek et al. (2014), Geophys. Astro. Fluid, 108(6), 639-666.

A lichen protected by a super-hydrophobic and breathable structure.

PubMed

Shirtcliffe, Neil J; Brian Pyatt, F; Newton, Michael I; McHale, Glen

2006-11-01

A species of lichen, Lecanora conizaeoides, is shown to be super-hydrophobic. It uses a combination of hydrophobic compounds and multi-layered roughness to shed water effectively. This is combined with gas channels to produce a biological analogue of a waterproof, breathable garment. The particular lichen grows mostly during wet seasons and is unusually resistant to acid rain [Hauck, M., 2003. The Bryologist 106(2), 257-269; Honegger, R., 1998. Lichenologist 30(3),193-212]. The waterproof, breathable surface allows this lichen to photosynthesise when other species are covered with a layer of water. In addition, rainwater runs off the surface of the organism, reducing its intake of water from above and probably contributing to its resistance to acid rain.

Volatility of Common Protective Oxides in High-Temperature Water Vapor: Current Understanding and Unanswered Questions

NASA Technical Reports Server (NTRS)

Opila, Elizabeth J.

2004-01-01

Many structural materials rely on the formation of chromia, silica or alumina as a protective layer when exposed in high temperature oxidizing environments. The presence of these oxide layers provides a protective diffusion barrier which slows down further oxidation. In atmospheres containing water vapor, however, reactions to form volatile hydroxide species occur which remove the surface oxide, thus, lowering the protective capability of the oxide scale. This paper summarizes the current understanding of volatility of chromia, silica and alumina in water vapor containing combustion environments. In addition unanswered questions in each system are discussed. Th current paper represents an update on the considerable information learned in the past five years for these systems.

UV Grafting Modification of Polyethylene Separator for Liion Battery

NASA Astrophysics Data System (ADS)

Lv, Xiaoyuan; Li, Hua; Zhang, Zhiqiang; Chang, Hiunam; Jiang, Li; Liu, Hezhou

Polyethylene (PE) separator was modified by UV grafting methyl acrylate (MA) and nano-SiO2 composite layer. The structure of functional group and morphology of the separator were analyzed by Fourier transform infrared spectrum (FT-IR) and scanning electron microscope (SEM). The wetting behavior and the heat resistance of the separator were also investigated by contact angle test and thermal shrinkage test respectively. The results show that MA/nano-SiO2 composite layer is successfully grafted onto the PE separator, and the addition of the DI water and butanol can make the nano-SiO2 dispersed better and lead to a microporous structure of the grafting layer. The grafted separator has a better wettability and heat resistance than the pristine one.

Can Degradation of Adhesive Interfaces Due to Water Storage Affect Stress Distributions? A Finite-Element Stress Analysis Study.

PubMed

Belli, Sema; Eraslan, Oğuz; Eskitaşcıoğlu, Gürcan

The aim of this finite-element stress analysis (FEA) was to determine the effect of degradation due to water storage on stress distributions in root-filled premolar models restored with composite using either a self-etch (SE) or an etch-and-rinse (E&R) adhesive. Four premolar FEA models including root filling, MOD cavity, and composite restorations were created. The cavities were assumed to be treated by SE or E&R adhesives and stored in water for 18 months. The elastic properties of the adhesive-dentin interface after 24-h and 18-month water storage were obtained from the literature and applied to the FEA models. A 300-N load was applied on the functional cusps of the models. The SolidWorks/Cosmosworks structural analysis program was used and the results were presented considering the von Mises stresses. Stresses in the cervical region increased over time on the load-application side of the main tooth models (SE: 84.11 MPa to 87.51 MPa; E&R: 100.24 MPa to 120.8 MPa). When the adhesive interfaces (hybrid layer, adhesive layer) and dentin were evaluated separately, the stresses near the root canal orifices increased over time in both models; however, this change was more noticeable in the E&R models. Stresses at the cavity corners decreased in the E&R model (within the adhesive layer), while SE models showed the opposite (within the hybrid layer). Change in the elastic modulus of the adhesive layer, hybrid layer, and dentin due to water storage has an effect on stresses in root-filled premolar models. The location and the level of the stresses differed depending on the adhesive used.

Valles Marineris as a Cryokarstic Structure Formed by a Giant Dyke System: Support From New Analogue Experiments

NASA Astrophysics Data System (ADS)

Ozeren, M. S.; Sengor, A. M. C.; Acar, D.; Ülgen, S. C.; Onsel, I. E.

2014-12-01

Valles Marineris is the most significant near-linear depression on Mars. It is some 4000 km long, up to about 200 km wide and some 7 km deep. Although its margins look parallel at first sight, the entire structure has a long spindle shape with significant enlargement in its middle (Melas Chasma) caused by cuspate slope retreat mechanisms. Farther to its north is Hebes Chasma which is an entirely closed depression with a more pronounced spindle shape. Tithonium Chasma is a parallel, but much narrower depression to its northeast. All these chasmae have axes parallel with one another and such structures occur nowhere else on Mars. A scabland surface exists to the east of the Valles Marineris and the causative water mass seems to have issued from it. The great resemblance of these chasmae on mars to poljes in the karstic regions on earth have led us to assume that they owed their existence to dissolution of rock layers underlying them. We assumed that the dissolving layer consisted of water ice forming substantial layers, in fact entirely frozen seas of several km depth. We have simulated this geometry by using bentonite and flour layers (in different experiments) overlying layers of ice in which a resistant coil was used to simulate a dyke. We used different thicknesses of bentonite and flour overlying ice layers again of various thicknesses. The flour seems to simulate the Martian crust better because on Mars, g is only about 3/8ths of its value on Earth, so (for equal crustal density) the depth to which the cohesion term C remains important in the Mohr-Coulomb shear failure criterion is about 8/3 times greater. As examples we show two of those experiments in which both the rock analogue and ice layers were of 1.5 cm. thick. Perfect analogues of the Valles Marineris formed above the dyke analogue thermal source complete with the near-linear structure, overall flat spindle shape, cuspate margins, a central ridge, parallel side faults, parallel depressions resembling the Tithonium Chasma. When water was allowed to drain from the beginning, closed depressions formed that have an amazing resemblance to Hebes chasma. We postulate that the entire system of chasmae here discussed formed atop a major dyke swarm some 4000 km length, not dissimilar to the 3500 km long Mesoproterozoic (Ectasian) dyke swarm disrupting the Canadian Shield.

Influence of smectite suspension structure on sheet orientation in dry sediments: XRD and AFM applications.

PubMed

Zbik, Marek S; Frost, Ray L

2010-06-15

The structure-building phenomena within clay aggregates are governed by forces acting between clay particles. Measurements of such forces are important to understand in order to manipulate the aggregate structure for applications such as dewatering of mineral processing tailings. A parallel particle orientation is required when conducting XRD investigation on the oriented samples and conduct force measurements acting between basal planes of clay mineral platelets using atomic force microscopy (AFM). To investigate how smectite clay platelets were oriented on silicon wafer substrate when dried from suspension range of methods like SEM, XRD and AFM were employed. From these investigations, we conclude that high clay concentrations and larger particle diameters (up to 5 microm) in suspension result in random orientation of platelets in the substrate. The best possible laminar orientation in the clay dry film, represented in the XRD 001/020 intensity ratio of 47 was obtained by drying thin layers from 0.02 wt.% clay suspensions of the natural pH. Conducted AFM investigations show that smectite studied in water based electrolytes show very long-range repulsive forces lower in strength than electrostatic forces from double-layer repulsion. It was suggested that these forces may have structural nature. Smectite surface layers rehydrate in water environment forms surface gel with spongy and cellular texture which cushion approaching AFM probe. This structural effect can be measured in distances larger than 1000 nm from substrate surface and when probe penetrate this gel layer, structural linkages are forming between substrate and clay covered probe. These linkages prevent subsequently smooth detachments of AFM probe on way back when retrieval. This effect of tearing new formed structure apart involves larger adhesion-like forces measured in retrieval. It is also suggested that these effect may be enhanced by the nano-clay particles interaction. 2010 Elsevier Inc. All rights reserved.

Periodic density functional theory calculations of bulk and the (010) surface of goethite

PubMed Central

Kubicki, James D; Paul, Kristian W; Sparks, Donald L

2008-01-01

Background Goethite is a common and reactive mineral in the environment. The transport of contaminants and anaerobic respiration of microbes are significantly affected by adsorption and reduction reactions involving goethite. An understanding of the mineral-water interface of goethite is critical for determining the molecular-scale mechanisms of adsorption and reduction reactions. In this study, periodic density functional theory (DFT) calculations were performed on the mineral goethite and its (010) surface, using the Vienna Ab Initio Simulation Package (VASP). Results Calculations of the bulk mineral structure accurately reproduced the observed crystal structure and vibrational frequencies, suggesting that this computational methodology was suitable for modeling the goethite-water interface. Energy-minimized structures of bare, hydrated (one H2O layer) and solvated (three H2O layers) (010) surfaces were calculated for 1 × 1 and 3 × 3 unit cell slabs. A good correlation between the calculated and observed vibrational frequencies was found for the 1 × 1 solvated surface. However, differences between the 1 × 1 and 3 × 3 slab calculations indicated that larger models may be necessary to simulate the relaxation of water at the interface. Comparison of two hydrated surfaces with molecularly and dissociatively adsorbed H2O showed a significantly lower potential energy for the former. Conclusion Surface Fe-O and (Fe)O-H bond lengths are reported that may be useful in surface complexation models (SCM) of the goethite (010) surface. These bond lengths were found to change significantly as a function of solvation (i.e., addition of two extra H2O layers above the surface), indicating that this parameter should be carefully considered in future SCM studies of metal oxide-water interfaces. PMID:18477389

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.

Simulation Computation of 430 Ferritic Stainless Steel Solidification

NASA Astrophysics Data System (ADS)

Pang, Ruipeng; Li, Changrong; Wang, Fuming; Hu, Lifu

The solidification structure of 430 ferritic stainless steel has been calculated in the solidification process by using 3D-CAFE model under the condition of water cooling. The calculated results consistent with those obtained from experiment. Under watercooling condition, the solidification structure consists of chilled layer, columnar grain zone, transition zone and equiaxed grain zone.

Bottom-water observations in the Vema fracture zone

NASA Astrophysics Data System (ADS)

Eittreim, Stephen L.; Biscaye, Pierre E.; Jacobs, Stanley S.

1983-03-01

The Vema fracture zone trough, at 11°N between 41° and 45°E, is open to the west at the 5000-m level but is silled at the 4650-m level on the east where it intersects the axis of the Mid-Atlantic Ridge. The trough is filled with Antarctic Bottom Water (AABW) with a potential temperature of 1.32°C and salinity of 34.82 ppt. The bottom water is thermally well mixed in a nearly homogeneous layer about 700 m thick. The great thickness of this bottom layer, as compared with the bottom-water structure of the western Atlantic basin, may result from enhanced mixing induced by topographic constriction at the west end of the fracture zone trough. A benthic thermocline, with potential temperature gradients of about 1.2 mdeg m-1, is associated with an abrupt increase in turbidity with depth at about 1200 m above bottom. A transitional layer of more moderate temperature gradients, about 0.4 mdeg m-1, lies between the benthic thermocline above and the AABW below. The AABW layer whose depth-averaged suspended paniculate concentrations range from 8 to 19 μg L-1, is consistently higher in turbidity than the overlying waters. At the eastern end of the trough, 140 m below sill depth, very low northeastward current velocities, with maximums of 3 cm s-1, were recorded for an 11-day period.

Protein-lipid interactions at the air/water interface.

PubMed

Lad, Mitaben D; Birembaut, Fabrice; Frazier, Richard A; Green, Rebecca J

2005-10-07

Surface pressure measurements and external reflection FTIR spectroscopy have been used to probe protein-lipid interactions at the air/water interface. Spread monomolecular layers of stearic acid and phosphocholine were prepared and held at different compressed phase states prior to the introduction of protein to the buffered subphase. Contrasting interfacial behaviour of the proteins, albumin and lysozyme, was observed and revealed the role of both electrostatic and hydrophobic interactions in protein adsorption. The rate of adsorption of lysozyme to the air/water interface increased dramatically in the presence of stearic acid, due to strong electrostatic interactions between the negatively charged stearic acid head group and lysozyme, whose net charge at pH 7 is positive. Introduction of albumin to the subphase resulted in solubilisation of the stearic acid via the formation of an albumin-stearic acid complex and subsequent adsorption of albumin. This observation held for both human and bovine serum albumin. Protein adsorption to a PC layer held at low surface pressure revealed adsorption rates similar to adsorption to the bare air/water interface and suggested very little interaction between the protein and the lipid. For PC layers in their compressed phase state some adsorption of protein occurred after long adsorption times. Structural changes of both lysozyme and albumin were observed during adsorption, but these were dramatically reduced in the presence of a lipid layer compared to that of adsorption to the pure air/water interface.

Vertical stratification of bacterial communities driven by multiple environmental factors in the waters (0-5000 m) off the Galician coast (NW Iberian margin)

NASA Astrophysics Data System (ADS)

Dobal-Amador, Vladimir; Nieto-Cid, Mar; Guerrero-Feijoo, Elisa; Hernando-Morales, Victor; Teira, Eva; Varela-Rozados, Marta M.

2016-08-01

The processes mediated by microbial planktonic communities occur along the entire water column, yet the microbial activity and composition have been studied mainly in surface waters. This research examined the vertical variation in bacterial abundance, activity and community composition and structure from surface down to 5000 m depth following a longitudinal transect off the Galician coast (NW Iberian margin, from 43°N, 9°W to 43°N, 15°W). Community activity and composition changed with depth. The leucine incorporation rates decreased from the euphotic layer to the bathypelagic waters by three orders of magnitude, whereas prokaryotic abundance decreased only by one order of magnitude. The relative abundance of SAR11 and Alteromonas, determined by catalyzed reported deposition fluorescence in situ hybridization (CARD-FISH), decreased with depth. Meanwhile, the contribution of SAR 202 and SAR324 was significantly higher in the deeper layers (i.e. NEADW, North East Atlantic Deep Water and LDW, Lower Deep Water) than in the euphotic zone. Bacterial community structure, assessed by Automated Ribosomal Intergenic Spacer Analysis (ARISA), was depth-specific. A distance based linear model (DistLM) revealed that the variability found in bacterial community structure was mainly explained by temperature nitrate, phosphate, dissolved organic matter (DOM) fluorescence, prokaryotic abundance, leucine incorporation and to a lesser extent salinity, oxygen, CDOM absorbance and dissolved organic carbon concentration. Our results displayed a bacterial community structure shaped not only by depth-related physicochemical features but also by DOM quality, indicating that different prokaryotic taxa have the potential to metabolize particular DOM sources.

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

Nayak, Pradipta K.; Wang, Zhenwei; Anjum, D. H.

We report highly stable gate-bias stress performance of thin film transistors (TFTs) using zinc oxide (ZnO)/hafnium oxide (HfO{sub 2}) multilayer structure as the channel layer. Positive and negative gate-bias stress stability of the TFTs was measured at room temperature and at 60 °C. A tremendous improvement in gate-bias stress stability was obtained in case of the TFT with multiple layers of ZnO embedded between HfO{sub 2} layers compared to the TFT with a single layer of ZnO as the semiconductor. The ultra-thin HfO{sub 2} layers act as passivation layers, which prevent the adsorption of oxygen and water molecules in the ZnOmore » layer and hence significantly improve the gate-bias stress stability of ZnO TFTs.« less

Optimisation of multi-layer rotationally moulded foamed structures

NASA Astrophysics Data System (ADS)

Pritchard, A. J.; McCourt, M. P.; Kearns, M. P.; Martin, P. J.; Cunningham, E.

2018-05-01

Multi-layer skin-foam and skin-foam-skin sandwich constructions are of increasing interest in the rotational moulding process for two reasons. Firstly, multi-layer constructions can improve the thermal insulation properties of a part. Secondly, foamed polyethylene sandwiched between solid polyethylene skins can increase the mechanical properties of rotationally moulded structural components, in particular increasing flexural properties and impact strength (IS). The processing of multiple layers of polyethylene and polyethylene foam presents unique challenges such as the control of chemical blowing agent decomposition temperature, and the optimisation of cooling rates to prevent destruction of the foam core; therefore, precise temperature control is paramount to success. Long cooling cycle times are associated with the creation of multi-layer foam parts due to their insulative nature; consequently, often making the costs of production prohibitive. Devices such as Rotocooler®, a rapid internal mould water spray cooling system, have been shown to have the potential to significantly decrease cooling times in rotational moulding. It is essential to monitor and control such devices to minimise the warpage associated with the rapid cooling of a moulding from only one side. The work presented here demonstrates the use of threaded thermocouples to monitor the polymer melt in multi-layer sandwich constructions, in order to analyse the cooling cycle of multi-layer foamed structures. A series of polyethylene skin-foam test mouldings were produced, and the effect of cooling medium on foam characteristics, mechanical properties, and process cycle time were investigated. Cooling cycle time reductions of 45%, 26%, and 29% were found for increasing (1%, 2%, and 3%) chemical blowing agent (CBA) amount when using internal water cooling technology from ˜123°C compared with forced air cooling (FAC). Subsequently, a reduction of IS for the same skin-foam parts was found to be 1%, 4%, and 16% compared with FAC.

Detecting a liquid and solid H2O layer by geophysical methods

NASA Astrophysics Data System (ADS)

Yoshikawa, K.; Romanovsky, V.; Tsapin, A.; Brown, J.

2002-12-01

The objective is to detect the hydrological and cryological structure of the cold continuous permafrost subsurface using geophysical methods. We believe that a lot of water potentially exists as solid and liquid phases underground on Mars. It is likely that the liquid fluid would be high in saline concentration (brine). The ground freezing process involves many hydrological processes including enrichment of the brine layer. The brine layer is an important environment for ancient and/or current life to exist on terrestrial permafrost regions. The existence of a Martian brine layer would increase the possibility of the existence of life, as on Earth. In situ electric resistivity measurement will be the most efficient method to determine brine layer as well as massive H2O ice in the permafrost. However, the wiring configuration is unlikely to operate on the remote planetary surface. Satellite-born Radar and/or EM methods will be the most accessible methods for detecting the hydrological and cryological structure. We are testing several geophysical methods at the brine layer site in Barrow and massive pingo ice site in Fairbanks, Alaska. The radar system is affected by the dielectric properties of subsurface materials, which allows for evidence of liquid phase in the frozen ground. The dielectric constant varies greatly between liquid water and frozen ground. The depth of the terrestrial (and probably Martian) brine layer is frequently located deeper than the maximum detecting depth of the impulse type of the ground penetrating radar system. Once we develop a radar system with a deeper penetrating capability (Lower frequency), the dispersion of the ground ice will be the key function for interpretation of these signals. We will improve and use radar signals to understand the hydrological and cryological structure in the permafrost. The core samples and borehole temperature data validate these radar signals.

Three-dimensional hydration layer mapping on the (10.4) surface of calcite using amplitude modulation atomic force microscopy.

PubMed

Marutschke, Christoph; Walters, Deron; Walters, Deron; Hermes, Ilka; Bechstein, Ralf; Kühnle, Angelika

2014-08-22

Calcite, the most stable modification of calcium carbonate, is a major mineral in nature. It is, therefore, highly relevant in a broad range of fields such as biomineralization, sea water desalination and oil production. Knowledge of the surface structure and reactivity of the most stable cleavage plane, calcite (10.4), is pivotal for understanding the role of calcite in these diverse areas. Given the fact that most biological processes and technical applications take place in an aqueous environment, perhaps the most basic - yet decisive - question addresses the interaction of water molecules with the calcite (10.4) surface. In this work, amplitude modulation atomic force microscopy is used for three-dimensional (3D) mapping of the surface structure and the hydration layers above the surface. An easy-to-use scanning protocol is implemented for collecting reliable 3D data. We carefully discuss a comprehensible criterion for identifying the solid-liquid interface within our data. In our data three hydration layers form a characteristic pattern that is commensurate with the underlying calcite surface.

Reactive Fe(II) layers in deep-sea sediments

NASA Astrophysics Data System (ADS)

König, Iris; Haeckel, Matthias; Drodt, Matthias; Suess, Erwin; Trautwein, Alfred X.

1999-05-01

The percentage of the structural Fe(II) in clay minerals that is readily oxidized to Fe(III) upon contact with atmospheric oxygen was determined across the downcore tan-green color change in Peru Basin sediments. This latent fraction of reactive Fe(II) was only found in the green strata, where it proved to be large enough to constitute a deep reaction layer with respect to the pore water O 2 and NO 3-. Large variations were detected in the proportion of the reactive Fe(II) concentration to the organic matter content along core profiles. Hence, the commonly observed tan-green color change in marine sediments marks the top of a reactive Fe(II) layer, which may represent the major barrier to the movement of oxidation fronts in pelagic subsurface sediments. This is also demonstrated by numerical model simulations. The findings imply that geochemical barriers to pore water oxidation fronts form diagenetically in the sea floor wherever the stage of iron reduction is reached, provided that the sediments contain a significant amount of structural iron in clay minerals.

Mn{sub 0.95}I{sub 0.02}[PO{sub 3}(OH)] · 2H{sub 2}O phosphate–iodate, an inorganic analogue of phosphonates

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

Belokoneva, E. L., E-mail: elbel@geol.msu.ru; Dimitrova, O. V.; Volkov, A. S.

2015-09-15

The new Mn{sub 0.95}I{sub 0.02}[PO{sub 3}(OH)] · 2H{sub 2}O phosphate–iodate (space group Pnam = Pnma, D{sub 2h}{sup 16}) is obtained under hydrothermal conditions. The crystal structure is determined without preliminary knowledge of the chemical formula. The structure consists of layers of MnO{sub 6} octahedra connected with PO{sub 4} tetrahedra. Water molecules are located between the layers. [IO3]{sup –} groups having a typical umbrella-like coordination are statistically implanted in layers of MnO{sub 6} octahedra at a distance of 1.2 Å from Mn atoms. Their content in the crystal is minor. The structures of the phosphate–iodate coincides with the structures of phosphonatesmore » with consideration for the replacement of one (OH) vertex of the PO{sub 4} tetrahedron by the organic methyl radical CH{sub 3}. In the structures of phosphonates and earlier studied phosphates, identical layers are distinguished and the cause of the existence of two MDO varieties is established based on the analysis within the OD theory. Possible hybrid structures derived from the prototypes under consideration are predicted.« less

The nepheloid bottom layer and water masses at the shelf break of the western Ross Sea

NASA Astrophysics Data System (ADS)

Capello, Marco; Budillon, Giorgio; Cutroneo, Laura; Tucci, Sergio

2009-06-01

In the austral summers of 2000/2001 and 2002/2003 the Italian CLIMA Project carried out two oceanographic cruises along the northwestern margin of the Ross Sea, where the Antarctic Bottom Water forms. Here there is an interaction between the water masses on the sea floor of the outer shelf and slope with a consequent evolution of benthic nepheloid layers and an increase in total particulate matter. We observed three different situations: (a) the presence of triads (bottom structures characterized by a concomitant jump in turbidity, temperature, and salinity data) and high re-suspension phenomena related to the presence of the Circumpolar Deep Water and its mixing with cold, salty shelf waters associated with gravity currents; (b) the absence of triads with high re-suspension, implying that when the gravity currents are no longer active the benthic nepheloid layer may persist until the suspended particles settle to the sea floor, suggesting that the turbidity data can be used to study recent gravity current events; and (c) the absence of turbidity and sediment re-suspension phenomena supports the theory that a steady situation had been re-established and the current interaction no longer occurred or had finished sometime before.

Exposed water ice on the nucleus of comet 67P/Churyumov-Gerasimenko.

PubMed

Filacchione, G; De Sanctis, M C; Capaccioni, F; Raponi, A; Tosi, F; Ciarniello, M; Cerroni, P; Piccioni, G; Capria, M T; Palomba, E; Bellucci, G; Erard, S; Bockelee-Morvan, D; Leyrat, C; Arnold, G; Barucci, M A; Fulchignoni, M; Schmitt, B; Quirico, E; Jaumann, R; Stephan, K; Longobardo, A; Mennella, V; Migliorini, A; Ammannito, E; Benkhoff, J; Bibring, J P; Blanco, A; Blecka, M I; Carlson, R; Carsenty, U; Colangeli, L; Combes, M; Combi, M; Crovisier, J; Drossart, P; Encrenaz, T; Federico, C; Fink, U; Fonti, S; Ip, W H; Irwin, P; Kuehrt, E; Langevin, Y; Magni, G; McCord, T; Moroz, L; Mottola, S; Orofino, V; Schade, U; Taylor, F; Tiphene, D; Tozzi, G P; Beck, P; Biver, N; Bonal, L; Combe, J-Ph; Despan, D; Flamini, E; Formisano, M; Fornasier, S; Frigeri, A; Grassi, D; Gudipati, M S; Kappel, D; Mancarella, F; Markus, K; Merlin, F; Orosei, R; Rinaldi, G; Cartacci, M; Cicchetti, A; Giuppi, S; Hello, Y; Henry, F; Jacquinod, S; Reess, J M; Noschese, R; Politi, R; Peter, G

2016-01-21

Although water vapour is the main species observed in the coma of comet 67P/Churyumov-Gerasimenko and water is the major constituent of cometary nuclei, limited evidence for exposed water-ice regions on the surface of the nucleus has been found so far. The absence of large regions of exposed water ice seems a common finding on the surfaces of many of the comets observed so far. The nucleus of 67P/Churyumov-Gerasimenko appears to be fairly uniformly coated with dark, dehydrated, refractory and organic-rich material. Here we report the identification at infrared wavelengths of water ice on two debris falls in the Imhotep region of the nucleus. The ice has been exposed on the walls of elevated structures and at the base of the walls. A quantitative derivation of the abundance of ice in these regions indicates the presence of millimetre-sized pure water-ice grains, considerably larger than in all previous observations. Although micrometre-sized water-ice grains are the usual result of vapour recondensation in ice-free layers, the occurrence of millimetre-sized grains of pure ice as observed in the Imhotep debris falls is best explained by grain growth by vapour diffusion in ice-rich layers, or by sintering. As a consequence of these processes, the nucleus can develop an extended and complex coating in which the outer dehydrated crust is superimposed on layers enriched in water ice. The stratigraphy observed on 67P/Churyumov-Gerasimenko is therefore the result of evolutionary processes affecting the uppermost metres of the nucleus and does not necessarily require a global layering to have occurred at the time of the comet's formation.

High flux filtration medium based on nanofibrous substrate with hydrophilic nanocomposite coating.

PubMed

Wang, Xuefen; Chen, Xuming; Yoon, Kyunghwan; Fang, Dufei; Hsiao, Benjamin S; Chu, Benjamin

2005-10-01

A novel high flux filtration medium, consisting of a three-tier composite structure, i.e., a nonporous hydrophilic nanocomposite coating top layer, an electrospun nanofibrous substrate midlayer, and a conventional nonwoven microfibrous support, was demonstrated for oil/water emulsion separations for the first time. The nanofibrous substrate was prepared by electrospinning of poly(vinyl alcohol) (PVA) followed by chemical cross-linking with glutaraldehyde (GA) in acetone. The resulting cross-linked PVA substrates showed excellent water resistance and good mechanical properties. The top coating was based on a nanocomposite layer containing hydrophilic polyether-b-polyamide copolymer or a cross-linked PVA hydrogel incorporated with surface-oxidized multiwalled carbon nanotubes (MWNTs). Scanning electron microscopy (SEM) examinations indicated that the nanocomposite layer was nonporous within the instrumental resolution and MWNTs were well dispersed in the polymer matrix. Oil/ water emulsion tests showed that this unique type of filtration media exhibited a high flux rate (up to 330 L/m2-h at the feed pressure of 100 psi) and an excellent total organic solute rejection rate (99.8%) without appreciable fouling. The increase in the concentration of surface-oxidized MWNT in the coating layer generally improves the flux rate, which can be attributed to the generation of more effective hydrophilic nanochannels for water passage in the composite membranes.

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

On Controlling the Hydrophobicity of Nanostructured Zinc-Oxide Layers Grown by Pulsed Electrodeposition

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

Klochko, N. P., E-mail: klochko-np@mail.ru; Klepikova, K. S.; Kopach, V. R.

The possibility of fabricating highly hydrophobic nanostructured zinc-oxide layers by the inexpensive method of pulsed electrodeposition from aqueous solutions without water-repellent coatings, adapted for large-scale production, is shown. The conditions of the deposition of highly hydrophobic nanostructured zinc-oxide layers exhibiting the “rose-petal” effect with specific morphology, optical properties, crystal structure and texture are determined. The grown ZnO nanostructures are promising for micro- and nanoelectronics as an adaptive material able to reversibly transform to the hydrophilic state upon exposure to ultraviolet radiation.

