Glass Formation, Chemical Properties and Surface Analysis of Cu-Based Bulk Metallic Glasses

PubMed Central

Qin, Chunling; Zhao, Weimin; Inoue, Akihisa

2011-01-01

This paper reviews the influence of alloying elements Mo, Nb, Ta and Ni on glass formation and corrosion resistance of Cu-based bulk metallic glasses (BMGs). In order to obtain basic knowledge for application to the industry, corrosion resistance of the Cu–Hf–Ti–(Mo, Nb, Ta, Ni) and Cu–Zr–Ag–Al–(Nb) bulk glassy alloy systems in various solutions are reported in this work. Moreover, X-ray photoelectron spectroscopy (XPS) analysis is performed to clarify the surface-related chemical characteristics of the alloy before and after immersion in the solutions; this has lead to a better understanding of the correlation between the surface composition and the corrosion resistance. PMID:21731441

Structure, optical and phonon properties of bulk and nanocrystalline Al2-xScx(WO4)3 solid solutions doped with Cr3+

NASA Astrophysics Data System (ADS)

Mączka, M.; Hermanowicz, K.; Pietraszko, A.; Yordanova, A.; Koseva, I.

2014-01-01

Pure and Cr3+ doped nanosized Al2-xScx(WO4)3 solid solutions were prepared by co-precipitation method as well as Al2-xScx(WO4)3 single crystals were grown by high-temperature flux method. The obtained samples were characterized by X-ray, Raman, IR, absorption and luminescence methods. Single crystal X-ray diffraction showed that AlSc(WO4)3 is orthorhombic at room temperature with space group Pnca and trivalent cations are statistically distributed. Raman and IR studies showed that Al2-xScx(WO4)3 solid solutions show "two mode" behavior. They also showed that vibrational properties of nanosized samples have been weakly modified in comparison with the bulk materials. The luminescence and absorption spectra revealed that chromium ions occupy two sites of weak and strong crystal field strength.

Spray-dried chitosan as a direct compression tableting excipient.

PubMed

Chinta, Dakshinamurthy Devanga; Graves, Richard A; Pamujula, Sarala; Praetorius, Natalie; Bostanian, Levon A; Mandal, Tarun K

2009-01-01

The objective of this study was to prepare and evaluate a novel spray-dried tableting excipient using a mixture of chitosan and lactose. Three different grades of chitosan (low-, medium-, and high-molecular-weight) were used for this study. Propranolol hydrochloride was used as a model drug. A specific amount of chitosan (1, 1.9, and 2.5 g, respectively) was dissolved in 50 mL of an aqueous solution of citric acid (1%) and later mixed with 50 mL of an aqueous solution containing lactose (20, 19.1, and 18.5 g, respectively) and propanolol (2.2 g). The resultant solution was sprayed through a laboratory spray drier at 1.4 mL/min. The granules were evaluated for bulk density, tap density, Carr index, particle size distribution, surface morphology, thermal properties, and tableting properties. Bulk density of the granules decreased from 0.16 to 0.13 g/mL when the granules were prepared using medium- or high-molecular-weight chitosan compared with the low-molecular-weight chitosan. The relative proportion of chitosan also showed a significant effect on the bulk density. The granules prepared with 1 g of low-molecular-weight chitosan showed the minimum Carr index (11.1%) indicating the best flow properties among all five formulations. All three granules prepared with 1 g chitosan, irrespective of their molecular weight, showed excellent flow properties. Floating tablets prepared by direct compression of these granules with sodium bicarbonate showed 50% drug release between 30 and 35 min. In conclusion, the spray-dried granules prepared with chitosan and lactose showed excellent flow properties and were suitable for tableting.

A model for hydrostatic consolidation of Pierre shale

USGS Publications Warehouse

Savage, W.Z.; Braddock, W.A.

1991-01-01

This paper presents closed-form solutions for consolidation of transversely isotropic porous media under hydrostatic stress. The solutions are applied to model the time variation of pore pressure, volume strain and strains parallel and normal to bedding, and to obtain coefficients of consolidation and permeability, as well as other properties, and the bulk modulus resulting from hydrostatic consolidation of Pierre shale. It is found that the coefficients consolidation and permeability decrease and the bulk moduli increase with increasing confining pressure, reflecting the closure of voids in the rock. ?? 1991.

Concurrent Solution and Adsorption of Hydrocarbons in Gas Chromatographic Columns Packed with Different Loadings of 3-Methylsydnone on Chromosorb P

PubMed

Castells; Romero; Nardillo

1997-08-01

Thermodynamic properties of solution in 3-methylsydnone (3MS) and of adsorption at the nitrogen/3MS interface were gas chromatographically measured for a group of fifteen hydrocarbons at infinite dilution conditions. Retention volumes were measured at five temperatures within the range 37-52°C in six columns containing different loadings of 3MS on Chromosorb P AW. Partition and adsorption coefficients were calculated and from their temperature dependence the corresponding enthalpies were obtained, although with considerable error; infinite dilution activity coefficients of the hydrocarbons in the bulk and in the surface phases demonstrated a strong correlation. Bulk activity coefficients in 3MS were very much smaller than those previously measured for the same solutes in formamide (FA) and in ethyleneglycol (EG), and were also smaller than what could be predicted on account of 3MS cohesive energy density as estimated from the quotient sigma/v1/3 (sigma, surface tension; v, molar volume). There was not such a large difference between the surface activity coefficients in the three solvents; furthermore, the quotients (surface activity coefficient/bulk activity coefficient) for a given solute in 3MS were twice as large as in FA and about three times larger than in EG. These results make evident the difficulties inherent in the prediction of surface phase properties from those in the bulk