Nano-confined water in the interlayers of hydrocalumite: Reorientational dynamics probed by neutron spectroscopy and molecular dynamics computer simulations

NASA Astrophysics Data System (ADS)

Kalinichev, A. G.; Faraone, A.; Udovic, T.; Kolesnikov, A. I.; de Souza, N. R.; Reinholdt, M. X.; Kirkpatrick, R.

2008-12-01

Layered double hydroxides (LDHs, anionic clays) represent excellent model systems for detailed molecular- level studies of the structure, dynamics, and energetics of nano-confined water in mineral interlayers and nano-pores, because LDH interlayers can have a well-defined structures and contain H2O molecules and a wide variety of anions in structurally well-defined positions and coordinations. [Ca2Al(OH)6]Cl·2H2O, also known as hydrocalumite or Friedel's salt, has a well- ordered Ca,Al distribution in the hydroxide layer and a very high degree of H2O,Cl ordering in the interlayer. It is also one of the only LDH phase for which a single crystal structure refinement is available. Thus, it is currently the best model compound for understanding the structure and dynamical behavior of interlayer and surface species in other, less-ordered, LDHs. We investigated the structural and dynamic behavior of water in the interlayers of hydrocalumite using inelastic (INS) and quasielastic (QENS) neutron scattering and molecular dynamics computer simulations. The comperehensive neutron scattering studies were performed for one fully hydrated and one dehydrated sample of hydrocalumite using several complementary instruments (HFBS, DCS and FANS at NCNR; HRMECS and QENS at IPNS) at temperatures above and below the previously discovered order-disorder interlayer phase transition. Together the experimental and molecular modeling results capture the important details of the dynamics of nano-confined water and the effects of the orientational ordering of H2O molecules above and below the phase transition. They provide otherwise unobtainable experimental information about the transformation of H2O librational and diffusional modes across the order-disorder phase transition and significantly add to our current understanding of the structure and dynamics of water in LDH phases based on the earlier NMR, IR, X-ray, and calorimetric measurements. The approach can now be extended to probe the dynamics of nano-confined and interfacial water in more disordered phases (LDH, clays, cement, etc.), for which much less initial structural information is available.

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.

Seasonal Variation of Barrier Layer in the Southern Ocean

NASA Astrophysics Data System (ADS)

Pan, Li; Zhong, Yisen; Liu, Hailong; Zhou, Lei; Zhang, Zhaoru; Zhou, Meng

2018-03-01

The seasonal variability of barrier layer (BL) and its formation mechanism in the Southern Ocean are investigated using the most recent Argo data. The results reveal that the BL is a persistent feature in the Southern Ocean with a strong seasonal cycle. The thickest BL appears in winter with the maximum amplitude exceeding 250 m while it dramatically decreases to less than 50 m in summer. The spatial distribution of BL is zonally oriented in the Pacific and Indian Ocean sectors, which is in agreement with that of the mixed layer depth (MLD) and the isothermal layer depth (ILD). Two areas with the most prominent BL are identified. One is located south of Australia and the other in the southeastern Pacific. The BL formation in both areas is generally attributed to a shallow mixed layer controlled by surface freshwater intrusion and a deep isothermal layer modulated by seasonal vertical convection. In the former region, the cold and fresh Antarctic Surface Water (ASW) is transported northward across the Subantarctic Front (SAF) by the Ekman effect and overlies the warm Subantarctic Mode Water (SAMW). The resulting inverse temperature structure facilitates the development of thick BLs. In the latter region, the BL emerges in the ventilation area where the shallow Surface Salinity Minimum Water (SSMW) coming from north leans against the deep vertical isotherms. In summer, positive surface heat flux into the ocean overwhelms other thermodynamic effects in the mixed layer heat budget. The MLD and ILD coincide and thus the BL is destroyed.

Determination of Surface Potential and Electrical Double-Layer Structure at the Aqueous Electrolyte-Nanoparticle Interface

NASA Astrophysics Data System (ADS)

Brown, Matthew A.; Abbas, Zareen; Kleibert, Armin; Green, Richard G.; Goel, Alok; May, Sylvio; Squires, Todd M.

2016-01-01

The structure of the electrical double layer has been debated for well over a century, since it mediates colloidal interactions, regulates surface structure, controls reactivity, sets capacitance, and represents the central element of electrochemical supercapacitors. The surface potential of such surfaces generally exceeds the electrokinetic potential, often substantially. Traditionally, a Stern layer of nonspecifically adsorbed ions has been invoked to rationalize the difference between these two potentials; however, the inability to directly measure the surface potential of dispersed systems has rendered quantitative measurements of the Stern layer potential, and other quantities associated with the outer Helmholtz plane, impossible. Here, we use x-ray photoelectron spectroscopy from a liquid microjet to measure the absolute surface potentials of silica nanoparticles dispersed in aqueous electrolytes. We quantitatively determine the impact of specific cations (Li+ , Na+ , K+ , and Cs+ ) in chloride electrolytes on the surface potential, the location of the shear plane, and the capacitance of the Stern layer. We find that the magnitude of the surface potential increases linearly with the hydrated-cation radius. Interpreting our data using the simplest assumptions and most straightforward understanding of Gouy-Chapman-Stern theory reveals a Stern layer whose thickness corresponds to a single layer of water molecules hydrating the silica surface, plus the radius of the hydrated cation. These results subject electrical double-layer theories to direct and falsifiable tests to reveal a physically intuitive and quantitatively verified picture of the Stern layer that is consistent across multiple electrolytes and solution conditions.

Swelling equilibrium of dentin adhesive polymers formed on the water-adhesive phase boundary: Experiments and micromechanical model

PubMed Central

Misra, Anil; Parthasarathy, Ranganathan; Ye, Qiang; Singh, Viraj; Spencer, Paulette

2013-01-01

During their application to the wet, oral environment, dentin adhesives can experience phase separation and composition change which can compromise the quality of the hybrid layer formed at the dentin-adhesive interface. The chemical composition of polymer phases formed in the hybrid layer can be represented using a ternary water-adhesive phase diagram. In this paper, these polymer phases have been characterized using a suite of mechanical tests and swelling experiments. The experimental results were evaluated using granular micromechanics based model that incorporates poro-mechanical effects and polymer-solvent thermodynamics. The variation of the model parameters and model-predicted polymer properties has been studied as a function of composition along the phase boundary. The resulting structure-property correlations provide insight into interactions occurring at the molecular level in the saturated polymer system. These correlations can be used for modeling the mechanical behavior of hybrid layer, and are expected to aid in the design and improvement of water-compatible dentin adhesive polymers. PMID:24076070

Experimental and theoretical evidence for bilayer-by-bilayer surface melting of crystalline ice

PubMed Central

Sánchez, M. Alejandra; Kling, Tanja; Ishiyama, Tatsuya; van Zadel, Marc-Jan; Mezger, Markus; Jochum, Mara N.; Cyran, Jenée D.; Smit, Wilbert J.; Bakker, Huib J.; Shultz, Mary Jane; Morita, Akihiro; Donadio, Davide; Nagata, Yuki; Bonn, Mischa; Backus, Ellen H. G.

2017-01-01

On the surface of water ice, a quasi-liquid layer (QLL) has been extensively reported at temperatures below its bulk melting point at 273 K. Approaching the bulk melting temperature from below, the thickness of the QLL is known to increase. To elucidate the precise temperature variation of the QLL, and its nature, we investigate the surface melting of hexagonal ice by combining noncontact, surface-specific vibrational sum frequency generation (SFG) spectroscopy and spectra calculated from molecular dynamics simulations. Using SFG, we probe the outermost water layers of distinct single crystalline ice faces at different temperatures. For the basal face, a stepwise, sudden weakening of the hydrogen-bonded structure of the outermost water layers occurs at 257 K. The spectral calculations from the molecular dynamics simulations reproduce the experimental findings; this allows us to interpret our experimental findings in terms of a stepwise change from one to two molten bilayers at the transition temperature. PMID:27956637

Molecular resolution friction microscopy of Cu phthalocyanine thin films on dolomite (104) in water

NASA Astrophysics Data System (ADS)

Nita, Paweł; Pimentel, Carlos; Luo, Feng; Milián-Medina, Begoña; Gierschner, Johannes; Pina, Carlos M.; Gnecco, Enrico

2014-06-01

The reliability of ultrathin organic layers as active components for molecular electronic devices depends ultimately on an accurate characterization of the layer morphology and ability to withstand mechanical stresses on the nanoscale. To this end, since the molecular layers need to be electrically decoupled using thick insulating substrates, the use of AFM becomes mandatory. Here, we show how friction force microscopy (FFM) in water allows us to identify the orientation of copper(ii)phthalocyanine (CuPc) molecules previously self-assembled on a dolomite (104) mineral surface in ultra-high vacuum. The molecular features observed in the friction images show that the CuPc molecules are stacked in parallel rows with no preferential orientation with respect to the dolomite lattice, while the stacking features resemble well the single CuPc crystal structure. This proves that the substrate induction is low and makes friction force microscopy in water a suitable alternative to more demanding dynamic AFM techniques in ultra-high vacuum.

Molecular resolution friction microscopy of Cu phthalocyanine thin films on dolomite (104) in water.

PubMed

Nita, Paweł; Pimentel, Carlos; Luo, Feng; Milián-Medina, Begoña; Gierschner, Johannes; Pina, Carlos M; Gnecco, Enrico

2014-07-21

The reliability of ultrathin organic layers as active components for molecular electronic devices depends ultimately on an accurate characterization of the layer morphology and ability to withstand mechanical stresses on the nanoscale. To this end, since the molecular layers need to be electrically decoupled using thick insulating substrates, the use of AFM becomes mandatory. Here, we show how friction force microscopy (FFM) in water allows us to identify the orientation of copper(ii)phthalocyanine (CuPc) molecules previously self-assembled on a dolomite (104) mineral surface in ultra-high vacuum. The molecular features observed in the friction images show that the CuPc molecules are stacked in parallel rows with no preferential orientation with respect to the dolomite lattice, while the stacking features resemble well the single CuPc crystal structure. This proves that the substrate induction is low and makes friction force microscopy in water a suitable alternative to more demanding dynamic AFM techniques in ultra-high vacuum.

Vertical stratification of microbial communities in the Red Sea revealed by 16S rDNA pyrosequencing.

PubMed

Qian, Pei-Yuan; Wang, Yong; Lee, On On; Lau, Stanley C K; Yang, Jiangke; Lafi, Feras F; Al-Suwailem, Abdulaziz; Wong, Tim Y H

2011-03-01

The ecosystems of the Red Sea are among the least-explored microbial habitats in the marine environment. In this study, we investigated the microbial communities in the water column overlying the Atlantis II Deep and Discovery Deep in the Red Sea. Taxonomic classification of pyrosequencing reads of the 16S rRNA gene amplicons showed vertical stratification of microbial diversity from the surface water to 1500 m below the surface. Significant differences in both bacterial and archaeal diversity were observed in the upper (20 [corrected] and 50 m) and deeper layers (200 and 1500 m). There were no obvious differences in community structure at the same depth for the two sampling stations. The bacterial community in the upper layer was dominated by Cyanobacteria whereas the deeper layer harbored a large proportion of Proteobacteria. Among Archaea, Euryarchaeota, especially Halobacteriales, were dominant in the upper layer but diminished drastically in the deeper layer where Desulfurococcales belonging to Crenarchaeota became the dominant group. The results of our study indicate that the microbial communities sampled in this study are different from those identified in water column in other parts of the world. The depth-wise compositional variation in the microbial communities is attributable to their adaptations to the various environments in the Red Sea.

Structural evolution of gypsum under high pressure: single-crystal X-ray experiments revisited

NASA Astrophysics Data System (ADS)

Li, Tsung-Lung; Lee, Pei-Lun

2018-05-01

The structures of gypsum at pressures up to approximately 4 GPa are studied with density functional theory (DFT) and thoroughly compared with single-crystal X-ray diffraction experiments reported in the literature [Comodi et al. in (Am Miner 93:1530-1537, 2008)]. It is found that the exchange-correlation density functional revPBE (revised Perdew-Burke-Ernzerhof) in conjunction with a nonlocal van der Waals (vdW) correction is capable of modeling the lattice constants, axial compressibility, and bulk modulus with good accuracy, suggesting that the inclusion of the vdW functional is crucially important for understanding the structure of hydrous minerals. To gain further physical insights, the geometric parameters associated with the constituting components of gypsum (water molecules, SO4 tetrahedra, and CaO8 polyhedra) are analyzed and compared with the experimental values. DFT simulations show that, under pressure, the polyhedral layers remain as nearly planar sheets of interconnecting SO4 tetrahedra and CaO8 polyhedra without further crinkling. DFT analysis on the layer compressibility along the major crystal axis reveals that, in contrast to experimental reports, the hydrous interlayer is less compressible than the polyhedral layer. Squeezed by the lateral pressure, the water molecules in the hydrous interlayer become better affixed along the major axis, making the interlayer harder to compress along this axis.

Colonization and community structure of root-associated microorganisms of Sabina vulgaris with soil depth in a semiarid desert ecosystem with shallow groundwater.

PubMed

Taniguchi, Takeshi; Usuki, Hiroyuki; Kikuchi, Junichi; Hirobe, Muneto; Miki, Naoko; Fukuda, Kenji; Zhang, Guosheng; Wang, Linhe; Yoshikawa, Ken; Yamanaka, Norikazu

2012-08-01

Arbuscular mycorrhizal fungi (AMF) have been observed in deep soil layers in arid lands. However, change in AMF community structure with soil depth and vertical distributions of the other root-associated microorganisms are unclear. Here, we examined colonization by AMF and dark septate fungi (DSF), as well as the community structure of AMF and endophytic fungi (EF) and endophytic bacteria (EB) in association with soil depth in a semiarid desert with shallow groundwater. Roots of Sabina vulgaris and soils were collected from surface to groundwater level at 20-cm intervals. Soil chemistry (water content, total N, and available P) and colonization of AMF and DSF were measured. Community structures of AMF, EF, and EB were examined by terminal restriction fragment length polymorphism analysis. AMF colonization decreased with soil depth, although it was mostly higher than 50%. Number of AMF phylotypes decreased with soil depth, but more than five phylotypes were observed at depths up to 100 cm. Number of AMF phylotypes had a significant and positive relationship with soil moisture level within 0-15% of soil water content. DSF colonization was high but limited to soil surface. Number of phylotypes of EF and EB were diverse even in deep soil layers, and the community composition was associated with the colonization and community composition of AMF. This study indicates that AMF species richness in roots decreases but is maintained in deep soil layers in semiarid regions, and change in AMF colonization and community structure associates with community structure of the other root-associated microorganisms.

The Sinking and Spreading of The Antarctic Deep Ice Shelf Water In The Ross Sea Studied By In Situ Observaions and Numerical Modeling

NASA Astrophysics Data System (ADS)

Rubino, A.; Budillon, G.; Pierini, S.; Spezie, G.

The sinking and spreading of the Deep Ice Shelf Water (DISW) in the Ross Sea are analyzed using in situ observations and the results of a nonlinear, reduced-gravity, frontal layered numerical "plume" model which is able to simulate the motion of a bottom-arrested current over realistic topography. The model is forced by prescribing the thickness of the DISW vein as well as its density structure at the southern model boundary. The ambient temperature and salinity are imposed using hydrographic data acquired by the Italian PNRA-CLIMA project. In the model water of the quiescent ambient ocean is allowed to entrain in the active deep layer due to a simple param- eterization of turbulent mixing. The importance of forcing the model with a realistic ambient density is demonstrated by carrying out a numerical simulation in which the bottom active layer is forced using an idealized ambient density. In a more realis- tic simulation the path and the density structure of the DISW vein flowing over the Challenger Basin are obtained and are found to be in good agreement with data. The evolution of the deep current beyond the continental shelf is also simulated. It provides useful information on the water flow and mixing in a region of the Ross Sea where the paucity of experimental data does not allow for a detailed description of the deep ocean dynamics.

Ab initio and classical molecular dynamics studies of the structural and dynamical behavior of water near a hydrophobic graphene sheet.

PubMed

Rana, Malay Kumar; Chandra, Amalendu

2013-05-28

The behavior of water near a graphene sheet is investigated by means of ab initio and classical molecular dynamics simulations. The wetting of the graphene sheet by ab initio water and the relation of such behavior to the strength of classical dispersion interaction between surface atoms and water are explored. The first principles simulations reveal a layered solvation structure around the graphene sheet with a significant water density in the interfacial region implying no drying or cavitation effect. It is found that the ab initio results of water density at interfaces can be reproduced reasonably well by classical simulations with a tuned dispersion potential between the surface and water molecules. Calculations of vibrational power spectrum from ab initio simulations reveal a shift of the intramolecular stretch modes to higher frequencies for interfacial water molecules when compared with those of the second solvation later or bulk-like water due to the presence of free OH modes near the graphene sheet. Also, a weakening of the water-water hydrogen bonds in the vicinity of the graphene surface is found in our ab initio simulations as reflected in the shift of intermolecular vibrational modes to lower frequencies for interfacial water molecules. The first principles calculations also reveal that the residence and orientational dynamics of interfacial water are somewhat slower than those of the second layer or bulk-like molecules. However, the lateral diffusion and hydrogen bond relaxation of interfacial water molecules are found to occur at a somewhat faster rate than that of the bulk-like water molecules. The classical molecular dynamics simulations with tuned Lennard-Jones surface-water interaction are found to produce dynamical results that are qualitatively similar to those of ab initio molecular dynamics simulations.

Efficient gas barrier properties of multi-layer films based on poly(lactic acid) and fish gelatin.

PubMed

Hosseini, Seyed Fakhreddin; Javidi, Zahra; Rezaei, Masoud

2016-11-01

Multi-layer film structures of poly(lactic acid) (PLA) and fish gelatin (FG), prepared using the solvent casting technique, were studied in an effort to produce bio-based films with low oxygen (OP) and water vapor permeability (WVP). The scanning electron microscopy (SEM) images of triple-layer film showed that the outer PLA layers are being closely attached to the inner FG layer to make continuous film. The OP of multi-layer film (5.02cm 3 /m 2 daybar) decreased more than 8-fold compared with that of the PLA film, and the WVP of multi-layer film (0.125gmm/kPah m 2 ) also decreased 11-fold compared with that of the FG film. Lamination with PLA profoundly increased the water resistance of the bare gelatin film. Meanwhile, the tensile strength of the triple-layer film (25±2.13MPa) was greater than that of FG film (7.48±1.70MPa). At the same time, the resulting film maintains high optical clarity. Differential scanning calorimetry (DSC) analysis also revealed that the materials were compatible showing only one T g which decreased with FG deposition. This material exhibits an environmental-friendliness potential and a high versatility in food packaging. Copyright © 2016 Elsevier B.V. All rights reserved.

Crystallization, melting, and structure of water nanoparticles at atmospherically relevant temperatures.

PubMed

Johnston, Jessica C; Molinero, Valeria

2012-04-18

Water nanoparticles play an important role in atmospheric processes, yet their equilibrium and nonequilibrium liquid-ice phase transitions and the structures they form on freezing are not yet fully elucidated. Here we use molecular dynamics simulations with the mW water model to investigate the nonequilibrium freezing and equilibrium melting of water nanoparticles with radii R between 1 and 4.7 nm and the structure of the ice formed by crystallization at temperatures between 150 and 200 K. The ice crystallized in the particles is a hybrid form of ice I with stacked layers of the cubic and hexagonal ice polymorphs in a ratio approximately 2:1. The ratio of cubic ice to hexagonal ice is insensitive to the radius of the water particle and is comparable to that found in simulations of bulk water around the same temperature. Heating frozen particles that contain multiple crystallites leads to Ostwald ripening and annealing of the ice structures, accompanied by an increase in the amount of ice at the expense of the liquid water, before the particles finally melt from the hybrid ice I to liquid, without a transition to hexagonal ice. The melting temperatures T(m) of the nanoparticles are not affected by the ratio of cubic to hexagonal layers in the crystal. T(m) of the ice particles decreases from 255 to 170 K with the particle size and is well described by the Gibbs-Thomson equation, T(m)(R) = T(m)(bulk) - K(GT)/(R - d), with constant K(GT) = 82 ± 5 K·nm and a premelted liquid of width d = 0.26 ± 0.05 nm, about one monolayer. The freezing temperatures also decrease with the particles' radii. These results are important for understanding the composition, freezing, and melting properties of ice and liquid water particles under atmospheric conditions. © 2012 American Chemical Society

The asymptotic structure of nonpremixed methane-air flames with oxidizer leakage of order unity

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

Seshadri, K.; Ilincic, N.

1995-04-01

The asymptotic structure of nonpremixed methane-air flames is analyzed using a reduced three-step mechanism. The three global steps of this reduced mechanism are similar to those used in a previous analysis. The rates of the three steps are related to the rates of the elementary reactions appearing in the C{sub 1}-mechanism for oxidation of methane. The present asymptotic analysis differs from the previous analysis in that oxygen is presumed to leak from the reaction zone to the leading order. Chemical reactions are presumed to occur in three asymptotically thin layers: the fuel-consumption layer, the nonequilibrium layer for the water-gas shiftmore » reaction and the oxidation layer. The structure of the fuel-consumption layer is presumed to be identical to that analyzed previously and in this layer the fuel reacts with the radicals to form primarily CO and H{sub 2} and some CO{sub 2} and H{sub 2}O In the oxidation layer the CO and H{sub 2} formed in the fuel-consumption layer are oxidized to CO{sub 2} and H{sub 2}O. The present analysis of the oxidation layer is simpler than the previous analysis because the variation in the values of the concentration of oxygen can be neglected to the leading order and this is a better representation of the flame structure in the vicinity of the critical conditions of extinction. The predictions of the critical conditions of extinction of the present model are compared with the predictions of previous models. It is anticipated that the present simple model can be easily extended to more complex problems such as pollutant formation in flames or chemical inhibition of flames.« less

Long-Range Interactions Restrict Water Transport in Pyrophyllite Interlayers

DOE PAGES

Zarzycki, Piotr; Gilbert, Benjamin

2016-04-27

Water diffusion within smectite clay interlayers is reduced by confinement and hence is highly determined by the interlayer spacings that are adopted during swelling. However, a molecular understanding of the short-and long-range forces governing interlayer water structure and dynamics is lacking. Using molecular dynamics simulations of water intercalated between pyrophyllite (smectite prototype) layers we provide a detailed picture of the variation of interlayered water mobility accompanying smectite expansion. Subtle changes in hydrogen bond network structure cause significant changes in water mobility that is greater for stable hydration states and reduced for intermediate separations. By studying pyrophyllite with and without externalmore » water we reveal that long-range electrostatic forces apply a restraining effect upon interlayer water mobility. Our findings are relevant for broad range of confining nanostructures with walls thin enough to permit long-range interactions that could affect the mobility of confined solvent molecules and solute species.« less

Long-Range Interactions Restrict Water Transport in Pyrophyllite Interlayers

PubMed Central

Zarzycki, Piotr; Gilbert, Benjamin

2016-01-01

Water diffusion within smectite clay interlayers is reduced by confinement and hence is highly determined by the interlayer spacings that are adopted during swelling. However, a molecular understanding of the short- and long-range forces governing interlayer water structure and dynamics is lacking. Using molecular dynamics simulations of water intercalated between pyrophyllite (smectite prototype) layers we provide a detailed picture of the variation of interlayered water mobility accompanying smectite expansion. Subtle changes in hydrogen bond network structure cause significant changes in water mobility that is greater for stable hydration states and reduced for intermediate separations. By studying pyrophyllite with and without external water we reveal that long-range electrostatic forces apply a restraining effect upon interlayer water mobility. Our findings are relevant for broad range of confining nanostructures with walls thin enough to permit long-range interactions that could affect the mobility of confined solvent molecules and solute species. PMID:27118164

Turbidity currents with equilibrium basal driving layers: a mechanism for long-runout turbidity currents

NASA Astrophysics Data System (ADS)

Luchi, R.; Balachandar, S.; Seminara, G.; Parker, G.

2017-12-01

Turbidity currents in lakes and oceans involve leveed channels that document coherent runouts of 100's and up to 1000's of km. They do so without dissipating themselves via excess entrainment of ambient water. It is generally known that currents associated with stable stratification, such as thermohaline underflows, undergo dissipation as they entrain ambient water. Here we ask why some continuous turbidity currents do not follow this tendency, as they can run out extremely long distances while maintaining their coherency. A current that becomes ever thicker downstream due to ambient water entrainment cannot select the scales necessary to maintain a coherent, slowly-varying channel depth and width over 1000 km. It has been assumed that a turbidity current may tend to a state with a densimetric Froude so low that ambient water entrainment is largely suppressed. Here, we show that such an argument is a case of special pleading. Instead, suspended sediment 'fights back' against upward mixing through its fall velocity; the water may be entrained, but the sediment need not follow. We use a formulation capturing the flow vertical structure to show the conditions under which a turbidity current can asymptotically partition itself into two layers. The lower 'driving layer' approaches an asymptotic state with invariant flow thickness, velocity profile and suspended sediment concentration profile when traversing a constant bed slope under bypass conditions. This thickness provides a scale for channel characteristics. The upper 'driven layer' continues to entrain ambient water, but the concentration there becomes ever more dilute, and the layer ultimately has no interaction with near-bed processes (and by implication bed morphology). This partition is a likely candidate for the mechanism by which the driving layer is able to run out long distances, maintaining coherence and keeping confined, over repeated flow events, within a leveed subaqueous channel of its own creation.

Keratin-lipid structural organization in the corneous layer of snake.

PubMed

Ripamonti, Alberto; Alibardi, Lorenzo; Falini, Giuseppe; Fermani, Simona; Gazzano, Massimo

2009-12-01

The shed epidermis (molt) of snakes comprises four distinct layers. The upper two layers, here considered as beta-layer, contain essentially beta-keratin. The following layer, known as mesos-layer, is similar to the human stratum corneum, and is formed by thin cells surrounded by intercellular lipids. The latter layer mainly contains alpha-keratin. In this study, the molecular assemblies of proteins and lipids contained in these layers have been analyzed in the scale of two species of snakes, the elapid Tiger snake (TS, Notechis scutatus) and the viperid Gabon viper (GV, Bitis gabonica). Scanning X-ray micro-diffraction, FTIR and Raman spectroscopies, thermal analysis, and scanning electron microscopy experiments confirm the presence of the three layers in the GV skin scale. Conversely, in the TS molt a typical alpha-keratin layer appears to be absent. In the latter, experimental data suggest the presence of two domains similar to those found in the lipid intercellular matrix of stratum corneum. X-ray diffraction data also allow to determine the relative orientation of keratins and lipids. The keratin fibrils are randomly oriented inside the layers parallel to the surface of scales while the lipids are organized in lamellar structures having aliphatic chains normal to the scale surface. The high ordered lipid organization in the mature mesos layer probably increases its effectiveness in limiting water-loss.

Structure and properties of the egg mass of the ommastrephid squid Todarodes pacificus

PubMed Central

Puneeta, Pandey; Yamamoto, Jun; Adachi, Kohsuke; Kato, Yoshiki; Sakurai, Yasunori

2017-01-01

The Japanese flying squid, Todarodes pacificus, is thought to spawn neutrally buoyant egg masses that retain a specific location in the water column by floating at the interface between water layers of slightly different densities. It is important to understand the physical process that determines the vertical distribution of the egg masses to predict their horizontal drift in relation to embryo survival and subsequent recruitment. Here, mesocosm experiments were conducted in a 300 m3 tank by creating a thermally stratified (17–22°C) water column to obtain egg masses. A cage net methodology was developed to sustain egg masses for detailed observation. We measured the density of the egg masses of T. pacificus, and used this information to infer the vertical distribution patterns of the egg masses at the spawning grounds (Tsushima Strait, Japan). When measured separately, the density of the outer jelly of each egg mass was 2.7 σ units higher than that of the surrounding water. The outer jelly and the specific gravity of embedded individual eggs (~1.10) cause the egg masses to have very slight negative buoyancy relative to the water in which they are formed. Analysis of the vertical profile of the spawning ground showed that water density (σθ) increased sharply at ~30 m depth; thus, egg masses might settle above the pycnocline layer. In conclusion, we suggest that T. pacificus egg masses might retain their location in the water column by floating at the interface between water layers of slightly different densities, which happen to be above the pycnocline layer (actual depth varies seasonally/annually) in the Tsushima Strait between Korea and Japan. PMID:28767686

Structure and properties of the egg mass of the ommastrephid squid Todarodes pacificus.

PubMed

Puneeta, Pandey; Vijai, Dharmamony; Yamamoto, Jun; Adachi, Kohsuke; Kato, Yoshiki; Sakurai, Yasunori

2017-01-01

The Japanese flying squid, Todarodes pacificus, is thought to spawn neutrally buoyant egg masses that retain a specific location in the water column by floating at the interface between water layers of slightly different densities. It is important to understand the physical process that determines the vertical distribution of the egg masses to predict their horizontal drift in relation to embryo survival and subsequent recruitment. Here, mesocosm experiments were conducted in a 300 m3 tank by creating a thermally stratified (17-22°C) water column to obtain egg masses. A cage net methodology was developed to sustain egg masses for detailed observation. We measured the density of the egg masses of T. pacificus, and used this information to infer the vertical distribution patterns of the egg masses at the spawning grounds (Tsushima Strait, Japan). When measured separately, the density of the outer jelly of each egg mass was 2.7 σ units higher than that of the surrounding water. The outer jelly and the specific gravity of embedded individual eggs (~1.10) cause the egg masses to have very slight negative buoyancy relative to the water in which they are formed. Analysis of the vertical profile of the spawning ground showed that water density (σθ) increased sharply at ~30 m depth; thus, egg masses might settle above the pycnocline layer. In conclusion, we suggest that T. pacificus egg masses might retain their location in the water column by floating at the interface between water layers of slightly different densities, which happen to be above the pycnocline layer (actual depth varies seasonally/annually) in the Tsushima Strait between Korea and Japan.

Structure and reactions in some amphiphilic association systems

NASA Astrophysics Data System (ADS)

Guo, Rong

1999-06-01

The partial determinations of phase diagrams for some typical surfactants, such as SDS, CTAB and Triton X-100, give the basic aggregated states of the surfactant systems. In the micellar solutions, the diffusion coefficients of some surfactant association systems are determined by the cyclic voltammetry without any probe and used to describe the phase structure. (1) The first CMC, which represents the formation of spherical micelles, and the second CMC, which represents the transformation from spherical to rod-like micelles, are measured. The first and the second CMC are 8.0 x 10-3 mol. L -1 and 5.6 x 10-3 mol. L-1 for SDS, 8.9 x 10-4 mol. L-1 and 2.1 x 10-2 mol. L-1 for CTAB, and 3.2 x 10 -4 mol. L-1 and 1.3 x 10-3 mol. L-1 for Triton X-100, respectively. (2) The addition of polar additives, such as ethanol and benzyl alcohol (BA) in SDS micelles, or hexanol in Triton X-100 micelles, increases the diffusion coefficients and diffusion activation energy, decreases the micropolarity of the micelles with different shape, and causes the transformation from rod-like micelles to spherical ones or from spherical micelles to bicontinuous structure. (3) The isotropic region, which connects to the water comer in the phase diagram, is probably not an area of a single O/W structure, but an area with three different structures---the rod structure, spherical structure and the bicontinuous one. In the lyotropic liquid crystalline phase, the measurements of the small angle X-ray diffraction indicate that the structure parameters, such as interlayer spacing and water penetration, are related to the compositions of the surfactant association systems. The lamellar liquid crystal has a high water penetration but the hexagonal liquid crystal only has a water penetration about 0.05. Some surfactant association systems have been applied in the hydrotrope action of vitamin C (VC) and preparation of nanoparticles, respectively. Vitamin C (VC) can be used as hydrotrope agent in the cationic surfactant CTAB system with various co-surfactants: n-pentanol, n-octanol, n-valeric acid, and n-caproic acid, but not in SDS or Triton X-100 systems. Presence of VC stabilizes both W/O and O/W microemulsions but destabilizes the lamellar liquid crystalline phase. Hence, the "phase transition" from the lamellar liquid crystalline phase to the isotropic phase of O/W, W/O and bicontinuous structure phase occurs with the addition of VC. The hydrotropic action of VC has been used in sunscreens to increase the solubility of sunscreen E 557. The UV absorption spectra of E557 in various media surprisingly had a dependence on the colloid structure. A new method, the preparation of water-soluble nanoparticles, has been found by employing the effect of the penetration of solvent from water layer to amphiphilic layer in lamellar liquid crystals on the solubility of inorganic salts. Water-insoluble nanoparticles have been synthesized by the reaction of two water-soluble inorganic salts in the lamellar liquid crystal. The particle size is less than 10nm and can be controlled by the thickness of the solvent layer in the lamellar liquid crystal. The lamellar liquid crystalline phase of the Triton X-100/decanol/water system has been chosen as a medium because of its large lamellar liquid crystal region and its stability when inorganic salts are added.

Modeling cation/anion-water interactions in functional aluminosilicate structures.

PubMed

Richards, A J; Barnes, P; Collins, D R; Christodoulos, F; Clark, S M

1995-02-01

A need for the computer simulation of hydration/dehydration processes in functional aluminosilicate structures has been noted. Full and realistic simulations of these systems can be somewhat ambitious and require the aid of interactive computer graphics to identify key structural/chemical units, both in the devising of suitable water-ion simulation potentials and in the analysis of hydrogen-bonding schemes in the subsequent simulation studies. In this article, the former is demonstrated by the assembling of a range of essential water-ion potentials. These span the range of formal charges from +4e to -2e, and are evaluated in the context of three types of structure: a porous zeolite, calcium silicate cement, and layered clay. As an example of the latter, the computer graphics output from Monte Carlo computer simulation studies of hydration/dehydration in calcium-zeolite A is presented.

Structure of a model TiO2 photocatalytic interface

NASA Astrophysics Data System (ADS)

Hussain, H.; Tocci, G.; Woolcot, T.; Torrelles, X.; Pang, C. L.; Humphrey, D. S.; Yim, C. M.; Grinter, D. C.; Cabailh, G.; Bikondoa, O.; Lindsay, R.; Zegenhagen, J.; Michaelides, A.; Thornton, G.

2017-04-01

The interaction of water with TiO2 is crucial to many of its practical applications, including photocatalytic water splitting. Following the first demonstration of this phenomenon 40 years ago there have been numerous studies of the rutile single-crystal TiO2(110) interface with water. This has provided an atomic-level understanding of the water-TiO2 interaction. However, nearly all of the previous studies of water/TiO2 interfaces involve water in the vapour phase. Here, we explore the interfacial structure between liquid water and a rutile TiO2(110) surface pre-characterized at the atomic level. Scanning tunnelling microscopy and surface X-ray diffraction are used to determine the structure, which is comprised of an ordered array of hydroxyl molecules with molecular water in the second layer. Static and dynamic density functional theory calculations suggest that a possible mechanism for formation of the hydroxyl overlayer involves the mixed adsorption of O2 and H2O on a partially defected surface. The quantitative structural properties derived here provide a basis with which to explore the atomistic properties and hence mechanisms involved in TiO2 photocatalysis.

Structure of a model TiO2 photocatalytic interface.

PubMed

Hussain, H; Tocci, G; Woolcot, T; Torrelles, X; Pang, C L; Humphrey, D S; Yim, C M; Grinter, D C; Cabailh, G; Bikondoa, O; Lindsay, R; Zegenhagen, J; Michaelides, A; Thornton, G

2017-04-01

The interaction of water with TiO 2 is crucial to many of its practical applications, including photocatalytic water splitting. Following the first demonstration of this phenomenon 40 years ago there have been numerous studies of the rutile single-crystal TiO 2 (110) interface with water. This has provided an atomic-level understanding of the water-TiO 2 interaction. However, nearly all of the previous studies of water/TiO 2 interfaces involve water in the vapour phase. Here, we explore the interfacial structure between liquid water and a rutile TiO 2 (110) surface pre-characterized at the atomic level. Scanning tunnelling microscopy and surface X-ray diffraction are used to determine the structure, which is comprised of an ordered array of hydroxyl molecules with molecular water in the second layer. Static and dynamic density functional theory calculations suggest that a possible mechanism for formation of the hydroxyl overlayer involves the mixed adsorption of O 2 and H 2 O on a partially defected surface. The quantitative structural properties derived here provide a basis with which to explore the atomistic properties and hence mechanisms involved in TiO 2 photocatalysis.

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.

Molecular dynamics simulations of the electrical double layer on smectite surfaces contacting concentrated mixed electrolyte (NaCl-CaCl2) solutions.

PubMed

Bourg, Ian C; Sposito, Garrison

2011-08-15

We report new molecular dynamics results elucidating the structure of the electrical double layer (EDL) on smectite surfaces contacting mixed NaCl-CaCl(2) electrolyte solutions in the range of concentrations relevant to pore waters in geologic repositories for CO(2) or high-level radioactive waste (0.34-1.83 mol(c) dm(-3)). Our results confirm the existence of three distinct ion adsorption planes (0-, β-, and d-planes), often assumed in EDL models, but with two important qualifications: (1) the location of the β- and d-planes are independent of ionic strength or ion type and (2) "indifferent electrolyte" ions can occupy all three planes. Charge inversion occurred in the diffuse ion swarm because of the affinity of the clay surface for CaCl(+) ion pairs. Therefore, at concentrations ≥0.34 mol(c) dm(-3), properties arising from long-range electrostatics at interfaces (electrophoresis, electro-osmosis, co-ion exclusion, colloidal aggregation) will not be correctly predicted by most EDL models. Co-ion exclusion, typically neglected by surface speciation models, balanced a large part of the clay mineral structural charge in the more concentrated solutions. Water molecules and ions diffused relatively rapidly even in the first statistical water monolayer, contradicting reports of rigid "ice-like" structures for water on clay mineral surfaces. Published by Elsevier Inc.

Guest-Induced Two-Way Structural Transformation in a Layered Metal-Organic Framework Thin Film.

PubMed

Haraguchi, Tomoyuki; Otsubo, Kazuya; Sakata, Osami; Fujiwara, Akihiko; Kitagawa, Hiroshi

2016-12-28

Fabrication of thin films made of metal-organic frameworks (MOFs) has been intensively pursued for practical applications that use the structural response of MOFs. However, to date, only physisorption-induced structural response has been studied in these films. Chemisorption can be expected to provide a remarkable structural response because of the formation of bonds between guest molecules and reactive metal sites in host MOFs. Here, we report that chemisorption-induced two-way structural transformation in a nanometer-sized MOF thin film. We prepared a two-dimensional layered-type MOF Fe[Pt(CN) 4 ] thin film using a step-by-step approach. Although the as-synthesized film showed poor crystallinity, the dehydrated form of this thin film had a highly oriented crystalline nature (Film-D) as confirmed by synchrotron X-ray diffraction (XRD). Surprisingly, under water and pyridine vapors, Film-D showed chemisorption-induced dynamic structural transformations to Fe(L) 2 [Pt(CN) 4 ] thin films [L = H 2 O (Film-H), pyridine (Film-P)], where water and pyridine coordinated to the open Fe 2+ site. Dynamic structural transformations were also confirmed by in situ XRD, sorption measurement, and infrared reflection absorption spectroscopy. This is the first report of chemisorption-induced dynamic structural response in a MOF thin film, and it provides useful insights, which would lead to future practical applications of MOFs utilizing chemisorption-induced structural responses.

Prediction of unsaturated flow and water backfill during infiltration in layered soils

NASA Astrophysics Data System (ADS)

Cui, Guotao; Zhu, Jianting

2018-02-01

We develop a new analytical infiltration model to determine water flow dynamics around layer interfaces during infiltration process in layered soils. The model mainly involves the analytical solutions to quadratic equations to determine the flux rates around the interfaces. Active water content profile behind the wetting front is developed based on the solution of steady state flow to dynamically update active parameters in sharp wetting front infiltration equations and to predict unsaturated flow in coarse layers before the front reaches an impeding fine layer. The effect of water backfill to saturate the coarse layers after the wetting front encounters the impeding fine layer is analytically expressed based on the active water content profiles. Comparison to the numerical solutions of the Richards equation shows that the new model can well capture water dynamics in relation to the arrangement of soil layers. The steady state active water content profile can be used to predict the saturation state of all layers when the wetting front first passes through these layers during the unsteady infiltration process. Water backfill effect may occur when the unsaturated wetting front encounters a fine layer underlying a coarse layer. Sensitivity analysis shows that saturated hydraulic conductivity is the parameter dictating the occurrence of unsaturated flow and water backfill and can be used to represent the coarseness of soil layers. Water backfill effect occurs in coarse layers between upper and lower fine layers when the lower layer is not significantly coarser than the upper layer.

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.

Frost induced damages within porous materials - from concrete technology to fuel cells technique

NASA Astrophysics Data System (ADS)

Palecki, Susanne; Gorelkov, Stanislav; Wartmann, Jens; Heinzel, Angelika

2017-12-01

Porous media like concrete or layers of membrane electrode assemblies (MEA) within fuel cells are affected by a cyclic frost exposure due to different damage mechanisms which could lead to essential degradation of the material. In general, frost damages can only occur in case of a specific material moisture content. In fuel cells, residual water is generally available after shut down inside the membrane i.e. the gas diffusion layer (GDL). During subsequent freezing, this could cause various damage phenomena such as frost heaves and delamination effects of the membrane electrode assembly, which depends on the location of pore water and on the pore structure itself. Porous materials possess a pore structure that could range over several orders of magnitudes with different properties and freezing behaviour of the pore water. Latter can be divided into macroscopic, structured and pre-structured water, influenced by surface interactions. Therefore below 0 °C different water modifications can coexist in a wide temperature range, so that during frost exposure a high amount of unfrozen and moveable water inside the pore system is still available. This induces transport mechanisms and shrinkage effects. The physical basics are similar for porous media. While the freezing behaviour of concrete has been studied over decades of years, in order to enhance the durability, the know-how about the influence of a frost attack on fuel cell systems is not fully understood to date. On the basis of frost damage models for concrete structures, an approach to describe the impact of cyclic freezing and thawing on membrane electrode assemblies has been developed within this research work. Major aim is beyond a better understanding of the frost induced mechanisms, the standardization of a suitable test procedure for the assessment of different MEA materials under such kind of attack. Within this contribution first results will be introduced.

Architecture and High-Resolution Structure of Bacillus thuringiensis and Bacillus cereus Spore Coat Surfaces

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

Plomp, M; Leighton, T; Wheeler, K

2005-02-18

We have utilized atomic force microscopy (AFM) to visualize the native surface topology and ultrastructure of Bacillus thuringiensis and Bacillus cereus spores in water and in air. AFM was able to resolve the nanostructure of the exosporium and three distinctive classes of appendages. Removal of the exosporium exposed either a hexagonal honeycomb layer (B. thuringiensis) or a rodlet outer spore coat layer (B. cereus). Removal of the rodlet structure from B. cereus spores revealed an underlying honeycomb layer similar to that observed with B. thuringiensis spores. The periodicity of the rodlet structure on the outer spore coat of B. cereusmore » was {approx}8 nm, and the length of the rodlets was limited to the cross-patched domain structure of this layer to {approx}200 nm. The lattice constant of the honeycomb structures was {approx}9 nm for both B. cereus and B. thuringiensis spores. Both honeycomb structures were composed of multiple, disoriented domains with distinct boundaries. Our results demonstrate that variations in storage and preparation procedures result in architectural changes in individual spore surfaces, which establish AFM as a useful tool for evaluation of preparation and processing ''fingerprints'' of bacterial spores. These results establish that high-resolution AFM has the capacity to reveal species-specific assembly and nanometer scale structure of spore surfaces. These species-specific spore surface structural variations are correlated with sequence divergences in a spore core structural protein SspE.« less

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.

Characterization of the water of crystallization in CsMnCl3.2H2O (2D2O) by Raman scattering

NASA Astrophysics Data System (ADS)

Jia, Weiyi; Strauss, E.; Yen, W. M.; Xia, Kehui; Zhao, Minguang

1989-06-01

Raman spectra of CsMnCl3.2H2O (2D2O) (CMC) were measured at low temperatures. The spectra demonstrated features which are related to the chain and layered structures of the compound. The vibration characteristics of the water of crystallization were investigated in detail, allowing us to derive the spatial orientation of the water molecules and the direction of their hydrogen bonds. Strong Raman scattering from the OH stretching mode in the (zz) configuration indicates the existence of hydrogen bonds linking the layers along the z axis. Various combination frequencies of the water vibrations were observed; for example, the OH (OD) stretching mode is seen to couple to vibrations of oxygen and chlorine atoms. These combination modes play an important role in quenching 4T1-->6A1 electronic transition of Mn2+ ions through multiphonon nonradiative processes.

Characterizing heterogeneous dynamics at hydrated electrode surfaces.

PubMed

Willard, Adam P; Limmer, David T; Madden, Paul A; Chandler, David

2013-05-14

In models of Pt 111 and Pt 100 surfaces in water, motions of molecules in the first hydration layer are spatially and temporally correlated. To interpret these collective motions, we apply quantitative measures of dynamic heterogeneity that are standard tools for considering glassy systems. Specifically, we carry out an analysis in terms of mobility fields and distributions of persistence times and exchange times. In so doing, we show that dynamics in these systems is facilitated by transient disorder in frustrated two-dimensional hydrogen bonding networks. The frustration is the result of unfavorable geometry imposed by strong metal-water bonding. The geometry depends upon the structure of the underlying metal surface. Dynamic heterogeneity of water on the Pt 111 surface is therefore qualitatively different than that for water on the Pt 100 surface. In both cases, statistics of this ad-layer dynamic heterogeneity responds asymmetrically to applied voltage.

Characterizing heterogeneous dynamics at hydrated electrode surfaces

NASA Astrophysics Data System (ADS)

Willard, Adam P.; Limmer, David T.; Madden, Paul A.; Chandler, David

2013-05-01

In models of Pt 111 and Pt 100 surfaces in water, motions of molecules in the first hydration layer are spatially and temporally correlated. To interpret these collective motions, we apply quantitative measures of dynamic heterogeneity that are standard tools for considering glassy systems. Specifically, we carry out an analysis in terms of mobility fields and distributions of persistence times and exchange times. In so doing, we show that dynamics in these systems is facilitated by transient disorder in frustrated two-dimensional hydrogen bonding networks. The frustration is the result of unfavorable geometry imposed by strong metal-water bonding. The geometry depends upon the structure of the underlying metal surface. Dynamic heterogeneity of water on the Pt 111 surface is therefore qualitatively different than that for water on the Pt 100 surface. In both cases, statistics of this ad-layer dynamic heterogeneity responds asymmetrically to applied voltage.

Modeling of water lighting process and calculation of the reactor-clarifier to improve energy efficiency

NASA Astrophysics Data System (ADS)

Skolubovich, Yuriy; Skolubovich, Aleksandr; Voitov, Evgeniy; Soppa, Mikhail; Chirkunov, Yuriy

2017-10-01

The article considers the current questions of technological modeling and calculation of the new facility for cleaning natural waters, the clarifier reactor for the optimal operating mode, which was developed in Novosibirsk State University of Architecture and Civil Engineering (SibSTRIN). A calculation technique based on well-known dependences of hydraulics is presented. A calculation example of a structure on experimental data is considered. The maximum possible rate of ascending flow of purified water was determined, based on the 24 hour clarification cycle. The fractional composition of the contact mass was determined with minimal expansion of contact mass layer, which ensured the elimination of stagnant zones. The clarification cycle duration was clarified by the parameters of technological modeling by recalculating maximum possible upward flow rate of clarified water. The thickness of the contact mass layer was determined. Likewise, clarification reactors can be calculated for any other lightening conditions.

Atomic Resolution of Calcium and Oxygen Sublattices of Calcite in Ambient Conditions by Atomic Force Microscopy Using qPlus Sensors with Sapphire Tips.

PubMed

Wastl, Daniel S; Judmann, Michael; Weymouth, Alfred J; Giessibl, Franz J

2015-01-01

Characterization and imaging at the atomic scale with atomic force microscopy in biocompatible environments is an ongoing challenge. We demonstrate atomically resolved imaging of the calcite (101̅4) surface plane using stiff quartz cantilevers ("qPlus sensors", stiffness k = 1280 N/m) equipped with sapphire tips in ambient conditions without any surface preparation. With 10 atoms in one surface unit cell, calcite has a highly complex surface structure comprising three different chemical elements (Ca, C, and O). We obtain true atomic resolution of calcite in air at relative humidity ranging from 20% to 40%, imaging atomic steps and single atomic defects. We observe a great durability of sapphire tips with their Mohs hardness of 9, only one step below diamond. Depending on the state of the sapphire tip, we resolve either the calcium or the oxygen sublattice. We determine the tip termination by comparing the experimental images with simulations and discuss the possibility of chemical tip identification in air. The main challenges for imaging arise from the presence of water layers, which form on almost all surfaces and have the potential to dissolve the crystal surface. Frequency shift versus distance spectra show the presence of at least three ordered hydration layers. The measured height of the first hydration layer corresponds well to X-ray diffraction data and molecular dynamic simulations, namely, ∼220 pm. For the following hydration layers we measure ∼380 pm for the second and third layer, ending up in a total hydration layer thickness of at least 1 nm. Understanding the influence of water layers and their structure is important for surface segregation, surface reactions including reconstructions, healing of defects, and corrosion.

Strong White Photoluminescence from Carbon-Incorporated Silicon Oxide Fabricated by Preferential Oxidation of Silicon in Nano-Structured Si:C Layer

NASA Astrophysics Data System (ADS)

Vasin, Andriy V.; Ishikawa, Yukari; Shibata, Noriyoshi; Salonen, Jarno; Lehto, Vesa-Pekka

2007-05-01

A new approach to development of light-emitting SiO2:C layers on Si wafer is demonstrated. Carbon-incorporated silicon oxide was fabricated by three-step procedure: (1) formation of the porous silicon (por-Si) layer by ordinary anodization in HF:ethanol solution; (2) carbonization at 1000 °C in acetylene flow (formation of por-Si:C layer); (3) oxidation in the flow of moisturized argon at 800 °C (formation of SiO2:C layer). Resulting SiO2:C layer exhibited very strong and stable white photoluminescence at room temperature. It is shown that high reactivity of water vapor with nano-crystalline silicon and inertness with amorphous carbon play a key role in the formation of light-emitting SiO2:C layer.

Titan's interior from its rotation axis orientation and its Love number

NASA Astrophysics Data System (ADS)

Baland, Rose-Marie; Gabriel, Tobie; Axel, Lefèvre

2013-04-01

The tidal Love number k2 of Titan has been recently estimated from Cassini flybys radio-tracking and is consistent with the presence of a global ocean in Titan's interior, located between two ice layers (Iess et al. 2012), in accordance with prediction from interior and evolutionary models for Titan. Previously, the orientation of the rotation axis of Titan has been measured on the basis of radar images from Cassini (Stiles et al. 2008). Titan's obliquity, is about 0.3. The measured orientation is more consistent with the presence of a global internal liquid ocean than with an entirely solid Titan (Baland et al. 2011). The global topography data of Titan seem to indicate some departure from the hydrostatic shape expected for a synchronous satellite under the influence of its rotation and the static tides raised by the central planet (Zebker et al. 2009). This may be explained by a differential tidal heating in the ice shell which flattens the poles (Nimmo and Bills 2010). A surface more flattened than expected implies compensation in depth to explain the measured gravity coefficients C20 and C22 of Iess et al. (2012). Here, all layers are assumed to have a tri-axial ellipsoid shape, but with polar and equatorial flattenings that differ from the hydrostatic expected ones. We assess the influence of this non-hydrostatic shape on the conclusions of Baland et al. (2011), which developped a Cassini state model for the orientation of the rotation axis of a synchronous satellite having an internal liquid layer. We assess the possibility to constrain Titan's interior (and particularly the structure of the water/ice layer) from both the rotation axis orientation and the Love number. We consider a range of internal structure models consistent with the mean density and the mean radius of Titan, and made of a shell, an ocean, a mantle, and a core, from the surface to the center, with various possible compositions (e.g. ammonia mixed with water for the ocean). The internal structure models consistent with the measured orientation of the rotation axis and Love number still have to be examined with respect to other constrains, such as the shell thickness estimation derived from electric-field measurement of the Huyges probe (Béghin et al. 2012) and the expected temperature profile of the water/ice layer. For instance, a thin shell would imply a rather thick ocean, based on water (or water/ammonia) phase diagram.

Turbulent Humidity Fluctuations in the Convective Boundary Layer: Case Studies Using Water Vapour Differential Absorption Lidar Measurements

NASA Astrophysics Data System (ADS)

Muppa, Shravan Kumar; Behrendt, Andreas; Späth, Florian; Wulfmeyer, Volker; Metzendorf, Simon; Riede, Andrea

2016-01-01

Turbulent humidity fluctuations in the convective boundary layer (CBL) under clear-sky conditions were investigated by deriving moments up to fourth-order. High-resolution humidity measurements were collected with a water vapour differential absorption lidar system during the HD(CP)}2 Observational Prototype Experiment (HOPE). Two cases, both representing a well-developed CBL around local noon, are discussed. While the first case (from the intensive observation period (IOP) 5 on 20 April 2013) compares well with what is considered typical CBL behaviour, the second case (from IOP 6 on 24 April 2013) shows a number of non-typical characteristics. Both cases show similar capping inversions and wind shear across the CBL top. However, a major difference between both cases is the advection of a humid layer above the CBL top during IOP 6. While the variance profile of IOP 5 shows a maximum at the interfacial layer, two variance peaks are observed near the CBL top for IOP 6. A marked difference can also be seen in the third-order moment and skewness profiles: while both are negative (positive) below (above) the CBL top for IOP 5, the structure is more complex for IOP 6. Kurtosis is about three for IOP 5, whereas for IOP 6, the distribution is slightly platykurtic. We believe that the entrainment of an elevated moist layer into the CBL is responsible for the unusual findings for IOP 6, which suggests that it is important to consider the structure of residual humidity layers entrained into the CBL.

Thermodynamic and radiative structure of stratocumulus-topped boundary layers*

DOE PAGES

Ghate, Virendra P.; Miller, Mark A.; Albrecht, Bruce A.; ...

2015-01-05

Stratocumulus Topped Boundary Layers (STBL) observed in three different regions with distinctive environments are described in the context of their thermodynamic and radiative properties. Here, the primary data set consisted of 131 soundings from the South East Pacific (SEP), 90 soundings from the island of Graciosa (GRW) in the North Atlantic and 83 soundings from the US Southern Great Plains (SGP). A new technique that preserves the depths of the sub-layers within a STBL is proposed for averaging the profiles of thermodynamic and radiative variables. The STBL was deepest over SEP and had the strongest radiative cooling rates near cloudmore » top among the three locations. Although the radiative cooling rates were comparable over GRW and SGP, the STBL was deeper over GRW compared to that over SGP. On average the STBL inversion was strongest over SEP (11.7 k and -5.43 g kg -1) and weakest over the SGP (6.89 k and -0.41 g kg -1). Significantly larger liquid water path, integrated water vapor, and variability in these two properties was found over GRW and evidence presented suggests that conditions at cloud top may play a lesser role in determining the resident cloud structure over GRW than over SEP. A modal analysis revealed ~26% of the STBL to be well-mixed, ~20% of STBL to be stable and ~30% STBL having a stable layer in-between a surface mixed layer and the cloud layer. Over all the three locations, the STBL was shallowest in well-mixed mode and deepest in the stable mode.« less

Planar waveguide sensor of ammonia

NASA Astrophysics Data System (ADS)

Rogoziński, Roman; Tyszkiewicz, Cuma; Karasiński, Paweł; Izydorczyk, Weronika

2015-12-01

The paper presents the concept of forming ammonia sensor based on a planar waveguide structure. It is an amplitude sensor produced on the basis of the multimode waveguide. The technological base for this kind of structure is the ion exchange method and the sol-gel method. The planar multimode waveguide of channel type is produced in glass substrate (soda-lime glass of Menzel-Glaser company) by the selective Ag+↔Na+ ion exchange. On the surface of the glass substrate a porous (~40%) silica layer is produced by the sol-gel method. This layer is sensitized to the presence of ammonia in the surrounding atmosphere by impregnation with Bromocresol Purple (BCP) dye. Therefore it constitutes a sensor layer. Spectrophotometric tests carried out showed about 50% reduction of cross-transmission changes of such sensor layer for a wave λ=593 nm caused by the presence of 25% ammonia water vapor in its ambience. The radiation source used in this type of sensor structure is a light emitting diode LED. The gradient channel waveguide is designed for frontal connection (optical glue) with a standard multimode telecommunications waveguide 62.5/125μm.

Synthesis, crystal structure, and photocatalytic activity of a new two-layer Ruddlesden-Popper phase, Li{sub 2}CaTa{sub 2}O{sub 7}

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

Liang Zhenhua; Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026; Tang Kaibin

2008-04-15

A new two-layer Ruddlesden-Popper phase Li{sub 2}CaTa{sub 2}O{sub 7} has been synthesized for the first time. The detailed structure determination of Li{sub 2}CaTa{sub 2}O{sub 7} performed by powder X-ray diffraction (XRD) and electron microscopy (ED) shows that it crystallizes in the space group Fmmm [a{approx}5.5153(1), b{approx}5.4646(1), c{approx}18.2375(3)A]. UV-visible diffuse reflection spectrum of the prepared Li{sub 2}CaTa{sub 2}O{sub 7} indicates that it had absorption in the UV region. The photocatalytic activity of the Li{sub 2}CaTa{sub 2}O{sub 7} powders was evaluated by degradation of RhB molecules in water under ultra visible light irradiation. The results showed that Li{sub 2}CaTa{sub 2}O{sub 7} hasmore » high photocatalytic activity at room temperature. Therefore, the preparation and properties studies of Li{sub 2}CaTa{sub 2}O{sub 7} with a two-layer Ruddlesden-Popper structure suggest potential future applications in photocatalysis. - Graphical abstract: Crystal structure of a two-layer Ruddlesden-Popper phase Li{sub 2}CaTa{sub 2}O{sub 7} A new two-layer Ruddlesden-Popper phase Li{sub 2}CaTa{sub 2}O{sub 7} has been synthesized for the first time. Li{sub 2}CaTa{sub 2}O{sub 7} crystallizes in the space group Fmmm determined by powder X-ray and electron diffraction. UV-visible diffuse reflection spectra and the photocatalytic degradation of RhB molecules in water under ultra visible light irradiation show that Li{sub 2}CaTa{sub 2}O{sub 7} is a potential material in photocatalysis.« less

From Two‐ to Three‐Dimensional Structures of a Supertetrahedral Boran Using Density Functional Calculations

PubMed Central

Getmanskii, Iliya V.; Steglenko, Dmitrii V.; Koval, Vitaliy V.; Zaitsev, Stanislav A.

2017-01-01

Abstract With help of the DFT calculations and imposing of periodic boundary conditions the geometrical and electronic structures were investigated of two‐ and three‐dimensional boron systems designed on the basis of graphane and diamond lattices in which carbons were replaced with boron tetrahedrons. The consequent studies of two‐ and three‐layer systems resulted in the construction of a three‐dimensional supertetrahedral borane crystal structure. The two‐dimensional supertetrahedral borane structures with less than seven layers are dynamically unstable. At the same time the three‐dimensional superborane systems were found to be dynamically stable. Lack of the forbidden electronic zone for the studied boron systems testifies that these structures can behave as good conductors. The low density of the supertetrahedral borane crystal structures (0.9 g cm−3) is close to that of water, which offers the perspective for their application as aerospace and cosmic materials. PMID:28402596

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

p-Type Transparent Conducting Oxide/n-Type Semiconductor Heterojunctions for Efficient and Stable Solar Water Oxidation.

PubMed

Chen, Le; Yang, Jinhui; Klaus, Shannon; Lee, Lyman J; Woods-Robinson, Rachel; Ma, Jie; Lum, Yanwei; Cooper, Jason K; Toma, Francesca M; Wang, Lin-Wang; Sharp, Ian D; Bell, Alexis T; Ager, Joel W

2015-08-05

Achieving stable operation of photoanodes used as components of solar water splitting devices is critical to realizing the promise of this renewable energy technology. It is shown that p-type transparent conducting oxides (p-TCOs) can function both as a selective hole contact and corrosion protection layer for photoanodes used in light-driven water oxidation. Using NiCo2O4 as the p-TCO and n-type Si as a prototypical light absorber, a rectifying heterojunction capable of light driven water oxidation was created. By placing the charge separating junction in the Si using a np(+) structure and by incorporating a highly active heterogeneous Ni-Fe oxygen evolution catalyst, efficient light-driven water oxidation can be achieved. In this structure, oxygen evolution under AM1.5G illumination occurs at 0.95 V vs RHE, and the current density at the reversible potential for water oxidation (1.23 V vs RHE) is >25 mA cm(-2). Stable operation was confirmed by observing a constant current density over 72 h and by sensitive measurements of corrosion products in the electrolyte. In situ Raman spectroscopy was employed to investigate structural transformation of NiCo2O4 during electrochemical oxidation. The interface between the light absorber and p-TCO is crucial to produce selective hole conduction to the surface under illumination. For example, annealing to produce more crystalline NiCo2O4 produces only small changes in its hole conductivity, while a thicker SiOx layer is formed at the n-Si/p-NiCo2O4 interface, greatly reducing the PEC performance. The generality of the p-TCO protection approach is demonstrated by multihour, stable, water oxidation with n-InP/p-NiCo2O4 heterojunction photoanodes.

Characterization and use of crystalline bacterial cell surface layers

NASA Astrophysics Data System (ADS)

Sleytr, Uwe B.; Sára, Margit; Pum, Dietmar; Schuster, Bernhard

2001-10-01

Crystalline bacterial cell surface layers (S-layers) are one of the most common outermost cell envelope components of prokaryotic organisms (archaea and bacteria). S-layers are monomolecular arrays composed of a single protein or glycoprotein species and represent the simplest biological membranes developed during evolution. S-layers as the most abundant of prokaryotic cellular proteins are appealing model systems for studying the structure, synthesis, genetics, assembly and function of proteinaceous supramolecular structures. The wealth of information existing on the general principle of S-layers have revealed a broad application potential. The most relevant features exploited in applied S-layer research are: (i) pores passing through S-layers show identical size and morphology and are in the range of ultrafiltration membranes; (ii) functional groups on the surface and in the pores are aligned in well-defined positions and orientations and accessible for chemical modifications and binding functional molecules in very precise fashion; (iii) isolated S-layer subunits from a variety of organisms are capable of recrystallizing as closed monolayers onto solid supports (e.g., metals, polymers, silicon wafers) at the air-water interface, on lipid films or onto the surface of liposomes; (iv) functional domains can be incorporated in S-layer proteins by genetic engineering. Thus, S-layer technologies particularly provide new approaches for biotechnology, biomimetics, molecular nanotechnology, nanopatterning of surfaces and formation of ordered arrays of metal clusters or nanoparticles as required for nanoelectronics.

Water structuring and collagen adsorption at hydrophilic and hydrophobic silicon surfaces.

PubMed

Cole, Daniel J; Payne, Mike C; Ciacchi, Lucio Colombi

2009-12-28

The adsorption of a collagen fragment on both a hydrophobic, hydrogen-terminated and a hydrophilic, natively oxidised Si surface is investigated using all-atom molecular dynamics. While favourable direct protein-surface interactions via localised contact points characterise adhesion to the hydrophilic surface, evenly spread surface/molecule contacts and stabilisation of the helical structure occurs upon adsorption on the hydrophobic surface. In the latter case, we find that adhesion is accompanied by a mutual fit between the hydrophilic/hydrophobic pattern within the protein and the layered water structure at the solid/liquid interface, which may provide an additional driving force to the classic hydrophobic effect.

Molecular dynamics simulations of structural transformation of perfluorooctane sulfonate (PFOS) at water/rutile interfaces.

PubMed

He, Guangzhi; Zhang, Meiyi; Zhou, Qin; Pan, Gang

2015-09-01

Concentration and salinity conditions are the dominant environmental factors affecting the behavior of perfluorinated compounds (PFCs) on the surfaces of a variety of solid matrices (suspended particles, sediments, and natural minerals). However, the mechanism has not yet been examined at molecular scales. Here, the structural transformation of perfluorooctane sulfonate (PFOS) at water/rutile interfaces induced by changes of the concentration level of PFOS and salt condition was investigated using molecular dynamics (MD) simulations. At low and intermediate concentrations all PFOS molecules directly interacted with the rutile (110) surface mainly by the sulfonate headgroups through electrostatic attraction, yielding a typical monolayer structure. As the concentration of PFOS increased, the molecules aggregated in a complex multi-layered structure, where an irregular assembling configuration was adsorbed on the monolayer structure by the van der Waals interactions between the perfluoroalkyl chains. When adding CaCl2 to the system, the multi-layered structure changed to a monolayer again, indicating that the addition of CaCl2 enhanced the critical concentration value to yield PFOS multilayer assemblies. The divalent Ca(2+) substituted for monovalent K(+) as the bridging counterion in PFOS adsorption. MD simulation may trigger wide applications in study of perfluorinated compounds (PFCs) from atomic/molecular scale. Copyright © 2015 Elsevier Ltd. All rights reserved.

Nontronite and Montmorillonite as Nutrient Sources for Life on Mars

NASA Technical Reports Server (NTRS)

Craig, P. I.; Mickol, R. L.; Archer, P. D.; Kral, T. A.

2017-01-01

Clay minerals have been identified on Mars' oldest (Noachian) terrain and their presence suggests long-term water-rock interactions. The most commonly identified clay minerals on Mars to date are nontronite (Fe-smectite) and montmorillonite (Al-smectite) [1], both of which contain variable amounts of water both adsorbed on their surface and within their structural layers. Over Mars' history, these clay miner-al-water assemblages may have served as nutrient sources for microbial life.

Investigation of porosity and heterojunction effects of a mesoporous hematite electrode on photoelectrochemical water splitting.

PubMed

Liu, Jingling; Shahid, Muhammad; Ko, Young-Seon; Kim, Eunchul; Ahn, Tae Kyu; Park, Jong Hyeok; Kwon, Young-Uk

2013-06-28

In this paper, we report the porosity and heterojunction effects of hematite (α-Fe2O3) on the photoelectrochemical (PEC) water splitting properties. The worm-like mesoporous hematite thin films (MHFs) with a pore size of ~9 nm and a wall thickness of ~5 nm were successfully obtained through the self-assembly process. MHFs formed on FTO showed much better PEC properties than those of nonporous hematite thin films (NP-HF) owing to the suppression of charge recombination. The PEC data of MHFs under front and back illumination conditions indicated that the porous structure allows the diffusion of electrolyte deep inside the MHF increasing the number of holes to be utilized in the water oxidation reaction. A heterojunction structure was formed by introducing a thin layer of SnO2 (~15 nm in thickness) between the MHF and FTO for a dramatically enhanced PEC response, which is attributed to the efficient electron transfer. Our spectroscopic and electrochemical data show that the SnO2 layer functions as an efficient electron transmitter, but does not affect the recombination kinetics of MHFs.

Femtosecond laser induced nanostructuring of graphite for the fabrication of quasi-periodic nanogratings and novel carbon nanostructures

NASA Astrophysics Data System (ADS)

Saikiran, V.; Dar, Mudasir H.; Rao, D. Narayana

2018-01-01

Here we have experimentally studied ultrafast femtosecond laser ablation of graphite in air and water environments for the fabrication of promising nanostructures on the graphite surface and also nanographite flakes, graphene quantum dots in water. After the fs laser irradiation in air quasi-periodic nanogratings were found on the graphite surface and when the irradiation is done in water we observed graphene quantum dots (GQDs) and graphitic flakes dispersed in the solution. The sheets consist of few layers of spongy kind of porous graphene, which form an irregular 3D porous structure. The field emission scanning electron microscopy reveals the formation of fluence dependent quasi-periodic deep-subwavelength nanogratings (Ʌ = 130-230 nm) on the surface. Several characterization methods have confirmed the formation of layered graphene and quantum dots. The studies on the solution confirmed the presence of GQDs with dimensions ranging about 2-4 nm. It is found that the formation of subwavelength structures and GQDs depends on the fs-laser energy and vary with different laser parameters such as fluence, energy, laser polarization.

Structural water engaged disordered vanadium oxide nanosheets for high capacity aqueous potassium-ion storage.

PubMed

Charles, Daniel Scott; Feygenson, Mikhail; Page, Katharine; Neuefeind, Joerg; Xu, Wenqian; Teng, Xiaowei

2017-05-23

Aqueous electrochemical energy storage devices using potassium-ions as charge carriers are attractive due to their superior safety, lower cost and excellent transport properties compared to other alkali ions. However, the accommodation of potassium-ions with satisfactory capacity and cyclability is difficult because the large ionic radius of potassium-ions causes structural distortion and instabilities even in layered electrodes. Here we report that water induces structural rearrangements of the vanadium-oxygen octahedra and enhances stability of the highly disordered potassium-intercalated vanadium oxide nanosheets. The vanadium oxide nanosheets engaged by structural water achieves high capacity (183 mAh g -1 in half-cells at a scan rate of 5 mV s -1 , corresponding to 0.89 charge per vanadium) and excellent cyclability (62.5 mAh g -1 in full cells after 5,000 cycles at 10 C). The promotional effects of structural water on the disordered vanadium oxide nanosheets will contribute to the exploration of disordered structures from earth-abundant elements for electrochemical energy storage.

Structural water engaged disordered vanadium oxide nanosheets for high capacity aqueous potassium-ion storage

DOE PAGES

Charles, Daniel Scott; Feygenson, Mikhail; Page, Katharine; ...

2017-05-23

Aqueous electrochemical energy storage devices using potassium-ions as charge carriers are attractive due to their superior safety, lower cost and excellent transport properties compared to other alkali ions. However, the accommodation of potassium-ions with satisfactory capacity and cyclability is difficult because large ionic radius of potassium-ions causes structural distortion and instabilities even in layered electrodes. Here we report that water induces structural rearrangements of the vanadium-oxygen octahedra and enhances stability of the highly disordered potassium-intercalated vanadium oxide nanosheets. The vanadium oxide nanosheets engaged by structural water achieves high capacity (183 mAh g -1 in half-cells at a scan rate ofmore » 5 mV s -1, corresponding to 0.89 charge per vanadium) and excellent cyclability (62.5 mAh g -1 in full-cells after 5,000 cycles at 10 C). Finally, the promotional effects of structural water on the disordered vanadium oxide nanosheets will contribute to the exploration of disordered structures from earth-abundant elements for electrochemical energy storage.« less

Structural water engaged disordered vanadium oxide nanosheets for high capacity aqueous potassium-ion storage

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

Charles, Daniel Scott; Feygenson, Mikhail; Page, Katharine

Aqueous electrochemical energy storage devices using potassium-ions as charge carriers are attractive due to their superior safety, lower cost and excellent transport properties compared to other alkali ions. However, the accommodation of potassium-ions with satisfactory capacity and cyclability is difficult because large ionic radius of potassium-ions causes structural distortion and instabilities even in layered electrodes. Here we report that water induces structural rearrangements of the vanadium-oxygen octahedra and enhances stability of the highly disordered potassium-intercalated vanadium oxide nanosheets. The vanadium oxide nanosheets engaged by structural water achieves high capacity (183 mAh g -1 in half-cells at a scan rate ofmore » 5 mV s -1, corresponding to 0.89 charge per vanadium) and excellent cyclability (62.5 mAh g -1 in full-cells after 5,000 cycles at 10 C). Finally, the promotional effects of structural water on the disordered vanadium oxide nanosheets will contribute to the exploration of disordered structures from earth-abundant elements for electrochemical energy storage.« less

Development of the crack sealant adhesion test.

DOT National Transportation Integrated Search

2009-04-01

Crack sealants are widely used in Texas to prevent water from entering into lower structural layers thereby : extending pavement life. However, most current crack sealants have been reported to have a very short life mainly due : to adhesive failures...

A new solution chemical method to make low dimensional thermoelectric materials

NASA Astrophysics Data System (ADS)

Ding, Zhongfen

2001-11-01

Bismuth telluride and its alloys are currently the best thermoelectric materials known at room temperature and are therefore used for portable solid-state refrigeration. If the thermal electric figure of merit ZT could be improved by a factor of about 3, quiet and rugged solid-state devices could eventually replace conventional compressor based cooling systems. In order to test a theory that improved one-dimensional or two-dimensional materials could enhance ZT due to lower thermal conductivity, we are developing solution processing methods to make low dimensional materials. Bismuth telluride and its p-type and n-type alloys have layered structures consisting of 5 atom thick Te-Bi-Te-Bi-Te sheets, each sheet about 10 A thick. Lithium ions are intercalated into the layered materials using liquid ammonia. The lithium-intercalated materials are then exfoliated in water to form colloidal suspensions with narrow particle size distributions and are stable for more than 24 hours. The layers are then deposited on substrates, which after annealing at low temperatures, form highly c-axis oriented thin films. The exfoliated layers can potentially be restacked with other ions or layered materials in between the sheets to form novel structures. The restacked layers when treated with nitric acid and sonication form high yield nanorod structured materials. This new intercalation and exfoliation followed by sonication method could potentially be used for many other layered materials to make nanorod structured materials. The low dimensional materials are characterized by powder X-ray diffraction, atomic force microscopy (AFM), transmission electron microscopy (TEM), scanning electron microscopy (SEM), inductively coupled plasma (ICP) and dynamic light scattering.

Light penetration structures the deep acoustic scattering layers in the global ocean.

PubMed

Aksnes, Dag L; Røstad, Anders; Kaartvedt, Stein; Martinez, Udane; Duarte, Carlos M; Irigoien, Xabier

2017-05-01

The deep scattering layer (DSL) is a ubiquitous acoustic signature found across all oceans and arguably the dominant feature structuring the pelagic open ocean ecosystem. It is formed by mesopelagic fishes and pelagic invertebrates. The DSL animals are an important food source for marine megafauna and contribute to the biological carbon pump through the active flux of organic carbon transported in their daily vertical migrations. They occupy depths from 200 to 1000 m at daytime and migrate to a varying degree into surface waters at nighttime. Their daytime depth, which determines the migration amplitude, varies across the global ocean in concert with water mass properties, in particular the oxygen regime, but the causal underpinning of these correlations has been unclear. We present evidence that the broad variability in the oceanic DSL daytime depth observed during the Malaspina 2010 Circumnavigation Expedition is governed by variation in light penetration. We find that the DSL depth distribution conforms to a common optical depth layer across the global ocean and that a correlation between dissolved oxygen and light penetration provides a parsimonious explanation for the association of shallow DSL distributions with hypoxic waters. In enhancing understanding of this phenomenon, our results should improve the ability to predict and model the dynamics of one of the largest animal biomass components on earth, with key roles in the oceanic biological carbon pump and food web.

Building a road map for tailoring multilayer polyelectrolyte films

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

Ankner, John Francis; Bardoel, Agatha A; Sukishvili, Svetlana

2012-01-01

Researchers are moving a step closer to a definite road map for building layer-by-layer (LbL) assembled polyelectrolyte films, with the assistance of the Liquids Reflectometer at Oak Ridge National Laboratory's Spallation Neutron Source, in Oak Ridge, Tennessee. Scientists using the liquids reflectometer have successfully taken snapshots in close to real time of these multilayered structures for different applications when they modify the structure and function parameters. Polyelecrolytes are polymers that carry charge in aqueous solutions. They contain chemical groups that dissociate in water, making such polymers charged. Most polyelectrolytes are water soluble. They are important components in foods, soaps, shampoos,more » and cosmetics products. They show promise for such environmental work as oil recovery and water treatment. Polyelectrolytes are compelling because researchers can chemically modify how they interact with water for multiple applications. When two types of polyelectrolytes of opposite charge are assembled at a surface in a sequential way using the LbL assembly technique, 'the result is the forming of surface films, useful for coatings, biomedical implants and devices, controlling adhesion of biological molecules, and controlling delivery of therapeutic molecules from surfaces,' said Svetlana Sukhishvili of the Stevens Institute of Technology in New Jersey, the lead chemist on the collaboration. 'Medical doctors often prefer to deliver multiple therapeutic compounds from the coatings in a time-resolved manner,' Sukhishvili said. 'To assist them, material scientists need to learn how to build coatings in which polymer layering will not be compromised when exposed to normal physiological conditions.' 'Being able to control these properties, understanding how what you do to the materials affects their properties, this allows you to apply them to situations where interacting with an environment is very helpful, whether in a biological context or any other kind of water soluble context,' said John Ankner, lead instrument scientist for the Liquids Reflectometer. Ankner said that when several parameters are systematically altered, that allows researchers to map out the whole range of structures in the polymer. 'This work really sets a road map for how to get started with synthesizing polyelectrolyte materials for specific applications. Then, one can say, ok, this methylated material, the one that is 30% charged, is going to be what we want to use for a particular application.' The ORNL collaboration with the Stevens Institute has been conducting a series of experiments at the SNS to study layered film stratification in these polymers. Researchers stitch the polyelectrolyte chains in the LbL films together through what is called ionic pairing and arrange them within fuzzy, ultrathin layers that lie parallel to a solid surface substrate. Exposure of these films to aqueous solutions that contain salt (i.e., conditions that imitate real life) can compromise this film layering, as the salt ions act to weaken the ionic pairing that binds such layers together. So salt solutions are of key interest in studying how to make such layers for use in human applications. In the first research, Ankner, Sukhishvili and her student Li Xu looked at the effects of the layering of two types of LbL films of changing the charge density with a salt solution, and of blocking access to a charged site by nearby groups. The films were composed of positively charged variants of PDMA, a methyl polymer, and PDEA, an ethyl polymer. The other component of both systems is the ion exchanger polystyrene sulfonate (PSS) which features a fixed negative charge. First, a silicon substrate was dipped into solutions of PDMA and PDEA in dilute sodium chloride for a fixed time. Depending on the deposition time and the concentration of the solution, a nanometer-thick monolayer of the polymer adsorbs to the silicon surface. The film buildup is then continued by depositing a layer of PSS, and the cycle is repeated. The PDMA (methyl)/PSS and PDEA (ethyl)/PSS films were then annealed in varying concentrations of aqueous salt solutions. The chemists wanted to know if in these multi-layer cake-like assemblies, the structure can be systematically altered by varying the salt concentration, time in solution, and ultimately other environmental parameters, such as temperature or pH. Neutron reflectivity of the layered films exhibits the quality of the layering, in particular the concentration of the layers and how intermixed they are with adjacent layers. In this research, neutron reflectivity data from films built from 10%, 40%, and 100% charged PDMA or PDEA polyelectrolytes and 100% charged PSS were quantitatively compared to predicted, layered arrangements until the models produced reflectivity patterns matching those of the data.« 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

High mobility organic field-effect transistor based on water-soluble deoxyribonucleic acid via spray coating

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

Shi, Wei; Han, Shijiao; Huang, Wei

High mobility organic field-effect transistors (OFETs) by inserting water-soluble deoxyribonucleic acid (DNA) buffer layer between electrodes and pentacene film through spray coating process were fabricated. Compared with the OFETs incorporated with DNA in the conventional organic solvents of ethanol and methanol: water mixture, the water-soluble DNA based OFET exhibited an over four folds enhancement of field-effect mobility from 0.035 to 0.153 cm{sup 2}/Vs. By characterizing the surface morphology and the crystalline structure of pentacene active layer through atomic force microscope and X-ray diffraction, it was found that the adoption of water solvent in DNA solution, which played a key role inmore » enhancing the field-effect mobility, was ascribed to both the elimination of the irreversible organic solvent-induced bulk-like phase transition of pentacene film and the diminution of a majority of charge trapping at interfaces in OFETs.« less

Microstructure and rheology of particle stabilized emulsions: Effects of particle shape and inter-particle interactions.

PubMed

Katepalli, Hari; John, Vijay T; Tripathi, Anubhav; Bose, Arijit

2017-01-01

Using fumed and spherical silica particles of similar hydrodynamic size, we investigated the effects of particle shape and inter-particle interactions on the formation, stability and rheology of bromohexadecane-in-water Pickering emulsions. The interparticle interactions were varied from repulsive to attractive by modifying the salt concentration in the aqueous phase. Optical microscope images revealed smaller droplet sizes for the fumed silica stabilized emulsions. All the emulsions remained stable for several weeks. Cryo-SEM images of the emulsion droplets showed a hexagonally packed single layer of particles at oil-water interfaces in emulsions stabilized with silica spheres, irrespective of the nature of the inter-particle interactions. Thus, entropic, excluded volume interactions dominate the fate of spherical particles at oil-water interfaces. On the other hand, closely packed layers of particles were observed at oil-water interfaces for the fumed silica stabilized emulsions for both attractive and repulsive interparticle interactions. At the high salt concentrations, attractive inter-particles interactions led to aggregation of fumed silica particles, and multiple layers of these particles were then observed on the droplet surfaces. A network of fumed silica particles was also observed between the emulsion droplets, suggesting that enthalpic interactions are responsible for the determining particle configurations at oil-water interfaces as well as in the aqueous phase. Steady shear viscosity measurements over a range of shear stresses, as well as oscillatory shear measurements at 1Hz confirm the presence of a network in fumed silica suspensions and emulsions, and the lack of such a network when spherical particles are used. The fractal structure of fumed silica leads to several contact points and particle interlocking in the water as well as on the bromohexadecane-water interfaces, with corresponding effects on the structure and rheology of the emulsions. The attenuation of droplet motion due to the formation of a particle network can be exploited for stabilizing emulsions and for modulating their rheology. Copyright © 2016 Elsevier Inc. All rights reserved.

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.

Composition changes in the cuticular surface lipids of the helophytes Phragmites australis and Juncus effusus as result of pollutant exposure.

PubMed

Macherius, André; Kuschk, Peter; Haertig, Claus; Moeder, Monika; Shtemenko, Natalia I; Bayona, Antonio Heredia; Guerrero, José A Heredia; Gey, Manfred

2011-06-01

Helophytes like rush and reed are increasingly used for phytoremediation of contaminated water. This study characterises the response of rush and reed plants to chemical stressors such as chlorobenzene, benzene and methyl-tert-butyl ether. The extractable wax layer of the cuticle was chosen for detailed investigations due to its multiple, particularly, protective functions for plants and its easy availability for analysis. The chemical composition of the cuticle wax layer of reed and rush was studied in dependence on chemical stress caused by contaminated water under wetland cultivation conditions. The lipid layer of leaves was extracted, derivatised and investigated by GC-MS using retention time locking and a plant-specific data base. In case of rush, a remarkable increase of the total lipid layer and a prolongation of the mean chain length resulted as response on a chlorobenzene exposure. The significant difference in the substance profiles of exposed plants and controls could be confirmed by multivariate data analysis. The lipid layer of reed was not changed significantly when the plants were exposed to water polluted with benzene and methyl-tert-butyl ether. However, scanning electron microscopic images of the exposed reed leaves indicated alterations in the crystal structure of their wax surface. The composition and morphology of cuticular waxes indicated the plants' response to chemical stress very sensitively thus, changes in the wax layer could be used as an indication for growing in a contaminated area.

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.

Atomic layer deposition of a high-k dielectric on MoS2 using trimethylaluminum and ozone.

PubMed

Cheng, Lanxia; Qin, Xiaoye; Lucero, Antonio T; Azcatl, Angelica; Huang, Jie; Wallace, Robert M; Cho, Kyeongjae; Kim, Jiyoung

2014-08-13

We present an Al2O3 dielectric layer on molybdenum disulfide (MoS2), deposited using atomic layer deposition (ALD) with ozone/trimethylaluminum (TMA) and water/TMA as precursors. The results of atomic force microscopy and low-energy ion scattering spectroscopy show that using TMA and ozone as precursors leads to the formation of uniform Al2O3 layers, in contrast to the incomplete coverage we observe when using TMA/H2O as precursors. Our Raman and X-ray photoelectron spectroscopy measurements indicate minimal variations in the MoS2 structure after ozone treatment at 200 °C, suggesting its excellent chemical resistance to ozone.

Root attributes affecting water uptake of rice (Oryza sativa) under drought

PubMed Central

Henry, Amelia

2012-01-01

Lowland rice roots have a unique physiological response to drought because of their adaptation to flooded soil. Rice root attributes that facilitate growth under flooded conditions may affect rice response to drought, but the relative roles of root structural and functional characteristics for water uptake under drought in rice are not known. Morphological, anatomical, biochemical, and molecular attributes of soil-grown rice roots were measured to investigate the genotypic variability and genotype×environment interactions of water uptake under variable soil water regimes. Drought-resistant genotypes had the lowest night-time bleeding rates of sap from the root system in the field. Diurnal fluctuation predominated as the strongest source of variation for bleeding rates in the field and root hydraulic conductivity (Lp r) in the greenhouse, and was related to expression trends of various PIP and TIP aquaporins. Root anatomy was generally more responsive to drought treatments in drought-resistant genotypes. Suberization and compaction of sclerenchyma layer cells decreased under drought, whereas suberization of the endodermis increased, suggesting differential roles of these two cell layers for the retention of oxygen under flooded conditions (sclerenchyma layer) and retention of water under drought (endodermis). The results of this study point to the genetic variability in responsiveness to drought of rice roots in terms of morphology, anatomy, and function. PMID:22791828

Root attributes affecting water uptake of rice (Oryza sativa) under drought.

PubMed

Henry, Amelia; Cal, Andrew J; Batoto, Tristram C; Torres, Rolando O; Serraj, Rachid

2012-08-01

Lowland rice roots have a unique physiological response to drought because of their adaptation to flooded soil. Rice root attributes that facilitate growth under flooded conditions may affect rice response to drought, but the relative roles of root structural and functional characteristics for water uptake under drought in rice are not known. Morphological, anatomical, biochemical, and molecular attributes of soil-grown rice roots were measured to investigate the genotypic variability and genotype×environment interactions of water uptake under variable soil water regimes. Drought-resistant genotypes had the lowest night-time bleeding rates of sap from the root system in the field. Diurnal fluctuation predominated as the strongest source of variation for bleeding rates in the field and root hydraulic conductivity (Lpr) in the greenhouse, and was related to expression trends of various PIP and TIP aquaporins. Root anatomy was generally more responsive to drought treatments in drought-resistant genotypes. Suberization and compaction of sclerenchyma layer cells decreased under drought, whereas suberization of the endodermis increased, suggesting differential roles of these two cell layers for the retention of oxygen under flooded conditions (sclerenchyma layer) and retention of water under drought (endodermis). The results of this study point to the genetic variability in responsiveness to drought of rice roots in terms of morphology, anatomy, and function.

The effect of solvent polarity on the accumulation of leachables from pharmaceutical product containers.

PubMed

Jenke, Dennis; Odufu, Alex; Poss, Mitchell

2006-02-01

Material/water equilibrium interaction constants (E(b)) were determined for 12 organic model solutes and a plastic material used in pharmaceutical product containers (non-PVC polyolefin). An excellent correlation was obtained between the measured interaction constants and the organic solute's octanol/water partition coefficient. The effect of solvent polarity on E(b) was assessed by examining the interaction between the plastic and selected model solutes in binary ethanol/water mixtures. In general, logE(b) could be linearily related to the polarity of the ethanol/water mixture. This information, coupled with the interaction model, was used to estimate the levels to which container leachables could accumulate in contacted solutions. Such estimates were made for six known leachables of the polyolefin material and compared to the leachable's measured accumulation levels in binary ethanol/water systems. In general, the accumulation level of the leachables increased with increasing solution polarity. For most of the leachables, the measured accumulation level was less than the calculated levels, suggesting that equilibrium was not achieved in the leaching portion of this study. This lack of equilibrium is attributable to the layered structure of the material studied, as such layering retards the migration of the leachables that are derived from the material's non-solution contact layers.

Oil Contact Angles in a Water-Decane-Silicon Dioxide System: Effects of Surface Charge

NASA Astrophysics Data System (ADS)

Xu, Shijing; Wang, Jingyao; Wu, Jiazhong; Liu, Qingjie; Sun, Chengzhen; Bai, Bofeng

2018-04-01

Oil wettability in the water-oil-rock systems is very sensitive to the evolution of surface charges on the rock surfaces induced by the adsorption of ions and other chemical agents in water flooding. Through a set of large-scale molecular dynamics simulations, we reveal the effects of surface charge on the oil contact angles in an ideal water-decane-silicon dioxide system. The results show that the contact angles of oil nano-droplets have a great dependence on the surface charges. As the surface charge density exceeds a critical value of 0.992 e/nm2, the contact angle reaches up to 78.8° and the water-wet state is very apparent. The variation of contact angles can be confirmed from the number density distributions of oil molecules. With increasing the surface charge density, the adsorption of oil molecules weakens and the contact areas between nano-droplets and silicon dioxide surface are reduced. In addition, the number density distributions, RDF distributions, and molecular orientations indicate that the oil molecules are adsorbed on the silicon dioxide surface layer-by-layer with an orientation parallel to the surface. However, the layered structure of oil molecules near the silicon dioxide surface becomes more and more obscure at higher surface charge densities.

Oil Contact Angles in a Water-Decane-Silicon Dioxide System: Effects of Surface Charge.

PubMed

Xu, Shijing; Wang, Jingyao; Wu, Jiazhong; Liu, Qingjie; Sun, Chengzhen; Bai, Bofeng

2018-04-19

Oil wettability in the water-oil-rock systems is very sensitive to the evolution of surface charges on the rock surfaces induced by the adsorption of ions and other chemical agents in water flooding. Through a set of large-scale molecular dynamics simulations, we reveal the effects of surface charge on the oil contact angles in an ideal water-decane-silicon dioxide system. The results show that the contact angles of oil nano-droplets have a great dependence on the surface charges. As the surface charge density exceeds a critical value of 0.992 e/nm 2 , the contact angle reaches up to 78.8° and the water-wet state is very apparent. The variation of contact angles can be confirmed from the number density distributions of oil molecules. With increasing the surface charge density, the adsorption of oil molecules weakens and the contact areas between nano-droplets and silicon dioxide surface are reduced. In addition, the number density distributions, RDF distributions, and molecular orientations indicate that the oil molecules are adsorbed on the silicon dioxide surface layer-by-layer with an orientation parallel to the surface. However, the layered structure of oil molecules near the silicon dioxide surface becomes more and more obscure at higher surface charge densities.

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.

Roll-to-roll suitable short-pulsed laser scribing of organic photovoltaics and close-to-process characterization

NASA Astrophysics Data System (ADS)

Kuntze, Thomas; Wollmann, Philipp; Klotzbach, Udo; Fledderus, Henri

2017-03-01

The proper long term operation of organic electronic devices like organic photovoltaics OPV depends on their resistance to environmental influences such as permeation of water vapor. Major efforts are spent to encapsulate OPV. State of the art is sandwich-like encapsulation between two ultra-barrier foils. Sandwich encapsulation faces two major disadvantages: high costs ( 1/3 of total costs) and parasitic intrinsic water (sponge effects of the substrate foil). To fight these drawbacks, a promising approach is to use the OPV substrate itself as barrier by integration of an ultra-barrier coating, followed by alternating deposition and structuring of OPV functional layers. In effect, more functionality will be integrated into less material, and production steps are reduced in number. All processing steps must not influence the underneath barrier functionality, while all electrical functionalities must be maintained. As most reasonable structuring tool, short and ultrashort pulsed lasers USP are used. Laser machining applies to three layers: bottom electrode made of transparent conductive materials (P1), organic photovoltaic operative stack (P2) and top electrode (P3). In this paper, the machining of functional 110…250 nm layers of flexible OPV by USP laser systems is presented. Main focus is on structuring without damaging the underneath ultra-barrier layer. The close-to-process machining quality characterization is performed with the analysis tool "hyperspectral imaging" (HSI), which is checked crosswise with the "gold standard" Ca-test. It is shown, that both laser machining and quality controlling, are well suitable for R2R production of OPV.

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.

Effect of the ordered interfacial water layer in protein complex formation: A nonlocal electrostatic approach

NASA Astrophysics Data System (ADS)

Rubinstein, A.; Sabirianov, R. F.; Mei, W. N.; Namavar, F.; Khoynezhad, A.

2010-08-01

Using a nonlocal electrostatic approach that incorporates the short-range structure of the contacting media, we evaluated the electrostatic contribution to the energy of the complex formation of two model proteins. In this study, we have demonstrated that the existence of an ordered interfacial water layer at the protein-solvent interface reduces the charging energy of the proteins in the aqueous solvent, and consequently increases the electrostatic contribution to the protein binding (change in free energy upon the complex formation of two proteins). This is in contrast with the finding of the continuum electrostatic model, which suggests that electrostatic interactions are not strong enough to compensate for the unfavorable desolvation effects.

Effect of the ordered interfacial water layer in protein complex formation: A nonlocal electrostatic approach.

PubMed

Rubinstein, A; Sabirianov, R F; Mei, W N; Namavar, F; Khoynezhad, A

2010-08-01

Using a nonlocal electrostatic approach that incorporates the short-range structure of the contacting media, we evaluated the electrostatic contribution to the energy of the complex formation of two model proteins. In this study, we have demonstrated that the existence of an ordered interfacial water layer at the protein-solvent interface reduces the charging energy of the proteins in the aqueous solvent, and consequently increases the electrostatic contribution to the protein binding (change in free energy upon the complex formation of two proteins). This is in contrast with the finding of the continuum electrostatic model, which suggests that electrostatic interactions are not strong enough to compensate for the unfavorable desolvation effects.

Architecture of Pd-Au bimetallic nanoparticles in sodium bis(2-ethylhexyl)sulfosuccinate reverse micelles as investigated by X-ray absorption spectroscopy.

PubMed

Chen, Ching-Hsiang; Sarma, Loka Subramanyam; Chen, Jium-Ming; Shih, Shou-Chu; Wang, Guo-Rung; Liu, Din-Goa; Tang, Mau-Tsu; Lee, Jyh-Fu; Hwang, Bing-Joe

2007-09-01

In this study, we demonstrate the unique application of X-ray absorption spectroscopy (XAS) as a fundamental characterization tool to help in designing and controlling the architecture of Pd-Au bimetallic nanoparticles within a water-in-oil microemulsion system of water/sodium bis(2-ethylhexyl)sulfosuccinate (AOT)/n-heptane. Structural insights obtained from the in situ XAS measurements recorded at each step during the formation process revealed that Pd-Au bimetallic clusters with various Pd-Au atomic stackings are formed by properly performing hydrazine reduction and redox transmetalation reactions sequentially within water-in-oil microemulsions. A structural model is provided to explain reasonably each reaction step and to give detailed insight into the nucleation and growth mechanism of Pd-Au bimetallic clusters. The combination of in situ XAS analysis at both the Pd K-edge and the Au L(III)-edge and UV-vis absorption spectral features confirms that the formation of Pd-Au bimetallic clusters follows a (Pd(nuclei)-Au(stack))-Pd(surf) stacking. This result further implies that the thickness of Au(stack) and Pd(surf) layers may be modulated by varying the dosage of the Au precursor and hydrazine, respectively. In addition, a bimetallic (Pd-Au)(alloy) nanocluster with a (Pd(nuclei)-Au(stack))-(Pd-Au(alloy))(surf) stacking was also designed and synthesized in order to check the feasibility of Pd(surf) layer modification. The result reveals that the Pd(surf) layer of the stacked (Pd(nuclei)-Au)(stack) bimetallic clusters can be successfully modified to form a (Au-Pd alloy)(surf) layer by a co-reduction of Pd and Au ions by hydrazine. Further, we demonstrate the alloying extent or atomic distribution of Pd and Au in Pd-Au bimetallic nanoparticles from the derived XAS structural parameters. The complete XAS-based methodology, demonstrated here on the Pd-Au bimetallic system, can easily be extended to design and control the alloying extent or atomic distribution, atomic stacking, and electronic structure to construct many other types of bimetallic systems for interesting applications.

Ultrasonically assisted solvothermal synthesis of novel Ni/Al layered double hydroxide for capturing of Cd(II) from contaminated water

NASA Astrophysics Data System (ADS)

Rahmanian, Omid; Maleki, Mohammad Hassan; Dinari, Mohammad

2017-11-01

A novel adsorbent of nickel aluminum layered double hydroxide (Ni/Al-LDH) was prepared through the precipitation of metal nitrates by ultrasonically assisted solvothermal method. The surface morphology, chemical structure and thermal properties of this compound were examined by X-ray diffraction (XRD), Fourier Transform Infrared (FT-IR), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA) techniques. The XRD, TEM and FE-SEM results established that the synthesized LDH have a well-ordered layer structure with good crystalline nature. Then it was applied to remove excessive Cd(II) ions from water and the effects of contact time, pH and adsorbent dose were examined at initial Cd(II) concentration of 10 mg/L. Results show that the time required to reach equilibrium was fast (40 min) and working pH solution was neutral (pH 7). Langmuir and Freundlich model of adsorption isotherms were explored; the results show that the Freundlich model was better fitted than that Langmuir model. This results predicting a multilayer adsorption of Cd(II) on LDH. The equilibrium kinetic adsorption data were fixed to the pseudo-second order kinetic equation.

Forward Osmosis Membranes under Null-Pressure Condition: Do Hydraulic and Osmotic Pressures Have Identical Nature?

PubMed

Kook, Seungho; Swetha, Chivukula D; Lee, Jangho; Lee, Chulmin; Fane, Tony; Kim, In S

2018-03-20

Forward osmosis (FO) membranes fall into the category of nonporous membranes, based on the assumption that water and solute transport occur solely based on diffusion. The solution-diffusion (S-D) model has been widely used in predicting their performances in the coexistence of hydraulic and osmotic driving forces, a model that postulates the hydraulic and osmotic driving forces have identical nature. It was suggested, however, such membranes may have pores and mass transport could occur both by convection (i.e., volumetric flow) as well as by diffusion assuming that the dense active layer of the membranes is composed of a nonporous structure with defects which induce volumetric flow through the membranes. In addition, the positron annihilation technique has revealed that the active layers can involve relatively uniform porous structures. As such, the assumption of a nonporous active layer in association with hydraulic pressure is questionable. To validate this assumption, we have tested FO membranes under the conditions where hydraulic and osmotic pressures are equivalent yet in opposite directions for water transport, namely the null-pressure condition. We have also established a practically valid characterization method which quantifies the vulnerability of the FO membranes to hydraulic pressure.

Permeability of uncharged organic molecules in reverse osmosis desalination membranes.

PubMed

Dražević, Emil; Košutić, Krešimir; Svalina, Marin; Catalano, Jacopo

2017-06-01

Reverse osmosis (RO) membranes are primarily designed for removal of salts i.e. for desalination of brackish and seawater, but they have also found applications in removal of organic molecules. While it is clear that steric exclusion is the dominant removal mechanism, the fundamental explanation for how and why the separation occurs remains elusive. Until recently there was no strong microscopic evidences elucidating the structure of the active polyamide layers of RO membranes, and thus they have been conceived as "black boxes"; or as an array of straight capillaries with a distribution of radii; or as polymers with a small amount of polymer free domains. The knowledge of diffusion and sorption coefficients is a prerequisite for understanding the intrinsic permeability of any organic solute in any polymer. At the same time, it is technically challenging to accurately measure these two fundamental parameters in very thin (20-300 nm) water-swollen active layers. In this work we have measured partition and diffusion coefficients and RO permeabilities of ten organic solutes in water-swollen active layers of two types of RO membranes, low (SWC4+) and high flux (XLE). We deduced from our results and recent microscopic studies that the solute flux of organic molecules in polyamide layer of RO membranes occurs in two domains, dense polymer (the key barrier layer) and the water filled domains. Copyright © 2017 Elsevier Ltd. All rights reserved.

Liquid-phase tuning of porous PVDF-TrFE film on flexible substrate for energy harvesting

NASA Astrophysics Data System (ADS)

Chen, Dajing; Chen, Kaina; Brown, Kristopher; Hang, Annie; Zhang, John X. J.

2017-04-01

Emerging wearable and implantable biomedical energy harvesting devices demand efficient power conversion, flexible structures, and lightweight construction. This paper presents Polyvinylidene fluoride-trifluoroethylene (PVDF-TrFE) micro-porous structures, which can be tuned to specific mechanical flexibilities and optimized for piezoelectric power conversion. Specifically, the water vapor phase separation method was developed to control microstructure formation, pore diameter, porosity, and mechanical flexibility. Furthermore, we investigated the effects of the piezoelectric layer to supporting layer Young's modulus ratio, through using both analytical calculation and experimentation. Both structure flexibility and stress-induced voltage were considered in the analyses. Specification of electromechanical coupling efficiency, made possible by carefully designed three-dimensional porous structures, was shown to increase the power output by five-fold relative to uncoupled structures. Therefore, flexible PVDF-TrFE films with tunable microstructures, paired with substrates of different rigidities, provide highly efficient designs of compact piezoelectric energy generating devices.

Natural melanin composites by layer-by-layer assembly

NASA Astrophysics Data System (ADS)

Eom, Taesik; Shim, Bong Sub

2015-04-01

Melanin is an electrically conductive and biocompatible material, because their conjugated backbone structures provide conducting pathways from human skin, eyes, brain, and beyond. So there is a potential of using as materials for the neural interfaces and the implantable devices. Extracted from Sepia officinalis ink, our natural melanin was uniformly dispersed in mostly polar solvents such as water and alcohols. Then, the dispersed melanin was further fabricated to nano-thin layered composites by the layer-by-layer (LBL) assembly technique. Combined with polyvinyl alcohol (PVA), the melanin nanoparticles behave as an LBL counterpart to from finely tuned nanostructured films. The LBL process can adjust the smart performances of the composites by varying the layering conditions and sandwich thickness. We further demonstrated the melanin loading degree of stacked layers, combination nanostructures, electrical properties, and biocompatibility of the resulting composites by UV-vis spectrophotometer, scanning electron microscope (SEM), multimeter, and in-vitro cell test of PC12, respectively.

Layering transitions and Schlieren textures in Langmuir films of two organic radicals.

PubMed

Gallani, J-L; Bourgogne, C; Nakatsuji, S

2004-11-09

Two paramagnetic radicals have been investigated in terms of their film-forming properties at the air-water interface. Although the radicals failed to display any mesomorphic behavior in the bulk, they were found prone to built-up multilayer films on the Langmuir trough. The molecules seem to dimerize in the upper layers of the films that exhibit striking Schlieren textures when observed with Brewster angle microscopy. These Schlieren textures, together with the ability to form multilayers, indicate that the molecules came close to displaying smectic mesomorphism. A tentative model of the layers' structure is proposed, and a suggestion for synthesizing new molecules with actual mesomorphism is offered. The presented results show that the study of the behavior of molecules at the air-water interface can shed a new light on their behavior in the bulk and help in the design of new magnetic mesogens.

Green synthesis route for WS2 nanosheets using water intercalation

NASA Astrophysics Data System (ADS)

Jha, Ravindra; Santra, Sumita; Guha, Prasanta Kumar

2016-09-01

The exfoliation of layered materials has attracted a lot of attention in recent times. In this report, we have exfoliated WS2 in deionized water (without using any chemical solvents, surfactants, etc) using the thermal coefficient mismatch between WS2 and H2O along with other anomalous properties of water, such as the formation of five-, six- and seven-ring structures while freezing. Two different green synthesis routes have been proposed for WS2 exfoliation. We call them the ‘hard’ and ‘soft’ quenching methods. The nanosheets were investigated using different characterization tools and we found the exfoliation of the bulk into <4 layers with an average lateral dimension of 200 nm. The exfoliation method is unique in the sense of producing pristine nanosheets due to the absence of any organic solvents, which are difficult to remove.

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.

High Water Tolerance of a Core-Shell-Structured Zeolite for CO2 Adsorptive Separation under Wet Conditions.

PubMed

Miyamoto, Manabu; Ono, Shumpei; Kusukami, Kodai; Oumi, Yasunori; Uemiya, Shigeyuki

2018-06-11

Dehumidification in CO 2 adsorptive separation processes is an important issue, owing to its high energy consumption. However, available adsorbents such as low-silica zeolites show a significant decrease in CO 2 adsorption capacity when water vapor is present. A core-shell-structured MFI-type zeolite with a hydrophilic ZSM-5 coated with a hydrophobic silicalite-1 shell layer was applied in CO 2 adsorptive separation under wet conditions. This hybrid material demonstrated remarkably high water tolerance with stable CO 2 adsorption performance without additional thermal treatment for regeneration, whereas a significant decrease in the CO 2 adsorption amount because of water vapor was observed on the parent ZSM-5. The core-shell structure of zeolites with high pore volumes, such as LTA or CHA, could also be suitable candidates for high CO 2 adsorption capacity and high water tolerance for practical applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rapid water disinfection over a Ag/AgBr/covalent triazine-based framework composite under visible light.

PubMed

Li, Liuyi; Li, Xiaofen; Cheng, Zhi; Bi, Jinhong; Liang, Shijing; Zhang, Zizhong; Yu, Yan; Wu, Ling

2018-05-22

Development of visible-light-induced and rapid water disinfection is of significant importance. Covalent triazine-based frameworks (CTFs) with pre-designable structures and favorable semiconductive behaviors hold great promise for photocatalytic water disinfection. Here, we report an Ag/AgBr/CTF composite with a layered structure, which serves as an efficient photocatalyst for rapid water disinfection. Water disinfection with >99.99% inactivation of Escherichia coli within 12 min was achieved by using a small amount of Ag/AgBr/CTF under visible light irradiation. The inactivation efficiency of Ag/AgBr/CTF was ∼10 times better than that of bare Ag/AgBr. Rapid water disinfection by the Ag/AgBr/CTF composite mainly results from the greatly improved generation of reactive oxygen species through the synergistic effects among the three components and the affinity of CTF to the cell wall of bacteria.

Structure and Barrier Properties of Multinanolayered Biodegradable PLA/PBSA Films: Confinement Effect via Forced Assembly Coextrusion.

PubMed

Messin, Tiphaine; Follain, Nadège; Guinault, Alain; Sollogoub, Cyrille; Gaucher, Valérie; Delpouve, Nicolas; Marais, Stéphane

2017-08-30

Multilayer coextrusion processing was applied to produce 2049-layer film of poly(butylene succinate-co-butylene adipate) (PBSA) confined against poly(lactic acid) (PLA) using forced assembly, where the PBSA layer thickness was about 60 nm. This unique technology allowed to process semicrystalline PBSA as confined polymer and amorphous PLA as confining polymer in a continuous manner. The continuity of PBSA layers within the 80/20 wt % PLA/PBSA layered films was clearly evidenced by atomic force microscopy (AFM). Similar thermal events to the reference films were revealed by thermal studies; indicating no diffusion of polymers during the melt-processing. Mechanical properties were measured for the multilayer film and the obtained results were those expected considering the fraction of each polymer, revealing the absence of delamination in the PLA/PBSA multinanolayer film. The confinement effect induced by PLA led to a slight orientation of the crystals, an increase of the rigid amorphous fraction (RAF) in PBSA with a densification of this fraction without changing film crystallinity. These structural changes allowed to strongly improve the water vapor and gas barrier properties of the PBSA layer into the multilayer film up to two decades in the case of CO 2 gas. By confining the PBSA structure in very thin and continuous layers, it was then possible to improve the barrier performances of a biodegradable system and the resulting barrier properties were successfully correlated to the effect of confinement on the microstructure and the chain segment mobility of the amorphous phase. Such investigation on these multinanolayers of PLA/PBSA with the aim of evidencing relationships between microstructure implying RAF and barrier performances has never been performed yet. Besides, gas and water permeation results have shown that the barrier improvement obtained from the multilayer was mainly due to the reduction of solubility linked to the reduction of the free volume while the tortuosity effect, as usually expected, was not really observed. This work brings new insights in the field of physicochemical behaviors of new multilayer films made of biodegradable polyesters but also in interfacial processes due to the confinement effect induced in these multinanolayer structures obtained by the forced assembly coextrusion. This original coextrusion process was a very advantageous technique to produce eco-friendly materials with functional properties without the help of tie layer, additives, solvents, surface treatments, or inorganic fillers.

Preparation and characterization of highly water-soluble magnetic Fe3O4 nanoparticles via surface double-layered self-assembly method of sodium alpha-olefin sulfonate

NASA Astrophysics Data System (ADS)

Li, Honghong; Qin, Li; Feng, Ying; Hu, Lihua; Zhou, Chunhua

2015-06-01

A kind of double-layered self-assembly sodium alpha-olefin sulfonate (AOS) capped Fe3O4 magnetic nanoparticles (Fe3O4-AOS-MN) with highly water-solubility was prepared by a wet co-precipitation method with a pH of 4.8. The resulting Fe3O4-AOS-MN could be dispersed into water to form stable magnetic fluid without other treatments. The result of X-ray diffraction (XRD) indicated that the Fe3O4-AOS-MN maintained original crystalline structure and exhibited a diameter of about 7.5 nm. The iron oxide phase of nanoparticles determined by Raman spectroscopy is Fe3O4. Transmission electron microscopy (TEM) analysis confirmed that the Fe3O4-AOS-MN with spherical morphology were uniformly dispersed in water. FT-IR spectroscopy (FT-IR) and thermo-gravimetric analysis (TGA) verified the successful preparation of Fe3O4-AOS-MN capped with double-layered self-assembled AOS. The corresponding capacities of monolayer chemical absorption and the second-layer self-assembly absorption were respectively 4.07 and 14.71 wt% of Fe3O4-MN, which were much lower than those of other surfactants. Vibrating sample magnetometer (VSM) test result showed Fe3O4-AOS-MN possessed superparamagnetic behavior with the saturation magnetization value of about 44.45 emu/g. The blocking temperature TB of Fe3O4-AOS-MN capped with double-layered AOS is 170 K.

Simulating Carbon cycle and phenology in complex forests using a multi-layer process based ecosystem model; evaluation and use of 3D-CMCC-Forest Ecosystem Model in a deciduous and an evergreen neighboring forests, within the area of Brasschaat (Be)

NASA Astrophysics Data System (ADS)

Marconi, S.; Collalti, A.; Santini, M.; Valentini, R.

2013-12-01

3D-CMCC-Forest Ecosystem Model is a process based model formerly developed for complex forest ecosystems to estimate growth, water and carbon cycles, phenology and competition processes on a daily/monthly time scale. The Model integrates some characteristics of the functional-structural tree models with the robustness of the light use efficiency approach. It treats different heights, ages and species as discrete classes, in competition for light (vertical structure) and space (horizontal structure). The present work evaluates the results of the recently developed daily version of 3D-CMCC-FEM for two neighboring different even aged and mono specific study cases. The former is a heterogeneous Pedunculate oak forest (Quercus robur L. ), the latter a more homogeneous Scot pine forest (Pinus sylvestris L.). The multi-layer approach has been evaluated against a series of simplified versions to determine whether the improved model complexity in canopy structure definition increases its predictive ability. Results show that a more complex structure (three height layers) should be preferable to simulate heterogeneous scenarios (Pedunculate oak stand), where heights distribution within the canopy justify the distinction in dominant, dominated and sub-dominated layers. On the contrary, it seems that using a multi-layer approach for more homogeneous stands (Scot pine stand) may be disadvantageous. Forcing the structure of an homogeneous stand to a multi-layer approach may in fact increase sources of uncertainty. On the other hand forcing complex forests to a mono layer simplified model, may cause an increase in mortality and a reduction in average DBH and Height. Compared with measured CO2 flux data, model results show good ability in estimating carbon sequestration trends, on both a monthly/seasonal and daily time scales. Moreover the model simulates quite well leaf phenology and the combined effects of the two different forest stands on CO2 fluxes.

Thermal effects on electronic properties of CO/Pt(111) in water.

PubMed

Duan, Sai; Xu, Xin; Luo, Yi; Hermansson, Kersti; Tian, Zhong-Qun

2013-08-28

Structure and adsorption energy of carbon monoxide molecules adsorbed on the Pt(111) surfaces with various CO coverages in water as well as work function of the whole systems at room temperature of 298 K were studied by means of a hybrid method that combines classical molecular dynamics and density functional theory. We found that when the coverage of CO is around half monolayer, i.e. 50%, there is no obvious peak of the oxygen density profile appearing in the first water layer. This result reveals that, in this case, the external force applied to water molecules from the CO/Pt(111) surface almost vanishes as a result of the competitive adsorption between CO and water molecules on the Pt(111) surface. This coverage is also the critical point of the wetting/non-wetting conditions for the CO/Pt(111) surface. Averaged work function and adsorption energy from current simulations are consistent with those of previous studies, which show that thermal average is required for direct comparisons between theoretical predictions and experimental measurements. Meanwhile, the statistical behaviors of work function and adsorption energy at room temperature have also been calculated. The standard errors of the calculated work function for the water-CO/Pt(111) interfaces are around 0.6 eV at all CO coverages, while the standard error decreases from 1.29 to 0.05 eV as the CO coverage increases from 4% to 100% for the calculated adsorption energy. Moreover, the critical points for these electronic properties are the same as those for the wetting/non-wetting conditions. These findings provide a better understanding about the interfacial structure under specific adsorption conditions, which can have important applications on the structure of electric double layers and therefore offer a useful perspective for the design of the electrochemical catalysts.

Drug Loading and Release Behavior Depending on the Induced Porosity of Chitosan/Cellulose Multilayer Nanofilms.

PubMed

Park, Sohyeon; Choi, Daheui; Jeong, Hyejoong; Heo, Jiwoong; Hong, Jinkee

2017-10-02

The ability to control drug loading and release is the most important feature in the development of medical devices. In this research, we prepared a functional nanocoating technology to incorporate a drug-release layer onto a desired substrate. The multilayer films were prepared using chitosan (CHI) and carboxymethyl cellulose (CMC) polysaccharides by the layer-by-layer (LbL) method. By using chemical cross-linking to change the inner structure of the assembled multilayer, we could control the extent of drug loading and release. The cross-linked multilayer film had a porous structure and enhanced water wettability. Interestingly, more of the small-molecule drug was loaded into and released from the non-cross-linked multilayer film, whereas more of the macromolecular drug was loaded into and released from the cross-linked multilayer film. These results indicate that drug loading and release can be easily controlled according to the molecular weight of the desired drug by changing the structure of the film.

Tunable Oleo-Furan Surfactants by Acylation of Renewable Furans

DOE PAGES

Park, Dae Sung; Joseph, Kristeen E.; Koehle, Maura; ...

2016-10-19

One important advance in fluid surface control was the amphiphilic surfactant composed of coupled molecular structures (i.e., hydrophilic and hydrophobic) to reduce surface tension between two distinct fluid phases. However, implementation of simple surfactants has been hindered by the broad range of applications in water containing alkaline earth metals (i.e., hard water). This disrupts surfactant function and requires extensive use of undesirable and expensive chelating additives. We show that sugar-derived furans can be linked with triglyceride-derived fatty acid chains via Friedel–Crafts acylation within single layer (SPP) zeolite catalysts. Finally, these alkylfuran surfactants independently suppress the effects of hard water whilemore » simultaneously permitting broad tunability of size, structure, and function, which can be optimized for superior capability for forming micelles and solubilizing in water.« less

Tunable Oleo-Furan Surfactants by Acylation of Renewable Furans

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

Park, Dae Sung; Joseph, Kristeen E.; Koehle, Maura

2016-11-23

An important advance in fluid surface control was the amphiphilic surfactant comprised of coupled molecular structures (i.e. hydrophilic and hydrophobic) to reduce surface tension between two distinct fluid phases. However, implementation of simple surfactants has been hindered by the broad range of applications in water containing alkaline earth metals (i.e. hard water), which disrupt surfactant function and require extensive use of undesirable and expensive chelating additives. Here we show that sugar-derived furans can be linked with triglyceride-derived fatty acid chains via Friedel-Crafts acylation within single layer (SPP) zeolite catalysts. These alkylfuran surfactants independently suppress the effects of hard water whilemore » simultaneously permitting broad tunability of size, structure, and function, which can be optimized for superior capability for forming micelles and solubilizing in water.« less

Thermodiffusion as a probe of protein hydration for streptavidin and the streptavidin-biotin complex

NASA Astrophysics Data System (ADS)

Niether, Doreen; Sarter, Mona; König, Bernd; Zamponi, Michaela; Fitter, Jörg; Stadler, Andreas; Wiegand, Simone

2018-01-01

Molecular recognition via protein-ligand interactions is of fundamental importance to numerous processes in living organisms. Microscale thermophoresis (MST) uses the sensitivity of the thermophoretic response upon ligand binding to access information on the reaction kinetics. Additionally, thermophoresis is promising as a tool to gain information on the hydration layer, as the temperature dependence of the thermodiffusion behaviour is sensitive to solute-solvent interactions. To quantify the influence of structural fluctuations and conformational motion of the protein on the entropy change of its hydration layer upon ligand binding, we combine quasi-elastic incoherent neutron scattering (QENS) and isothermal titration calorimetry (ITC) data from literature. However, preliminary results show that replacing water with deuterated water leads to changes of the thermophoretic measurements, which are similar to the changes observed upon binding by biotin. In order to gain a better understanding of the hydration layer all measurements need to be performed in heavy water. This will open a route to develop a microscopic understanding of the correlation between the strength and number of hydrogen bonds and the thermophoretic behaviour.

Atomic Layer Deposition of Bismuth Vanadates for Solar Energy Materials.

PubMed

Stefik, Morgan

2016-07-07

The fabrication of porous nanocomposites is key to the advancement of energy conversion and storage devices that interface with electrolytes. Bismuth vanadate, BiVO4 , is a promising oxide for solar water splitting where the controlled fabrication of BiVO4 layers within porous, conducting scaffolds has remained a challenge. Here, the atomic layer deposition of bismuth vanadates is reported from BiPh3 , vanadium(V) oxytriisopropoxide, and water. The resulting films have tunable stoichiometry and may be crystallized to form the photoactive scheelite structure of BiVO4 . A selective etching process was used with vanadium-rich depositions to enable the synthesis of phase-pure BiVO4 after spinodal decomposition. BiVO4 thin films were measured for photoelectrochemical performance under AM 1.5 illumination. The average photocurrents were 1.17 mA cm(-2) at 1.23 V versus the reversible hydrogen electrode using a hole-scavenging sulfite electrolyte. The capability to deposit conformal bismuth vanadates will enable a new generation of nanocomposite architectures for solar water splitting. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydration properties of adenosine phosphate series as studied by microwave dielectric spectroscopy.

PubMed

Mogami, George; Wazawa, Tetsuichi; Morimoto, Nobuyuki; Kodama, Takao; Suzuki, Makoto

2011-02-01

Hydration properties of adenine nucleotides and orthophosphate (Pi) in aqueous solutions adjusted to pH=8 with NaOH were studied by high-resolution microwave dielectric relaxation (DR) spectroscopy at 20 °C. The dielectric spectra were analyzed using a mixture theory combined with a least-squares Debye decomposition method. Solutions of Pi and adenine nucleotides showed qualitatively similar dielectric properties described by two Debye components. One component was characterized by a relaxation frequency (f(c)=18.8-19.7 GHz) significantly higher than that of bulk water (17 GHz) and the other by a much lower f(c) (6.4-7.6 GHz), which are referred to here as hyper-mobile water and constrained water, respectively. By contrast, a hydration shell of only the latter type was found for adenosine (f(c)~6.7 GHz). The present results indicate that phosphoryl groups are mostly responsible for affecting the structure of the water surrounding the adenine nucleotides by forming one constrained water layer and an additional three or four layers of hyper-mobile water. Copyright © 2010 Elsevier B.V. All rights reserved.

Crystal water dynamics of guanosine dihydrate: analysis of atomic displacement parameters, time profile of hydrogen-bonding probability, and translocation of water by MD simulation.

PubMed

Yoneda, Shigetaka; Sugawara, Yoko; Urabe, Hisako

2005-01-27

The dynamics of crystal water molecules of guanosine dihydrate are investigated in detail by molecular dynamics (MD) simulation. A 2 ns simulation is performed using a periodic boundary box composed of 4 x 5 x 8 crystallographic unit cells and using the particle-mesh Ewald method for calculation of electrostatic energy. The simulated average atomic positions and atomic displacement parameters are remarkably coincident with the experimental values determined by X-ray analysis, confirming the high accuracy of this simulation. The dynamics of crystal water are analyzed in terms of atomic displacement parameters, orientation vectors, order parameters, self-correlation functions of the orientation vectors, time profiles of hydrogen-bonding probability, and translocations. The simulation clarifies that the average structure is composed of various stable and transient structures of the molecules. The simulated guanosine crystal forms a layered structure, with four water sites per asymmetric unit, classified as either interlayer water or intralayer water. From a detailed analysis of the translocations of water molecules in the simulation, columns of intralayer water molecules along the c axis appear to represent a pathway for hydration and dehydration by a kind of molecular valve mechanism.

Ceres’ impact craters: probes of near-surface internal structure and composition

NASA Astrophysics Data System (ADS)

Bland, Michael T.; Raymond, Carol; Park, Ryan; Schenk, Paul; McCord, Tom; Reddy, Vishnu; King, Scott; Sykes, Mark; Russell, Chris

2015-11-01

Dawn Framing Camera images of Ceres have revealed the existence of a heavily cratered surface. Shape models derived from these images indicate that most (though not all) large craters are quite deep: up to 6 km for craters larger than 100 km in diameter. The retention of deep craters is not consistent with a simple differentiated internal structure consisting of an outer layer composed solely of pure water ice (covered with a rocky lag) overlying a rocky core. Here we use finite element simulations to show that, for Ceres’ relatively warm surface temperatures, the timescale required to completely flatten a crater 60-km in diameter (or greater) is less than 100 Myr, assuming a relatively pure outer ice layer (for ice grain sizes ≤ 1 cm). Preserving substantial topography requires that the viscosity of Ceres’ outer-most layer (25-50 km thick) is substantially greater than that of pure water ice. A factor of ten increase in viscosity can be achieved by assuming the layer is a 50/50 ice-rock mixture by volume; however, our simulations show that such an increase is insufficient to prevent substantial relaxation over timescales of 1 Gyr. Only particulate volume fractions greater than 50% provide an increase in viscosity sufficient to prevent large-scale, rapid relaxation. Such volume fractions suggest an outer layer composed of frozen soil/regolith (i.e., more rock than ice by volume), a very salt-rich layer, or both. Notably, while most basins appear quite deep, a few relatively shallow basins have been observed (e.g., Coniraya), suggesting that relaxation may be occurring over very long timescales (e.g., 4 Ga), that Ceres’ interior is compositionally and spatial heterogeneous, and/or that temporal evolution of the interior structure and composition has occurred. If these shallow basins are in fact the result of relaxation, it places an upper limit on the viscosity of Ceres’ outer-most interior layer, implying at least some low-viscosity material is present and likely eliminating the possibility of a purely rocky (homogeneous, low density, high porosity) interior.

Turbulence structure of the marine stable boundary layer over the Baltic Sea

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

Smedman, A.S.; Hoegstroem, U.

For more than half of the year the land surfaces surrounding the Baltic Sea is warmer than the sea surface, and the marine boundary layer over the Baltic is stable. Observations, at various sites in the Baltic Sea area during the last decade. also indicate frequent occurrence of low-level jets at the top of the stable boundary layer. In many cases the marine jet can be considered as an analogy in space to the evolution of the nocturnal jet with time. The frictional decoupling occurs when warm air over the land is flowing out over the sea. Data from twomore » areas together with model simulations are used in this study to characterize turbulence structure in the marine boundary layer. The measurements include profiles of wind and temperature on towers situated at two isolated islands, together with turbulence recordings and aircraft measurements. Also wave height and water surface temperature have been measured. The model simulations are performed with a second-order closure model.« less

An ordered array of hierarchical spheres for surface-enhanced Raman scattering detection of traces of pesticide

NASA Astrophysics Data System (ADS)

Hu, Xiaoye; Zheng, Peng; Meng, Guowen; Huang, Qing; Zhu, Chuhong; Han, Fangming; Huang, Zhulin; Li, Zhongbo; Wang, Zhaoming; Wu, Nianqiang

2016-09-01

An ordered array of hierarchically-structured core-nanosphere@space-layer@shell-nanoparticles has been fabricated for surface-enhanced Raman scattering (SERS) detection. To fabricate this hierarchically-structured chip, a long-range ordered array of Au/Ag-nanospheres is first patterned in the nano-bowls on the planar surface of ordered nanoporous anodic titanium oxide template. A ultra-thin alumina middle space-layer is then conformally coated on the Au/Ag-nanospheres, and Ag-nanoparticles are finally deposited on the surface of the alumina space-layer to form an ordered array of Au/Ag-nanosphere@Al2O3-layer@Ag-nanoparticles. Finite-difference time-domain simulation shows that SERS hot spots are created between the neighboring Ag-nanoparticles. The ordered array of hierarchical nanostructures is used as the SERS-substrate for a trial detection of methyl parathion (a pesticide) in water and a limit of detection of 1 nM is reached, indicating its promising potential in rapid monitoring of organic pollutants in aquatic environment.

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.

Incorporation of layered double nanomaterials in thin film nanocomposite nanofiltration membrane for magnesium sulphate removal

NASA Astrophysics Data System (ADS)

Hanis Tajuddin, Muhammad; Yusof, Norhaniza; Salleh, Wan Norharyati Wan; Fauzi Ismail, Ahmad; Hanis Hayati Hairom, Nur; Misdan, Nurasyikin

2018-03-01

Thin film nanocomposite (TFN) membrane with copper-aluminium layered double hydroxides (LDH) incorporated into polyamide (PA) selective layer has been prepared for magnesium sulphate salt removal. 0, 0.05, 0.1, 0.15, 0.2 wt% of LDH were dispersed in the trimesoyl chloride (TMC) in n-hexane as organic solution and embedded into PA layer during interfacial polymerization with piperazine. The fabricated membranes were further characterized to evaluate its morphological structure and membrane surface hydrophilicity. The TFN membranes performance were evaluated with divalent salt magnesium sulphate (MgSO4) removal and compared with thin film composite (TFC). The morphological structures of TFN membranes were altered and the surface hydrophilicity were enhanced with addition of LDH. Incorporation of LDH has improved the permeate water flux by 82.5% compared to that of TFC membrane with satisfactory rejection of MgSO4. This study has experimentally validated the potential of LDH to improve the divalent salt separation performance for TFN membranes.

Flexible single-layer ionic organic-inorganic frameworks towards precise nano-size separation

NASA Astrophysics Data System (ADS)

Yue, Liang; Wang, Shan; Zhou, Ding; Zhang, Hao; Li, Bao; Wu, Lixin

2016-02-01

Consecutive two-dimensional frameworks comprised of molecular or cluster building blocks in large area represent ideal candidates for membranes sieving molecules and nano-objects, but challenges still remain in methodology and practical preparation. Here we exploit a new strategy to build soft single-layer ionic organic-inorganic frameworks via electrostatic interaction without preferential binding direction in water. Upon consideration of steric effect and additional interaction, polyanionic clusters as connection nodes and cationic pseudorotaxanes acting as bridging monomers connect with each other to form a single-layer ionic self-assembled framework with 1.4 nm layer thickness. Such soft supramolecular polymer frameworks possess uniform and adjustable ortho-tetragonal nanoporous structure in pore size of 3.4-4.1 nm and exhibit greatly convenient solution processability. The stable membranes maintaining uniform porous structure demonstrate precisely size-selective separation of semiconductor quantum dots within 0.1 nm of accuracy and may hold promise for practical applications in selective transport, molecular separation and dialysis systems.

Variation of turbulence in a coastal thermal internal boundary layer

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

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

1981-01-01

Internal boundary layers (IBL) form when an air mass encounters a change in surface characteristics. There are essentially two types of internal boundary layers - one caused by the change in surface roughness and the other by the variation in surface heating. The former is known as the aerodynamic internal boundary layer (AIBL) and the latter the thermal internal boundary layer (TIBL). Change in shear stress generally characterizes the AIBL and change in turbulence the TIBL. Results of some observations of the vertical component of turbulence made in a coastal TIBL over Long Island, New York from 1974 to 1978more » are reported. Vertical turbulence measured by a simple sail plane variometer in a thermal internal boundary layer over Long Island with onshore flows indicates the structure to depend significantly on the land-water temperature difference. The position of the vertical velocity fluctuation maximum seems to vary from one test to another but its variation could not be correlated to other parameters due to lack of a sufficient number of tests. The structure of vertical turbulence was found to be different for sea breeze flows as compared to gradient winds.« less

Resistivity structure and geochemistry of the Jigokudani Valley hydrothermal system, Mt. Tateyama, Japan

NASA Astrophysics Data System (ADS)

Seki, Kaori; Kanda, Wataru; Tanbo, Toshiya; Ohba, Takeshi; Ogawa, Yasuo; Takakura, Shinichi; Nogami, Kenji; Ushioda, Masashi; Suzuki, Atsushi; Saito, Zenshiro; Matsunaga, Yasuo

2016-10-01

This study clarifies the hydrothermal system of Jigokudani Valley near Mt. Tateyama volcano in Japan by using a combination of audio-frequency magnetotelluric (AMT) survey and hot-spring water analysis in order to assess the potential of future phreatic eruptions in the area. Repeated phreatic eruptions in the area about 40,000 years ago produced the current valley morphology, which is now an active solfatara field dotted with hot springs and fumaroles indicative of a well-developed hydrothermal system. The three-dimensional (3D) resistivity structure of the hydrothermal system was modeled by using the results of an AMT survey conducted at 25 locations across the valley in 2013-2014. The model suggests the presence of a near-surface highly conductive layer of < 50 m in thickness across the entire valley, which is interpreted as a cap rock layer. Immediately below the cap rock is a relatively resistive body interpreted as a gas reservoir. Field measurements of temperature, pH, and electrical conductivity (EC) were taken at various hot springs across the valley, and 12 samples of hot-spring waters were analyzed for major ion chemistry and H2O isotopic ratios. All hot-spring waters had low pH and could be categorized into three types on the basis of the Cl-/SO 42 - concentration ratio, with all falling largely on a mixing line between magmatic fluids and local meteoric water (LMW). The geochemical analysis suggests that the hydrothermal system includes a two-phase zone of vapor-liquid. A comparison of the resistivity structure and the geochemically inferred structure suggests that a hydrothermal reservoir is present at a depth of approximately 500 m, from which hot-spring water differentiates into the three observed types. The two-phase zone appears to be located immediately beneath the cap rock structure. These findings suggest that the hydrothermal system of Jigokudani Valley exhibits a number of factors that could trigger a future phreatic eruption.

Effect of Concentration on the Interfacial and Bulk Structure of Ionic Liquids in Aqueous Solution.

PubMed

Cheng, H-W; Weiss, H; Stock, P; Chen, Y-J; Reinecke, C R; Dienemann, J-N; Mezger, M; Valtiner, M

2018-02-27

Bio and aqueous applications of ionic liquids (IL) such as catalysis in micelles formed in aqueous IL solutions or extraction of chemicals from biologic materials rely on surface-active and self-assembly properties of ILs. Here, we discuss qualitative relations of the interfacial and bulk structuring of a water-soluble surface-active IL ([C 8 MIm][Cl]) on chemically controlled surfaces over a wide range of water concentrations using both force probe and X-ray scattering experiments. Our data indicate that IL structuring evolves from surfactant-like surface adsorption at low IL concentrations, to micellar bulk structure adsorption above the critical micelle concentration, to planar bilayer formation in ILs with <1 wt % of water and at high charging of the surface. Interfacial structuring is controlled by mesoscopic bulk structuring at high water concentrations. Surface chemistry and surface charges decisively steer interfacial ordering of ions if the water concentration is low and/or the surface charge is high. We also demonstrate that controlling the interfacial forces by using self-assembled monolayer chemistry allows tuning of interfacial structures. Both the ratio of the head group size to the hydrophobic tail volume as well as the surface charging trigger the bulk structure and offer a tool for predicting interfacial structures. Based on the applied techniques and analyses, a qualitative prediction of molecular layering of ILs in aqueous systems is possible.

Nanosized CaP-silk fibroin-PCL-PEG-PCL/PCL based bilayer membranes for guided bone regeneration.

PubMed

Türkkan, Sibel; Pazarçeviren, A Engin; Keskin, Dilek; Machin, Nesrin E; Duygulu, Özgür; Tezcaner, Ayşen

2017-11-01

Guided bone regeneration (GBR) concept has been developed to prevent the formation of non-functional scar tissue layer on defect site by undertaking barrier role. In this study, a new bilayer membrane which consisted of one layer of electrospun silk fibroin/PCL-PEG-PCL incorporating nanocalcium phosphate (SPCA) 1 and one layer of PCL membrane was developed for GBR. To improve the osteoconductivity of membranes, nanosized calcium phosphate particles synthesized by Flame Spray Pyrolysis method were incorporated into membranes at 10% (wt) (SPCA10) and 20% (wt) (SPCA20) of the polymer content. The structural and chemical analyses revealed the well-integrated two layers of membranes with a total thickness of ca 100μm. In the regenerative layer, the highly porous mesh structure had a thickness of 12.6μm with randomly oriented fibers having diameters around 760nm, and nanoparticles dispersed homogenously. The mechanical test results showed remarkable improvement on the tensile strength of membranes with incorporation of nanoparticles. Higher water affinity of nanoCaP included membranes was proved by lower contact angle values and higher percent water uptake capacity. Biomineralization assay revealed that nucleation and growth of apatites around fibers of SPCA10 and SPCA20 were apparent while on SPCA0 apatite minerals were barely detected after 10days. Human dental pulp stem cells (DPSC) were seeded on electrospun layer of the bilayer membranes for biocompatibility and osteo-compatibility study. Increasing nanoCaP amount resulted in higher cell adhesion, proliferation, ALP activity and calcium deposition on membranes. These overall results confirmed the biocompatibility and potential applicability of proposed membranes for GBR treatments. Copyright © 2017 Elsevier B.V. All rights reserved.

Similar Ring Structures on Mars and Tibetan Plateau confirm recent tectonism on Martian Northern polar region

NASA Astrophysics Data System (ADS)

Anglés, A.; Li, Y. L.

2017-10-01

The polar regions of Mars feature layered deposits, some of which exist as enclosed zoning structures. These deposits raised strong interest since their discovery and still remain one of the most controversial features on Mars. Zoning structures that are enclosed only appear in the Northern polar region, where the disappearance of water bodies may have left behind huge deposits of evaporate salts. The origin of the layered deposits has been widely debated. Here we propose that the enclosed nature of the zoning structures indicates the result of recent tectonism. We compared similar structures at an analogue site located in the western Qaidam Basin of Tibetan Plateau, a unique tectonic setting with abundant saline deposits. The enclosed structures, which we term Ring Structures, in both the analogue site and in the Northern polar region of Mars, were formed by uplift induced pressurization and buoyancy of salts as the result of recent tectonic activity.

Organic matter composition of soil macropore surfaces under different agricultural management practices

NASA Astrophysics Data System (ADS)

Glæsner, Nadia; Leue, Marin; Magid, Jacob; Gerke, Horst H.

2016-04-01

Understanding the heterogeneous nature of soil, i.e. properties and processes occurring specifically at local scales is essential for best managing our soil resources for agricultural production. Examination of intact soil structures in order to obtain an increased understanding of how soil systems operate from small to large scale represents a large gap within soil science research. Dissolved chemicals, nutrients and particles are transported through the disturbed plow layer of agricultural soil, where after flow through the lower soil layers occur by preferential flow via macropores. Rapid movement of water through macropores limit the contact between the preferentially moving water and the surrounding soil matrix, therefore contact and exchange of solutes in the water is largely restricted to the surface area of the macropores. Organomineral complex coated surfaces control sorption and exchange properties of solutes, as well as availability of essential nutrients to plant roots and to the preferentially flowing water. DRIFT (Diffuse Reflectance infrared Fourier Transform) Mapping has been developed to examine composition of organic matter coated macropores. In this study macropore surfaces structures will be determined for organic matter composition using DRIFT from a long-term field experiment on waste application to agricultural soil (CRUCIAL, close to Copenhagen, Denmark). Parcels with 5 treatments; accelerated household waste, accelerated sewage sludge, accelerated cattle manure, NPK and unfertilized, will be examined in order to study whether agricultural management have an impact on the organic matter composition of intact structures.

Liquid-Infused Smooth Surface for Improved Condensation Heat Transfer.

PubMed

Tsuchiya, Hirotaka; Tenjimbayashi, Mizuki; Moriya, Takeo; Yoshikawa, Ryohei; Sasaki, Kaichi; Togasawa, Ryo; Yamazaki, Taku; Manabe, Kengo; Shiratori, Seimei

2017-09-12

Control of vapor condensation properties is a promising approach to manage a crucial part of energy infrastructure conditions. Heat transfer by vapor condensation on superhydrophobic coatings has garnered attention, because dropwise condensation on superhydrophobic surfaces with rough structures leads to favorable heat-transfer performance. However, pinned condensed water droplets within the rough structure and a high thermodynamic energy barrier for nucleation of superhydrophobic surfaces limit their heat-transfer increase. Recently, slippery liquid-infused surfaces (SLIPS) have been investigated, because of their high water sliding ability and surface smoothness originating from the liquid layer. However, even on SLIPS, condensed water droplets are eventually pinned to degrade their heat-transfer properties after extended use, because the rough base layer is exposed as infused liquid is lost. Herein, we report a liquid-infused smooth surface named "SPLASH" (surface with π electron interaction liquid adsorption, smoothness, and hydrophobicity) to overcome the problems derived from the rough structures in previous approaches to obtain stable, high heat-transfer performance. The SPLASH displayed a maximum condensation heat-transfer coefficient that was 175% higher than that of an uncoated substrate. The SPLASH also showed higher heat-transfer performance and more stable dropwise condensation than superhydrophobic surfaces and SLIPS from the viewpoints of condensed water droplet mobility and the thermodynamic energy barrier for nucleation. The effects of liquid-infused surface roughness and liquid viscosity on condensation heat transfer were investigated to compare heat-transfer performance. This research will aid industrial applications using vapor condensation.

Crystal structure of dimanganese(II) zinc bis­[ortho­phosphate(V)] monohydrate

PubMed Central

Alhakmi, Ghaleb; Assani, Abderrazzak; Saadi, Mohamed; El Ammari, Lahcen

2015-01-01

The title compound, Mn2Zn(PO4)2·H2O, was obtained under hydro­thermal conditions. The structure is isotypic with other transition metal phosphates of the type M 3− xM′x(PO4)2·H2O, but shows no statistical disorder of the three metallic sites. The principal building units are distorted [MnO6] and [MnO5(H2O)] octa­hedra, a distorted [ZnO5] square pyramid and two regular PO4 tetra­hedra. The connection of the polyhedra leads to a framework structure. Two types of layers parallel to (-101) can be distinguished in this framework. One layer contains [Zn2O8] dimers linked to PO4 tetra­hedra via common edges. The other layer is more corrugated and contains [Mn2O8(H2O)2] dimers and [MnO6] octa­hedra linked together by common edges. The PO4 tetra­hedra link the two types of layers into a framework structure with channels parallel to [101]. The H atoms of the water mol­ecules point into the channels and form O—H⋯O hydrogen bonds (one of which is bifurcated) with framework O atoms across the channels. PMID:25878806

Effects of different regulatory methods on improvement of greenhouse saline soils, tomato quality, and yield.

PubMed

Maomao, Hou; Xiaohou, Shao; Yaming, Zhai

2014-01-01

To identify effective regulatory methods scheduling with the compromise between the soil desalination and the improvement of tomato quality and yield, a 3-year field experiment was conducted to evaluate and compare the effect of straw mulching and soil structure conditioner and water-retaining agent on greenhouse saline soils, tomato quality, and yield. A higher salt removing rate of 80.72% in plough layer with straw mulching was obtained based on the observation of salt mass fraction in 0 ~ 20 cm soil layer before and after the experiment. Salts were also found to move gradually to the deeper soil layer with time. Straw mulching enhanced the content of soil organic matter significantly and was conductive to reserve soil available N, P, and K, while available P and K in soils of plough layer with soil structure conditioner decreased obviously; thus a greater usage of P fertilizer and K fertilizer was needed when applying soil structure conditioner. Considering the evaluation indexes including tomato quality, yield, and desalination effects of different regulatory methods, straw mulching was recommended as the main regulatory method to improve greenhouse saline soils in south China. Soil structure conditioner was the suboptimal method, which could be applied in concert with straw mulching.

An NMR Study of Biomimetic Fluorapatite – Gelatine Mesocrystals

PubMed Central

Vyalikh, Anastasia; Simon, Paul; Rosseeva, Elena; Buder, Jana; Scheler, Ulrich; Kniep, Rüdiger

2015-01-01

The mesocrystal system fluoroapatite—gelatine grown by double-diffusion is characterized by hierarchical composite structure on a mesoscale. In the present work we apply solid state NMR to characterize its structure on the molecular level and provide a link between the structural organisation on the mesoscale and atomistic computer simulations. Thus, we find that the individual nanocrystals are composed of crystalline fluorapatite domains covered by a thin boundary apatite-like layer. The latter is in contact with an amorphous layer, which fills the interparticle space. The amorphous layer is comprised of the organic matrix impregnated by isolated phosphate groups, Ca3F motifs and water molecules. Our NMR data provide clear evidence for the existence of precursor complexes in the gelatine phase, which were not involved in the formation of apatite crystals, proving hence theoretical predictions on the structural pre-treatment of gelatine by ion impregnation. The interfacial interactions, which may be described as the glue holding the composite materials together, comprise hydrogen bond interactions with the apatite PO43− groups. The reported results are in a good agreement with molecular dynamics simulations, which address the mechanisms of a growth control by collagen fibers, and with experimental observations of an amorphous cover layer in biominerals. PMID:26515127

Diversity and community structure of marine microbes around the Benham Rise underwater plateau, northeastern Philippines.

PubMed

Gajigan, Andrian P; Yñiguez, Aletta T; Villanoy, Cesar L; San Diego-McGlone, Maria Lourdes; Jacinto, Gil S; Conaco, Cecilia

2018-01-01

Microbes are central to the structuring and functioning of marine ecosystems. Given the remarkable diversity of the ocean microbiome, uncovering marine microbial taxa remains a fundamental challenge in microbial ecology. However, there has been little effort, thus far, to describe the diversity of marine microorganisms in the region of high marine biodiversity around the Philippines. Here, we present data on the taxonomic diversity of bacteria and archaea in Benham Rise, Philippines, Western Pacific Ocean, using 16S V4 rRNA gene sequencing. The major bacterial and archaeal phyla identified in the Benham Rise are Proteobacteria, Cyanobacteria, Actinobacteria, Bacteroidetes, Marinimicrobia, Thaumarchaeota and, Euryarchaeota. The upper mesopelagic layer exhibited greater microbial diversity and richness compared to surface waters. Vertical zonation of the microbial community is evident and may be attributed to physical stratification of the water column acting as a dispersal barrier. Canonical Correspondence Analysis (CCA) recapitulated previously known associations of taxa and physicochemical parameters in the environment, such as the association of oligotrophic clades with low nutrient surface water and deep water clades that have the capacity to oxidize ammonia or nitrite at the upper mesopelagic layer. These findings provide foundational information on the diversity of marine microbes in Philippine waters. Further studies are warranted to gain a more comprehensive picture of microbial diversity within the region.

Diversity and community structure of marine microbes around the Benham Rise underwater plateau, northeastern Philippines

PubMed Central

Gajigan, Andrian P.; Yñiguez, Aletta T.; Villanoy, Cesar L.; San Diego-McGlone, Maria Lourdes; Jacinto, Gil S.

2018-01-01

Microbes are central to the structuring and functioning of marine ecosystems. Given the remarkable diversity of the ocean microbiome, uncovering marine microbial taxa remains a fundamental challenge in microbial ecology. However, there has been little effort, thus far, to describe the diversity of marine microorganisms in the region of high marine biodiversity around the Philippines. Here, we present data on the taxonomic diversity of bacteria and archaea in Benham Rise, Philippines, Western Pacific Ocean, using 16S V4 rRNA gene sequencing. The major bacterial and archaeal phyla identified in the Benham Rise are Proteobacteria, Cyanobacteria, Actinobacteria, Bacteroidetes, Marinimicrobia, Thaumarchaeota and, Euryarchaeota. The upper mesopelagic layer exhibited greater microbial diversity and richness compared to surface waters. Vertical zonation of the microbial community is evident and may be attributed to physical stratification of the water column acting as a dispersal barrier. Canonical Correspondence Analysis (CCA) recapitulated previously known associations of taxa and physicochemical parameters in the environment, such as the association of oligotrophic clades with low nutrient surface water and deep water clades that have the capacity to oxidize ammonia or nitrite at the upper mesopelagic layer. These findings provide foundational information on the diversity of marine microbes in Philippine waters. Further studies are warranted to gain a more comprehensive picture of microbial diversity within the region. PMID:29785352

The diffusive boundary layer of sediments: oxygen microgradients over a microbial mat

NASA Technical Reports Server (NTRS)

Jorgensen, B. B.; Des Marais, D. J.

1990-01-01

Oxygen microelectrodes were used to analyze the distribution of the diffusive boundary layer (DBL) at the sediment-water interface in relation to surface topography and flow velocity. The sediment, collected from saline ponds, was covered by a microbial mat that had high oxygen consumption rate and well-defined surface structure. Diffusion through the DBL constituted an important rate limitation to the oxygen uptake of the sediment. The mean effective DBL thickness decreased from 0.59 to 0.16 mm as the flow velocity of the overlying water was increased from 0.3 to 7.7 cm s-1 (measured 1 cm above the mat). The oxygen uptake rate concurrently increased from 3.9 to 9.4 nmol cm-2 min-1. The effects of surface roughness and topography on the thickness and distribution of the DBL were studied by three-dimensional mapping of the sediment-water interface and the upper DBL boundary at 0.1-mm spatial resolution. The DBL boundary followed mat structures that had characteristic dimensions > 1/2 DBL thickness but the DBL had a dampened relief relative to the mat. The effective surface area of the sediment-water interface and of the upper DBL boundary were 31 and 14% larger, respectively, than a flat plane. Surface topography thereby increased the oxygen flux across the sediment-water interface by 49% relative to a one-dimensional diffusion flux calculated from the vertical oxygen microgradients.

[Effects of short-term deep vertically rotary tillage on topsoil structure of lime concretion black soil and wheat growth in Huang-Huai-Hai Plain, China].

PubMed

Zhai, Zhen; Li, Yu Yi; Zhang, Li; Pang, Bo; Pang, Huan Cheng; Wei, Ben Hui; Wang, Qing Wei; Qi, Shao Wei

2017-04-18

Annual rotary tillage can often create a compacted plough pan and shallow arable layer which hampers the high crop yield in Huang-Huai-Hai region. A brand new farming method named Vertically Rotary Tillage was introduced to solve this problem. One short-term field experiment was conducted to explore the effect of deep vertically rotary tillage on soil physical properties and photosynthetic characteristics at flowering stage of winter wheat. Two tillage treatments were designed including subsoiling tillage with 20 cm depth (SS 20 , CK) and deep vertically rotary tillage with 30 cm depth (DVR 30 ). The result showed that compared with SS 20 treatment, DVR 30 treatment could thoroughly break the plow pan and loose the arable layer. The soil bulk density at 10-20 cm and 20-30 cm layers under DVR 30 treatment was decreased by 9.5% and 11.2% respectively than that under SS 20 treatment. Meanwhile, the penetration resistance at 20-30 cm layer under DVR 30 treatment was also decreased by 42.3% than that under SS 20 treatment. Moreover, water infiltration under DVR 30 treatment and the soil water storage in the deep soil layers was then increased. The mass water content of soil increased significantly with the increase of soil depth. There was significant difference of mass water content of 30-40 cm 40-50 cm between SS 20 and DVR 30 . The mass water content 30-40 cm and 40-50 cm layers under DVR 30 treatment was increased by 16.9% and 10.6% compared with SS 20 treatment, respectively. Furthermore, DVR 30 treatment promoted the improvement of the photosynthetic capacity of wheat which could contribute to the dry matter accumulation of winter wheat. The net photosynthesis rate and SPAD at flowering stage of winter wheat leaves under DVR 30 treatment were increased by 1.3% and 15.5% respectively than that under SS 20 treatment, thereby the above and underground dry matter accumulation of winter wheat under DVR 30 was increased significantly. Due to all the superiority of DVR 30 treatment over SS 20 treatment showed above, the winter wheat yield under DVR 30 treatment was increased by 12.4% than that under SS 20 . It was concluded that deep vertically rotary tillage could provide a new and effective way to break up the compacted plough pan, build a reasonable soil structure and increase crop yield.

Toward low friction in water for Mo2N/Ag coatings by tailoring the wettability

NASA Astrophysics Data System (ADS)

Dai, Xuan; Wen, Mao; Huang, Keke; Wang, Xin; Yang, Lina; Wang, Jia; Zhang, Kan

2018-07-01

Increasing demands for robust surfaces in harsh conditions, such as erosion, abrasion and sea-water, has stimulated the development of self-lubricated protective coatings. Meanwhile, due to the oil crisis, research in water lubrication again attracts much attention from both academics and practical engineers. Here, a higher hydrophilicity accompanying with a remarkable drop of friction coefficient in water environment was achieved successfully in Mo2N/Ag coatings by increasing Ag content. To do these, the Mo2N/Ag coatings with different Ag content were deposited by co-sputtering, which exhibit a nanocomposite structure consisting of precipitate Ag embedded in the Mo2N matrix. The high hydrophilicity can be ascribed to the combined contributions of the partial oxidation of Mo2N and high polarity of Ag precipitates. The decrease of friction coefficient is illustrated by the colloidal friction products and a mode with electric double layer. In which, enhanced hydrophilicity will result in forming a thin "water film" layer between the interface of counterpart and the coatings. And the MoOx/Ag2Mo4O13 derived from the hydrolysis action of Mo2N/Ag sliding in water could function as lubricant phase. Meanwhile, these negative charged MoOx/Ag2Mo4O13 colloidal particles induce the rearrangement of positive ions in the "water film" and form an electric double layer, which also contributes to the decrease of friction coefficient.

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.

Do lipids retard the evaporation of the tear fluid?

PubMed

Rantamäki, Antti H; Javanainen, Matti; Vattulainen, Ilpo; Holopainen, Juha M

2012-09-21

We examined in vitro the potential evaporation-retarding effect of the tear film lipid layer (TFLL). The artificial TFLL compositions used here were based on the present knowledge of TFLL composition. A custom-built system was developed to measure evaporation rates at 35°C. Lipids were applied to an air-water interface, and the evaporation rate through the lipid layer was defined as water loss from the interface. A thick layer of olive oil and a monolayer of long-chain alcohol were used as controls. The artificial TFLLs were composed of 1 to 4 lipid species: polar phosphatidylcholine (PC), nonpolar cholesteryl ester, triglycerides, and wax ester (WE). Brewster angle microscopy (BAM) and interfacial shear rheometry (ISR) were used to assess the lateral structure and shear stress response of the lipid layers, respectively. Olive oil and long-chain alcohol decreased evaporation by 54% and 45%, respectively. The PC monolayer and the four-component mixtures did not retard evaporation. WE was the most important evaporation-retardant TFLL lipid (∼20% decrease). In PC/WE mixtures, an ∼90% proportion of WE was required for evaporation retardation. Based on BAM and ISR, WE resulted in more condensed layers than the non-retardant layers. Highly condensed, solid-like lipid layers, such as those containing high proportions of WEs, are evaporation-retardant. In multi-component lipid layers, the evaporation-retardant interactions between carbon chains decrease and, therefore, these lipid layers do not retard evaporation.

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).

Structural control of coalbed methane production in Alabama

USGS Publications Warehouse

Pashin, J.C.; Groshong, R.H.

1998-01-01

Thin-skinned structures are distributed throughout the Alabama coalbed methane fields, and these structures affect the production of gas and water from coal-bearing strata. Extensional structures in Deerlick Creek and Cedar Cove fields include normal faults and hanging-wall rollovers, and area balancing indicates that these structures are detached in the Pottsville Formation. Compressional folds in Gurnee and Oak Grove fields, by comparison, are interpreted to be detachment folds formed above decollements at different stratigraphic levels. Patterns of gas and water production reflect the structural style of each field and further indicate that folding and faulting have affected the distribution of permeability and the overall success of coalbed methane operations. Area balancing can be an effective way to characterize coalbed methane reservoirs in structurally complex regions because it constrains structural geometry and can be used to determine the distribution of layer-parallel strain. Comparison of calculated requisite strain and borehole expansion data from calliper logs suggests that strain in coalbed methane reservoirs is predictable and can be expressed as fracturing and small-scale faulting. However, refined methodology is needed to analyze heterogeneous strain distributions in discrete bed segments. Understanding temporal variation of production patterns in areas where gas and water production are influenced by map-scale structure will further facilitate effective management of coalbed methane fields.Thin-skinned structures are distributed throughout the Alabama coalbed methane fields, and these structures affect the production of gas and water from coal-bearing strata. Extensional structures in Deerlick Creek and Cedar Cove fields include normal faults and hanging-wall rollovers, and area balancing indicates that these structures are detached in the Pottsville Formation. Compressional folds in Gurnee and Oak Grove fields, by comparison, are interpreted to be detachment folds formed above decollements at different stratigraphic levels. Patterns of gas and water production reflect the structural style of each field and further indicate that folding and faulting have affected the distribution of permeability and the overall success of coalbed methane operations. Area balancing can be an effective way to characterize coalbed methane reservoirs in structurally complex regions because it constrains structural geometry and can be used to determine the distribution of layer-parallel strain. Comparison of calculated requisite strain and borehole expansion data from calliper logs suggests that strain in coalbed methane reservoirs is predictable and can be expressed as fracturing and small-scale faulting. However, refined methodology is needed to analyze heterogeneous strain distributions in discrete bed segments. Understanding temporal variation of production patterns in areas where gas and water production are influenced by map-scale structure will further facilitate effective management of coalbed methane fields.

Controlling effects of mesoscale eddies on thermohaline structure and in situ chlorophyll distribution in the western North Pacific

NASA Astrophysics Data System (ADS)

Gao, Wei; Wang, Zhenyan; Zhang, Kainan

2017-11-01

Based on the conductivity, temperature and depth (CTD) data collected at 93 hydrographic stations during a marine cruise and on contemporary satellite altimeter observations, a series of eddies have been observed passing over the stratified upper water of the Parece Vela Basin. The results from hydrographic measurements and in situ chlorophyll fluorescence measurements have revealed that these eddies exerted significant controlling effects on the thermohaline structure and chlorophyll distribution, especially on the prevalent subsurface chlorophyll maximum layer (SCML). Based on these observations and particulate beam attenuation coefficient (cp) data, the in situ phytoplankton bloom around the pycnocline can be largely attributable to the formation of a well-developed SCML in the studied system. The uplift of the cold subsurface water within the cyclone, shoaling the pycnocline to a shallower layer, resulted in a low-temperature anomaly and different salinity anomalies at different depths. This uplift in the cyclone further caused the SCML to appear at a shallower depth with a higher in situ chlorophyll concentration than that in the normal domain. Conversely, the sinking of the warm surface water to the subsurface layer within the anticyclone depressed the pycnocline to a deeper layer and generated a high-temperature anomaly and opposite salinity anomalies compared with the cyclone. The sinking of the pycnocline within the anticyclone considerably influenced the characteristics of the SCML, which had a deeper depth and a lower in situ chlorophyll concentration than that of the normal sea. This study contributes rare quasi-synchronous CTD observations capturing mesoscale eddies and provides valuable descriptions of the variations in the SCML under the influence of mesoscale eddies based on in situ optical measurements from the seldom-discussed western North Pacific.

Structural definition of the BIL and DL: a new universal methodology to rationalize non-linear χ(2)(ω) SFG signals at charged interfaces, including χ(3)(ω) contributions.

PubMed

Pezzotti, Simone; Galimberti, Daria Ruth; Shen, Y Ron; Gaigeot, Marie-Pierre

2018-02-14

This work provides unambiguous definitions from theoretical simulations of the two interfacial regions named the BIL (binding interfacial layer) and DL (diffuse layer) at charged solid/water and air/water interfaces. The BIL and DL nomenclature follows the pioneering work of Wen et al. [Phys. Rev. Lett. 2016, 116, 016101]. Our definitions are based on the intrinsic structural properties of water only. Knowing the BIL and DL interfacial regions, one is then able to deconvolve the χ (2) (ω) non-linear SFG (sum frequency generation) response into χ(ω) and χ(ω) contributions, thus providing a detailed molecular interpretation of these signals and of the measured total SFG. We furthermore show that the χ(ω) spectrum arises from the χ (3) (ω) non-linear third order contribution of bulk liquid water, here calculated for several charged interfaces and shown to be universal. The χ(ω) contribution therefore has the same origin in terms of molecular normal modes at any charged interface. The molecular interpretation of χ(ω) is hence at the heart of the unambiguous molecular comprehension and interpretation of the measured total SFG signal at any charged interface.

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

Hammond, Glenn Edward; Bao, J; Huang, M

Hyporheic exchange is a critical mechanism shaping hydrological and biogeochemical processes along a river corridor. Recent studies on quantifying the hyporheic exchange were mostly limited to local scales due to field inaccessibility, computational demand, and complexity of geomorphology and subsurface geology. Surface flow conditions and subsurface physical properties are well known factors on modulating the hyporheic exchange, but quantitative understanding of their impacts on the strength and direction of hyporheic exchanges at reach scales is absent. In this study, a high resolution computational fluid dynamics (CFD) model that couples surface and subsurface flow and transport is employed to simulate hyporheicmore » exchanges in a 7-km long reach along the main-stem of the Columbia River. Assuming that the hyporheic exchange does not affect surface water flow conditions due to its negligible magnitude compared to the volume and velocity of river water, we developed a one-way coupled surface and subsurface water flow model using the commercial CFD software STAR-CCM+. The model integrates the Reynolds-averaged Navier-Stokes (RANS) equation solver with a realizable κ-ε two-layer turbulence model, a two-layer all y + wall treatment, and the volume of fluid (VOF) method, and is used to simulate hyporheic exchanges by tracking the free water-air interface as well as flow in the river and the subsurface porous media. The model is validated against measurements from acoustic Doppler current profiler (ADCP) in the stream water and hyporheic fluxes derived from a set of temperature profilers installed across the riverbed. The validated model is then employed to systematically investigate how hyporheic exchanges are influenced by surface water fluid dynamics strongly regulated by upstream dam operations, as well as subsurface structures (e.g. thickness of riverbed and subsurface formation layers) and hydrogeological properties (e.g. permeability). The results suggest that the thickness of riverbed alluvium layer is the dominant factor for reach-scale hyporheic exchanges, followed by the alluvium permeability, the depth of the underlying impermeable layer, and the assumption of hydrostatic pressure.« less

Variability of interleaving structure of Atlantic Water during its propagation along the Eurasian basin (Arctic Ocean) continental margin

NASA Astrophysics Data System (ADS)

Zhurbas, Nataliya; Kuzmina, Natalia; Lyzhkov, Dmitry; Ostapchuk, Alexey

2017-04-01

In order to give detailed description of the interleaving structure in the Eurasian basin results of observations carried out during NABOS 2008 and Polarstern cruise in 1996 were analyzed. The study was focused on interleaving parameters (structure and vertical scale of intrusions) variability in the upper (150-300 meters) and intermediate (300-700 meters) layers of the ocean. Based on θ,S/θ,σ-diagrams (θ, S and σ are the potential temperature, salinity and potential density, correspondingly) analysis two main results were obtained. First of all it was shown that intrusive layers carried by the mean current along the Eurasian Basin continental margin become deeper relatively isopycnals and thus stimulate ventilation of pycnocline. Second, the area in Eurasian Basin thermocline was found where intrusive layers of large and small scale were absent. This distinctive feature can be explained by intensive mixing between two branches of Atlantic Water, one of which propagates along Eurasian basin continental margin and the other spreads across the basin due to large scale interleaving processes. Among others, one of the possible methods of integral estimation of Atlantic water masses heat and salt contents variations during their expansion along basin continental margin was proposed. Thus it is reasonable to assess variation of square under the θ(S)-diagrams, which illustrate the data obtained from two CTD-stations located on diametrically opposite sides of Eurasian Basin, taking 0.5°C isotherm as a reference value. For verification of the introduced approach the estimates of heat and salt contents variations were made by different methods. Detailed discussion of the results is presented. Work was supported by the Russian Foundation for Basic Research (Grant No 15-05-01479-a).

Transition Helmholtz free energy, entropy, and heat capacity of free-standing smectic films in water: A mean-field treatment

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

Śliwa, Izabela, E-mail: izasliwa@ifmpan.poznan.pl; Zakharov, A. V., E-mail: alexandre.zakharov@yahoo.ca

Using the extended McMillan's mean field approach with anisotropic forces a study of both the structural and thermodynamic properties of free-standing smectic film (FSSF) in water on heating to the isotropic temperature is carried out numerically. By solving the self-consistent nonlinear equations for the order parameters, we obtained that the smectic-A-isotropic (AI) transition occurs through the series of layer-thinning transitions causing the films to thin in the stepwise manner as the temperature is increased above the bulk smectic-A-isotropic temperature T{sub AI}(bulk). With enhanced pair interactions in the bounding layers, the smectic-isotropic transition corresponds to smectic melting of the central layers.more » The effects of surface “enhanced” pair interactions in the bounding layers and of film thickness on the orientational and translational order parameters, the Helmholtz free energy and entropy, as well as the temperature dependence of the heat capacity of FSSFs, have also been investigated. Reasonable agreement between the theoretically predicted and the experimentally obtained – by means of optical microscopy and ellipsometry techniques – data of the temperature when the thin decylcyanobiphenyl smectic film immersing in water ruptures has been obtained.« less

A new nanocomposite forward osmosis membrane custom-designed for treating shale gas wastewater

PubMed Central

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

2015-01-01

Managing the wastewater discharged from oil and shale gas fields is a big challenge, because this kind of wastewater is normally polluted by high contents of both oils and salts. Conventional pressure-driven membranes experience little success for treating this wastewater because of either severe membrane fouling or incapability of desalination. In this study, we designed a new nanocomposite forward osmosis (FO) membrane for accomplishing simultaneous oil/water separation and desalination. This nanocomposite FO membrane is composed of an oil-repelling and salt-rejecting hydrogel selective layer on top of a graphene oxide (GO) nanosheets infused polymeric support layer. The hydrogel selective layer demonstrates strong underwater oleophobicity that leads to superior anti-fouling capability under various oil/water emulsions, and the infused GO in support layer can significantly mitigate internal concentration polarization (ICP) through reducing FO membrane structural parameter by as much as 20%. Compared with commercial FO membrane, this new FO membrane demonstrates more than three times higher water flux, higher removals for oil and salts (>99.9% for oil and >99.7% for multivalent ions) and significantly lower fouling tendency when investigated with simulated shale gas wastewater. These combined merits will endorse this new FO membrane with wide applications in treating highly saline and oily wastewaters. PMID:26416014

Water channel structures analysed by electron crystallography.

PubMed

Tani, Kazutoshi; Fujiyoshi, Yoshinori

2014-05-01

The mechanisms underlying water transport through aquaporin (AQP) have been debated for two decades. The water permeation phenomenon of AQP seems inexplicable because the Grotthuss mechanism does not allow for simultaneous fast water permeability and inhibition of proton transfer through the hydrogen bonds of water molecules. The AQP1 structure determined by electron crystallography provided the first insights into the proton exclusion mechanism despite fast water permeation. Although several studies have provided clues about the mechanism based on the AQP structure, each proposed mechanism remains incomplete. The present review is focused on AQP function and structure solved by electron crystallography in an attempt to fill the gaps between the findings in the absence and presence of lipids. Many AQP structures can be superimposed regardless of the determination method. The AQP fold is preserved even under conditions lacking lipids, but the water arrangement in the channel pore differs. The differences might be explained by dipole moments formed by the two short helices in the lipid bilayer. In addition, structure analyses of double-layered two-dimensional crystals of AQP suggest an array formation and cell adhesive function. Electron crystallography findings not only have contributed to resolve some of the water permeation mechanisms, but have also elucidated the multiple functions of AQPs in the membrane. The roles of AQPs in the brain remain obscure, but their multiple activities might be important in the regulation of brain and other biological functions. This article is part of a Special Issue entitled Aquaporins. © 2013.

Earth observations during STS-58

NASA Image and Video Library

1993-10-22

STS058-88-017 (18 Oct-1 Nov 1993) --- The eye-catching "bullseye" of the Richat Structure adds interest to the barren Gres de Chinguetti Plateau in central Mauretania, northwest Africa. It represents domally uplifted, layered (sedimentary) rocks that have been eroded by water and wind into the present shape. Desert sands have invaded the feature from the south. The origin of the structure is unknown. It is not an impact structure, because field work showed that strata are undisturbed and flat-lying in the middle of the feature, and no shock-altered rock could be found. There is no evidence for a salt dome or shale diapir, nor is there any geophysical evidence for an underlying dome of dense igneous rock having about the same density as the sedimentary layers.

Supramolecular structure formation of Langmuir-Blodgett films of comblike precursor and polyimide

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

Goloudina, S. I., E-mail: goloudina@mail.ru; Luchinin, V. V.; Rozanov, V. V.

2013-03-15

The surface structure of Langmuir-Blodgett films of a comblike polyimide precursor-a rigid-chain polyamic acid alkylamine salt bearing multichains of tertiary amine-and films of the corresponding polyimide were studied by atomic force microscopy (AFM). An analysis of the images of the surface of three-layer films revealed a domain structure. It was found that the Langmuir-Blodgett film formation of the precursor occurs as a result of the layer-by-layer deposition of two-dimensional domains (composed of polyamic acid salt molecules on the water surface) onto a substrate. The formation of domains in a monolayer is associated with the chemical structure of the precursor, tomore » be more precise, with the rigidity of the main chain and the presence of closely spaced aliphatic side chains in the polymer chain, whose total cross-section area is close to the surface area of the projection onto the plane of the repeating unit of the main chain. Polyimide films inherit the domain structure of the precursor films; the inhomogeneity of the film thickness substantially decreases, whereas the domain size and character of their distribution in the film remain unchanged.« less

Low-temperature atomic layer deposition of SiO2/Al2O3 multilayer structures constructed on self-standing films of cellulose nanofibrils.

PubMed

Putkonen, Matti; Sippola, Perttu; Svärd, Laura; Sajavaara, Timo; Vartiainen, Jari; Buchanan, Iain; Forsström, Ulla; Simell, Pekka; Tammelin, Tekla

2018-02-13

In this paper, we have optimized a low-temperature atomic layer deposition (ALD) of SiO 2 using AP-LTO® 330 and ozone (O 3 ) as precursors, and demonstrated its suitability to surface-modify temperature-sensitive bio-based films of cellulose nanofibrils (CNFs). The lowest temperature for the thermal ALD process was 80°C when the silicon precursor residence time was increased by the stop-flow mode. The SiO 2 film deposition rate was dependent on the temperature varying within 1.5-2.2 Å cycle -1 in the temperature range of 80-350°C, respectively. The low-temperature SiO 2 process that resulted was combined with the conventional trimethyl aluminium + H 2 O process in order to prepare thin multilayer nanolaminates on self-standing CNF films. One to six stacks of SiO 2 /Al 2 O 3 were deposited on the CNF films, with individual layer thicknesses of 3.7 nm and 2.6 nm, respectively, combined with a 5 nm protective SiO 2 layer as the top layer. The performance of the multilayer hybrid nanolaminate structures was evaluated with respect to the oxygen and water vapour transmission rates. Six stacks of SiO 2 /Al 2 O with a total thickness of approximately 35 nm efficiently prevented oxygen and water molecules from interacting with the CNF film. The oxygen transmission rates analysed at 80% RH decreased from the value for plain CNF film of 130 ml m -2  d -1 to 0.15 ml m -2  d -1 , whereas the water transmission rates lowered from 630 ± 50 g m -2  d -1 down to 90 ± 40 g m -2  d -1 This article is part of a discussion meeting issue 'New horizons for cellulose nanotechnology'. © 2017 The Author(s).

Low-temperature atomic layer deposition of SiO2/Al2O3 multilayer structures constructed on self-standing films of cellulose nanofibrils

NASA Astrophysics Data System (ADS)

Putkonen, Matti; Sippola, Perttu; Svärd, Laura; Sajavaara, Timo; Vartiainen, Jari; Buchanan, Iain; Forsström, Ulla; Simell, Pekka; Tammelin, Tekla

2017-12-01

In this paper, we have optimized a low-temperature atomic layer deposition (ALD) of SiO2 using AP-LTO® 330 and ozone (O3) as precursors, and demonstrated its suitability to surface-modify temperature-sensitive bio-based films of cellulose nanofibrils (CNFs). The lowest temperature for the thermal ALD process was 80°C when the silicon precursor residence time was increased by the stop-flow mode. The SiO2 film deposition rate was dependent on the temperature varying within 1.5-2.2 Å cycle-1 in the temperature range of 80-350°C, respectively. The low-temperature SiO2 process that resulted was combined with the conventional trimethyl aluminium + H2O process in order to prepare thin multilayer nanolaminates on self-standing CNF films. One to six stacks of SiO2/Al2O3 were deposited on the CNF films, with individual layer thicknesses of 3.7 nm and 2.6 nm, respectively, combined with a 5 nm protective SiO2 layer as the top layer. The performance of the multilayer hybrid nanolaminate structures was evaluated with respect to the oxygen and water vapour transmission rates. Six stacks of SiO2/Al2O with a total thickness of approximately 35 nm efficiently prevented oxygen and water molecules from interacting with the CNF film. The oxygen transmission rates analysed at 80% RH decreased from the value for plain CNF film of 130 ml m-2 d-1 to 0.15 ml m-2 d-1, whereas the water transmission rates lowered from 630 ± 50 g m-2 d-1 down to 90 ± 40 g m-2 d-1. This article is part of a discussion meeting issue `New horizons for cellulose nanotechnology'.

Patterns of chlorophyll-a distribution linked to mesoscale structures in two contrasting areas Campeche Canyon and Bank, Southern Gulf of Mexico

NASA Astrophysics Data System (ADS)

Durán-Campos, Elizabeth; Salas-de-León, David Alberto; Monreal-Gómez, María Adela; Coria-Monter, Erik

2017-05-01

The chlorophyll-a (Chl-a) distribution in Campeche Canyon and Campeche Bank, at the Southern Gulf of Mexico, as well as its relationship with hydrographic structure were analyzed. The results show the existence of the Gulf Common Water (GCW), the Caribbean Tropical Surface Water (CTSW) and the Caribbean Subtropical Underwater (CSUW) in the 120 m upper layer at the Campeche Canyon. While at the Campeche Bank only the Caribbean Tropical Surface Water (CTSW) was found. The 15 °C and 18.5 °C isotherms topography depict the presence of a mesoscale anticyclone-cyclone dipole. The nutrient pumping mechanism fertilizes the eutrophic zone promoted by the cyclonic eddy. Submesoscale processes in the border of an anticyclone and a cyclone results in maximum of nitrate concentration and vertically integrated Chl-a at the frontal zone. Two Chl-a vertical distribution patterns were found, a deep maximum at the base of the euphotic layer not associated to the thermocline over the Campeche Canyon and a peak associated to the thermocline related to the shallow bottom at the Campeche Bank. Oligotrophic conditions were observed in the 50 m upper layer and mesotrophic conditions were found below this layer. The differences between the Campeche Bank and Campeche Canyon are that: in the canyon, the nutrient and Chl-a peaks were linked with the cyclone, and the submesoscale processes in the border of an anticyclone and a cyclone, respectively. In the vertical the maximum Chl-a was associated to the base of the euphotic layer and dominated by coccolithophores. In the Campeche Bank the nutrient and Chl-a peaks were influenced by the shelf break in the vertical the maximum Chl-a was associated with the thermocline and the silicoflagellate was identified as the dominant species.

Simulation of annual plankton productivity cycle in the Black Sea by a one-dimensional physical-biological model

NASA Astrophysics Data System (ADS)

Oguz, Temel; Ducklow, Hugh; Malanotte-Rizzoli, Paola; Tugrul, Suleyman; Nezlin, Nikolai P.; Unluata, Umit

1996-07-01

The annual cycle of the plankton dynamics in the central Black Sea is studied by a one-dimensional vertically resolved physical-biological upper ocean model, coupled with the Mellor-Yamada level 2.5 turbulence closure scheme. The biological model involves interactions between the inorganic nitrogen (nitrate, ammonium), phytoplankton and herbivorous zooplankton biomasses, and detritus. Given a knowledge of physical forcing, the model simulates main observed seasonal and vertical characteristic features, in particular, formation of the cold intermediate water mass and yearly evolution of the upper layer stratification, the annual cycle of production with the fall and the spring blooms, and the subsurface phytoplankton maximum layer in summer, as well as realistic patterns of particulate organic carbon and nitrogen. The computed seasonal cycles of the chlorophyll and primary production distributions over the euphotic layer compare reasonably well with the data. Initiation of the spring bloom is shown to be critically dependent on the water column stability. It commences as soon as the convective mixing process weakens and before the seasonal stratification of surface waters begins to develop. It is followed by a weaker phytoplankton production at the time of establishment of the seasonal thermocline in April. While summer nutrient concentrations in the mixed layer are low enough to limit production, the layer between the thermocline and the base of the euphotic zone provides sufficient light and nutrient to support subsurface phytoplankton development. The autumn bloom takes place sometime between October and December depending on environmental conditions. In the case of weaker grazing pressure to control the growth rate, the autumn bloom shifts to December-January and emerges as the winter bloom, or, in some cases, is connected with the spring bloom to form one unified continuous bloom structure during the January-March period. These bloom structures are similar to the year-to-year variabilities present in the data.

An approach to the research on ion and water properties in the interphase between the plasma membrane and bulk extracellular solution.

PubMed

Hibino, Hiroshi; Takai, Madoka; Noguchi, Hidenori; Sawamura, Seishiro; Takahashi, Yasufumi; Sakai, Hideki; Shiku, Hitoshi

2017-07-01

In vivo, cells are immersed in an extracellular solution that contains a variety of bioactive substances including ions and water. Classical electrophysiological analyses of epithelial cells in the stomach and small intestine have revealed that within a distance of several hundred micrometers above their apical plasma membrane, lies an extracellular layer that shows ion concentration gradients undetectable in the bulk phase. This "unstirred layer", which contains stagnant solutes, may also exist between the bulk extracellular solution and membranes of other cells in an organism and may show different properties. On the other hand, an earlier study using a bacterial planar membrane indicated that H + released from a transporter migrates in the horizontal direction along the membrane surface much faster than it diffuses vertically toward the extracellular space. This result implies that between the membrane surface and unstirred layer, there is a "nanointerface" that has unique ionic dynamics. Advanced technologies have revealed that the nanointerface on artificial membranes possibly harbors a highly ordered assembly of water molecules. In general, hydrogen bonds are involved in formation of the ordered water structure and can mediate rapid transfer of H + between neighboring molecules. This description may match the phenomenon on the bacterial membrane. A recent study has suggested that water molecules in the nanointerface regulate the gating of K + channels. Here, the region comprising the unstirred layer and nanointerface is defined as the interphase between the plasma membrane and bulk extracellular solution (iMES). This article briefly describes the physicochemical properties of ions and water in the iMES and their physiological significance. We also describe the methodologies that are currently used or will be applicable to the interphase research.

Controlling the morphology and performance of FO membrane via adjusting the atmosphere humidity during casting procedure

NASA Astrophysics Data System (ADS)

Zuo, Hao-Ran; Cao, Gui-Ping; Wang, Meng; Zhang, Huan-Huan; Song, Chen-Chen; Fang, Xu; Wang, Tao

2018-03-01

Forward osmosis (FO) has received great interest for its considerable potential in a wide range of fields. In this work, the morphology and performance of FO membrane were regulated by adjusting the atmosphere humidity (HC) of casting procedure. The polysulfone support layer was casted under various atmosphere humidity levels ranging from 40% to 80%. By multi-techniques such as SEM, AFM, and XPS, it was proved that the atmosphere humidity had modified the surface morphology and thickness of the skin layer in support layer, which contributed up to 90% of the structure parameter, resulting in distinct morphology, thickness, and cross-linking degree of active layer. The active layer with sparse bead-like wrinkles on the smooth surface of support layer casted at HC = 65% showed the highest water permeability [26.9 (L/m2 h MPa)] and considerable low salt permeability [0.0390 (L/m2 h)]. It was found that the water flux of FO-65 was 27% and 46% higher than that of FO-80 in AL-DS and AL-FS mode, respectively, and the salt rejection was as high as 98%. Our work highlighted the importance of considering the effect of atmosphere humidity during casting when design an FO membrane for appropriate performance.

The role of organic soil layer on the fate of Siberian larch forest and near-surface permafrost under changing climate: A simulation study

NASA Astrophysics Data System (ADS)

SATO, H.; Iwahana, G.; Ohta, T.

2013-12-01

Siberian larch forest is the largest coniferous forest region in the world. In this vast region, larch often forms nearly pure stands, regenerated by recurrent fire. This region is characterized by a short and dry growing season; the annual mean precipitation for Yakutsk was only about 240 mm. To maintain forest ecosystem under such small precipitation, underlying permafrost and seasonal soil freezing-thawing-cycle have been supposed to play important roles; (1) frozen ground inhibits percolation of soil water into deep soil layers, and (2) excess soil water at the end of growing season can be carried over until the next growing season as ice, and larch trees can use the melt water. As a proof for this explanation, geographical distribution of Siberian larch region highly coincides with continuous and discontinuous permafrost zone. Recent observations and simulation studies suggests that existences of larch forest and permafrost in subsurface layer are co-dependent; permafrost maintains the larch forest by enhancing water use efficiency of trees, while larch forest maintains permafrost by inhibiting solar radiation and preventing heat exchanges between soil and atmosphere. Owing to such complexity and absence of enough ecosystem data available, current-generation Earth System Models significantly diverse in their prediction of structure and key ecosystem functions in Siberian larch forest under changing climate. Such uncertainty should in turn expand uncertainty over predictions of climate, because Siberian larch forest should have major role in the global carbon balance with its huge area and vast potential carbon pool within the biomass and soil, and changes in boreal forest albedo can have a considerable effect on Northern Hemisphere climate. In this study, we developed an integrated ecosystem model, which treats interactions between plant-dynamics and freeze-thaw cycles. This integrated model contains a dynamic global vegetation model SEIB-DGVM, which simulates plant and carbon dynamics. It also contains a one-dimensional land surface model NOAH 2.7.1, which simulates soil moisture (both liquid and frozen), soil temperature, snowpack depth and density, canopy water content, and the energy and water fluxes. This integrated model quantitatively reconstructs post-fire development of forest structure (i.e. LAI and biomass) and organic soil layer, which dampens heat exchanges between soil and atmosphere. With the post-fire development of LAI and the soil organic layer, the integrated model also quantitatively reconstructs changes in seasonal maximum of active layer depth. The integrated model is then driven by the IPCC A1B scenario of rising atmospheric CO2, and by climate changes during the twenty-first century resulting from the change in CO2. This simulation suggests that forecasted global warming would causes decay of Siberian larch ecosystem, but such responses could be delayed by "memory effect" of the soil organic layer for hundreds of years.

Atypical water lattices and their possible relevance to the amorphous ices: A density functional study

NASA Astrophysics Data System (ADS)

Anick, David J.

2013-04-01

Of the fifteen known crystalline forms of ice, eleven consist of a single topologically connected hydrogen bond network with four H-bonds at every O. The other four, Ices VI-VIII and XV, consist of two topologically connected networks, each with four H-bonds at every O. The networks interpenetrate but do not share H-bonds. This article presents two new periodic water lattice families whose topological connectivity is "atypical": they consist of many two-dimensional layers that share no H-bonds. Layers are held together only by dispersion forces. Within each layer there are still four H-bonds at each O. Called "Hexagonal Bilayer Water" (HBW) and "Pleated Sheet Water" (PSW), they have computed densities of about 1.1 g/mL and 1.3 g/mL respectively, and nearest neighbor O-coordination is 4.5 to 5.5 and 6 to 8 respectively. Using density functional theory (BLYP-D/TZVP), various proton ordered forms of HBW and PSW are optimized and categorized. There are simple pathways connecting Ice-Ih to HBW and HBW to PSW. Their computed properties suggest similarities to the high density and very high density amorphous ices (HDA and VHDA) respectively. It is unknown whether HDA, VHDA, and Low Density Amorphous Ice (LDA) are fully disordered glasses down to the molecular level, or whether there is some short-range local order. Based on estimated radial distribution functions (RDFs), one proton ordered form of HBW matches HDA best. The idea is explored that HDA could contain islands with this underlying structure, and likewise, that VHDA could contain regions of PSW. A "microlattice model version 1" (MLM1) is presented as a device to compare key experimental data on the amorphous ices with these atypical structures and with a microlattice form of Ice-XI for LDA. Resemblances are found with the amorphs' RDFs, densities, Raman spectra, and transition behaviors. There is not enough information in the static models to assign either a microlattice structure or a partial microlattice structure to any amorphous ice phase.

Distinguishing oil and water layers in a cracked porous medium using pulsed neutron logging data based on Hudson's crack theory

NASA Astrophysics Data System (ADS)

Zhang, Xueang; Yang, Zhichao; Tang, Bin; Wang, Renbo; Wei, Xiong

2018-05-01

During geophysical surveys, water layers may interfere with the detection of oil layers. In order to distinguish between oil and water layers in porous cracked media, research on the properties of the cracks, the oil and water layers, and their relation to pulsed neutron logging characteristics is essential. Using Hudson's crack theory, we simulated oil and water layers in a cracked porous medium with different crack parameters corresponding to the well log responses. We found that, in a cracked medium with medium-angle (40°-50°) cracks, the thermal neutron count peak value is higher and more sensitive than those in low-angle and high-angle crack environments; in addition, the thermal neutron density distribution shows more minimum values than in other cases. Further, the thermal neutron count and the rate of change for the oil layer are greater than those of the water layer, and the time spectrum count peak value for the water layer in middle-high-angle (40°-70°) cracked environments is higher than that of the oil layer. The thermal neutron density distribution sensitivity is higher in the water layer with a range of small crack angles (0°-30°) than in the oil layer with the same range of angles. In comparing the thermal neutron density distribution, thermal neutron count peak, thermal neutron density distribution sensitivity, and time spectrum maximum in the oil and water layers, we find that neutrons in medium-angle (40°-50°) cracked reservoirs are more sensitive to deceleration and absorption than those in water layers; neutrons in approximately horizontal (0°-30°) cracked water layers are more sensitive to deceleration than those in reservoirs. These results can guide future work in the cracked media neutron logging field.

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.

Using Neutron Reflectometry to Discern the Structure of Fibrinogen Adsorption at the Stainless Steel/Aqueous Interface.

PubMed

Wood, Mary H; Browning, Kathryn L; Barker, Robert D; Clarke, Stuart M

2016-06-23

Neutron reflectometry has been successfully used to study adsorption on a stainless steel surface by means of depositing a thin steel film on silicon. The film was characterized using XPS (X-ray photoelectron spectroscopy), TOF-SIMS (time-of-flight secondary ion mass spectrometry), and GIXRD (grazing incidence X-ray diffraction), demonstrating the retention both of the austenitic phase and of the required composition for 316L stainless steel. The adsorption of fibrinogen from a physiologically-relevant solution onto the steel surface was studied using neutron reflectometry and QCM (quartz crystal microbalance) and compared to that on a deposited chromium oxide surface. It was found that the protein forms an irreversibly bound layer at low concentrations, with maximum protein concentration a distance of around 20 Å from the surface. Evidence for a further diffuse reversibly-bound layer forming at higher concentrations was also observed. Both the structure of the layer revealed by the neutron reflectometry data and the high water retention predicted by the QCM data suggest that there is a significant extent of protein unfolding upon adsorption. A lower extent of adsorption was seen on the chromium surfaces, although the adsorbed layer structures were similar, suggesting comparable adsorption mechanisms.

Storm-induced water dynamics and thermohaline structure at the tidewater Flade Isblink Glacier outlet to the Wandel Sea (NE Greenland)

NASA Astrophysics Data System (ADS)

Kirillov, Sergei; Dmitrenko, Igor; Rysgaard, Søren; Babb, David; Toudal Pedersen, Leif; Ehn, Jens; Bendtsen, Jørgen; Barber, David

2017-11-01

In April 2015, an ice-tethered conductivity-temperature-depth (CTD) profiler and a down-looking acoustic Doppler current profiler (ADCP) were deployed from the landfast ice near the tidewater glacier terminus of the Flade Isblink Glacier in the Wandel Sea, NE Greenland. The 3-week time series showed that water dynamics and the thermohaline structure were modified considerably during a storm event on 22-24 April, when northerly winds exceeded 15 m s-1. The storm initiated downwelling-like water dynamics characterized by on-shore water transport in the surface (0-40 m) layer and compensating offshore flow at intermediate depths. After the storm, currents reversed in both layers, and the relaxation phase of downwelling lasted ˜ 4 days. Although current velocities did not exceed 5 cm s-1, the enhanced circulation during the storm caused cold turbid intrusions at 75-95 m depth, which are likely attributable to subglacial water from the Flade Isblink Ice Cap. It was also found that the semidiurnal periodicities in the temperature and salinity time series were associated with the lunar semidiurnal tidal flow. The vertical structure of tidal currents corresponded to the first baroclinic mode of the internal tide with a velocity minimum at ˜ 40 m. The tidal ellipses rotate in opposite directions above and below this depth and cause a divergence of tidal flow, which was observed to induce semidiurnal internal waves of about 3 m height at the front of the glacier terminus. Our findings provide evidence that shelf-basin interaction and tidal forcing can potentially modify coastal Wandel Sea waters even though they are isolated from the atmosphere by landfast sea ice almost year-round. The northerly storms over the continental slope cause an enhanced circulation facilitating a release of cold and turbid subglacial water to the shelf. The tidal flow may contribute to the removal of such water from the glacial terminus.

NMR relaxation studies on the hydrate layer of intrinsically unstructured proteins.

PubMed

Bokor, Mónika; Csizmók, Veronika; Kovács, Dénes; Bánki, Péter; Friedrich, Peter; Tompa, Peter; Tompa, Kálmán

2005-03-01

Intrinsically unstructured/disordered proteins (IUPs) exist in a disordered and largely solvent-exposed, still functional, structural state under physiological conditions. As their function is often directly linked with structural disorder, understanding their structure-function relationship in detail is a great challenge to structural biology. In particular, their hydration and residual structure, both closely linked with their mechanism of action, require close attention. Here we demonstrate that the hydration of IUPs can be adequately approached by a technique so far unexplored with respect to IUPs, solid-state NMR relaxation measurements. This technique provides quantitative information on various features of hydrate water bound to these proteins. By freezing nonhydrate (bulk) water out, we have been able to measure free induction decays pertaining to protons of bound water from which the amount of hydrate water, its activation energy, and correlation times could be calculated. Thus, for three IUPs, the first inhibitory domain of calpastatin, microtubule-associated protein 2c, and plant dehydrin early responsive to dehydration 10, we demonstrate that they bind a significantly larger amount of water than globular proteins, whereas their suboptimal hydration and relaxation parameters are correlated with their differing modes of function. The theoretical treatment and experimental approach presented in this article may have general utility in characterizing proteins that belong to this novel structural class.

Hydration structure of the barite (001)–water interface: Comparison of x-ray reflectivity with molecular dynamics simulations

DOE PAGES

Bracco, Jacquelyn N.; Lee, Sang Soo; Stubbs, Joanne E.; ...

2017-05-11

The three-dimensional structure of the barite (001)-water interface was studied using in situ specular and non-specular X-ray reflectivity (XR). Displacements of the barium and sulfate ions in the surface of a barite crystal and the interfacial water structure were defined in the analyses. The largest relaxations (0.13 Å lateral and 0.08 Å vertical) were observed for the barium and sulfate ions in the topmost unit cell layer, which diminished rapidly with depth. The best fit structure identified four distinct adsorbed species, which in comparison with molecular dynamics (MD) simulations, reveals that they are associated with positions of adsorbed water, eachmore » of which coordinates one or two surface ions (either barium, sulfate, or both). These water molecules also adsorb in positions consistent with those of bariums and sulfates in the bulk crystal lattice. These results demonstrate the importance of combining high resolution XR with MD simulations to fully describe the atomic structure of the hydrated mineral surface. As a result, the agreement between the results indicates both the uniqueness of the structural model obtained from the XR analysis and the accuracy of the force field used in the simulations.« less

Hydration structure of the barite (001)–water interface: Comparison of x-ray reflectivity with molecular dynamics simulations

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

Bracco, Jacquelyn N.; Lee, Sang Soo; Stubbs, Joanne E.

The three-dimensional structure of the barite (001)-water interface was studied using in situ specular and non-specular X-ray reflectivity (XR). Displacements of the barium and sulfate ions in the surface of a barite crystal and the interfacial water structure were defined in the analyses. The largest relaxations (0.13 Å lateral and 0.08 Å vertical) were observed for the barium and sulfate ions in the topmost unit cell layer, which diminished rapidly with depth. The best fit structure identified four distinct adsorbed species, which in comparison with molecular dynamics (MD) simulations, reveals that they are associated with positions of adsorbed water, eachmore » of which coordinates one or two surface ions (either barium, sulfate, or both). These water molecules also adsorb in positions consistent with those of bariums and sulfates in the bulk crystal lattice. These results demonstrate the importance of combining high resolution XR with MD simulations to fully describe the atomic structure of the hydrated mineral surface. As a result, the agreement between the results indicates both the uniqueness of the structural model obtained from the XR analysis and the accuracy of the force field used in the simulations.« less

Ice shelf structure from dispersion curve analysis of passive-source seismic data, Ross Ice Shelf, Antarctica

NASA Astrophysics Data System (ADS)

Diez, A.; Bromirski, P. D.; Gerstoft, P.; Stephen, R. A.; Anthony, R. E.; Aster, R. C.; Cai, C.; Nyblade, A.; Wiens, D.

2015-12-01

An L-shaped array of three-component short period seismic stations was deployed at the Ross Ice Shelf, Antarctica approximately 100 km south of the ice edge, near 180° longitude, from November 18 through 28, 2014. Polarization analysis of data from these stations clearly shows propagating waves from below the ice shelf for frequencies below 2 Hz. Energy above 2 Hz is dominated by Rayleigh and Love waves propagating from the north. Frequency-slowness plots were calculated using beamforming. Resulting Love and Rayleigh wave dispersion curves were inverted for the shear wave velocity profile, from which we derive a density profile. The derived shear wave velocity profiles differ within the firn for the inversions using Rayleigh and Love wave dispersion curves. This difference is attributed to an effective anisotropy due to fine layering. The layered structure of firn, ice, water, and ocean floor results in a characteristic dispersion curve pattern below 7 Hz. We investigate the observed structures in more detail by forward modeling of Rayleigh wave dispersion curves for representative firn, ice, water, sediment structures. Rayleigh waves are observed when wavelengths are long enough to span the distance from the ice shelf surface to the seafloor. Our results show that the analysis of high frequency Rayleigh waves on an ice shelf has the ability to resolve ice shelf thickness, water column thickness, and the physical properties of the underlying ocean floor using passive-source seismic data.

[Research of input water ratio's impact on the quality of effluent water from hydrolysis reactor].

PubMed

Liang, Kang-Qiang; Xiong, Ya; Qi, Mao-Rong; Lin, Xiu-Jun; Zhu, Min; Song, Ying-Hao

2012-11-01

Based on high SS/BOD and low C/N ratio of waste water of municipal wastewater treatment plant, the structure of currently existing hydrolysis reactor was reformed to improve the influent quality. In order to strengthen the sludge hydrolysis and improve effluent water quality, two layers water distributors were set up so that the sludge hydrolysis zone was formed between the two layers distribution. For the purpose of the hydrolysis reactor not only plays the role of the primary sedimentation tank but also improves the effluent water biodegradability, input water ratios of the upper and lower water distributor in the experiment were changed to get the best input water ratio to guide the large-scale application of this sort hydrolysis reactor. Results show, four kinds of input water ratio have varying degrees COD and SS removal efficiency, however, input water ratio for 1 : 1 can substantially increase SCOD/COD ratio and VFA concentration of effluent water compared with the other three input water ratios. To improve the effluent biodegradability, input water ratio for 1 : 1 was chosen for the best input water ratio. That was the ratio of flow of upper distributor was 50%, and the ratio of the lower one was 50%, at this case it can reduce the processing burden of COD and SS for follow-up treatment, but also improve the biodegradability of the effluent.

Evidence of linked biogeochemical and hydrological processes in homogeneous and layered vadose zone systems

NASA Astrophysics Data System (ADS)

McGuire, J. T.; Hansen, D. J.; Mohanty, B. P.

2010-12-01

Understanding chemical fate and transport in the vadose zone is critical to protect groundwater resources and preserve ecosystem health. However, prediction can be challenging due to the dynamic hydrologic and biogeochemical nature of the vadose zone. Additional controls on hydrobiogeochemical processes are added by subsurface structural heterogeneity. This study uses repacked soil column experiments to quantify linkages between microbial activity, geochemical cycling and hydrologic flow. Three “short” laboratory soil columns were constructed to evaluate the effects of soil layering: a homogenized medium-grained sand, homogenized organic-rich loam, and a sand-over-loam layered column. In addition, two “long” columns were constructed using either gamma-irradiated (sterilized) or untreated sediments to evaluate the effects of both soil layers and the presence of microorganisms. The long columns were packed identically; a medium-grained sand matrix with two vertically separated and horizontally offset lenses of organic-rich loam. In all 5 columns, downward and upward infiltration of water was evaluated to simulate rainfall and rising water table events respectively. In-situ colocated probes were used to measure soil water content, matric potential, Eh, major anions, ammonium, Fe2+, and total sulfide. Enhanced biogeochemical cycling was observed in the short layered column versus the short, homogeneous columns, and enumerations of iron and sulfate reducing bacteria were 1-2 orders of magnitude greater. In the long columns, microbial activity caused mineral bands and produced insoluble gases that impeded water flow through the pores of the sediment. Capillary barriers, formed around the lenses due to soil textural differences, retarded water flow rates through the lenses. This allowed reducing conditions to develop, evidenced by the production of Fe2+ and S2-. At the fringes of the lenses, Fe2+ oxidized to form Fe(III)-oxide bands that further retarded water flux. No such mineral bands developed in the sterilized column. As a consequence, water content in the lenses of the sterilized column was half that of the other column and flow rates through the lenses were an order of magnitude lower. This flow impedance limited the interaction and mixing of groundwater with infiltrating vadose zone water and led to the formation of geochemically distinct water masses residing in relatively close proximity to one another. Results provide a specific examples of the direct impact of biogeochemical cycling on water flow in the vadose zone and vice versa. In addition, these demonstrate that the presence of layers in vadose zone environments may be an important control on overall chemical fate and transport in subsurface systems.

RNA nanopatterning on graphene

NASA Astrophysics Data System (ADS)

Li, Q.; Froning, J. P.; Pykal, M.; Zhang, S.; Wang, Z.; Vondrák, M.; Banáš, P.; Čépe, K.; Jurečka, P.; Šponer, J.; Zbořil, R.; Dong, M.; Otyepka, M.

2018-07-01

Graphene-based materials enable the sensing of diverse biomolecules using experimental approaches based on electrochemistry, spectroscopy, or other methods. Although basic sensing was achieved, it had until now not been possible to understand and control biomolecules’ structural and morphological organization on graphene surfaces (i.e. their stacking, folding/unfolding, self-assembly, and nano-patterning). Here we present the insight into structural and morphological organization of biomolecules on graphene in water, using an RNA hairpin as a model system. We show that the key parameters governing the RNA’s behavior on the graphene surface are the number of graphene layers, RNA concentration, and temperature. At high concentrations, the RNA forms a film on the graphene surface with entrapped nanobubbles. The density and the size of the bubbles depend on the number of graphene layers. At lower concentrations, unfolded RNA stacks on the graphene and forms molecular clusters on the surface. Such a control over the conformational behavior of interacting biomolecules at graphene/water interfaces would facilitate new applications of graphene derivatives in biotechnology and biomedicine.

Numerical modeling of cracking pattern's influence on the dynamic response of thickened tailings disposals: a periodic approach

NASA Astrophysics Data System (ADS)

Ferrer, Gabriel; Sáez, Esteban; Ledezma, Christian

2018-01-01

Copper production is an essential component of the Chilean economy. During the extraction process of copper, large quantities of waste materials (tailings) are produced, which are typically stored in large tailing ponds. Thickened Tailings Disposal (TTD) is an alternative to conventional tailings ponds. In TTD, a considerable amount of water is extracted from the tailings before their deposition. Once a thickened tailings layer is deposited, it loses water and it shrinks, forming a relatively regular structure of tailings blocks with vertical cracks in between, which are then filled up with "fresh" tailings once the new upper layer is deposited. The dynamic response of a representative column of this complex structure made out of tailings blocks with softer material in between was analyzed using a periodic half-space finite element model. The tailings' behavior was modeled using an elasto-plastic multi-yielding constitutive model, and Chilean earthquake records were used for the seismic analyses. Special attention was given to the liquefaction potential evaluation of TTD.

The effects of surface-charged submicron polystyrene particles on the structure and performance of PSF forward osmosis membrane

NASA Astrophysics Data System (ADS)

Zuo, Hao-Ran; Fu, Jia-Bei; Cao, Gui-Ping; Hu, Nian; Lu, Hui; Liu, Hui-Qing; Chen, Peng-Peng; Yu, Jie

2018-04-01

Monodisperse surface-charged submicron polystyrene particles were designed, synthesized, and blended into polysulfone (PSF) support layer to prepare forward osmosis (FO) membrane with high performance. The membrane incorporated with particles were characterized with respect to morphology, porosity, and internal osmotic pressure (IOP). Results showed that the polymer particles not only increased the hydrophilicity and porosity of support layer, but also generated considerable IOP, which helped markedly decreasing the structure parameter from 1550 to 670 μm. The measured mass transfer parameters further confirmed the beneficial effects of the surface-charged submicron polymer particles on the performance of FO membrane. For instance, the water permeability coefficient (5.37 L m-2 h-1 bar-1) and water flux (49.7 L m-2 h-1) of the FO membrane incorporated with 5 wt% particles were almost twice as much as that of FO membrane without incorporation. This study suggests that monodisperse surface-charged submicron polymer particles are potential modifiers for improving the performance of FO membranes.

A modeling study of methane hydrate decomposition in contact with the external surface of zeolites.

PubMed

Smirnov, Konstantin S

2017-08-30

The behavior of methane hydrate (MH) enclosed between the (010) surfaces of the silicalite-1 zeolite was studied by means of molecular dynamics simulations at temperatures of 150 and 250 K. Calculations reveal that the interaction with the hydrophilic surface OH groups destabilizes the clathrate structure of hydrate. While MH mostly conserves the structure in the simulation at the low temperature, thermal motion at the high temperature breaks the fragilized cages of H-bonded water molecules, thus leading to the release of methane. The dissociation proceeds in a layer-by-layer manner starting from the outer parts of the MH slab until complete hydrate decomposition. The released CH 4 molecules are absorbed by the microporous solid, whereas water is retained at the surfaces of hydrophobic silicalite and forms a meniscus in the interlayer space. Methane uptake reaches 70% of the silicalite sorption capacity. The energy necessary for the endothermic MH dissociation is supplied by the exothermic methane absorption by the zeolite.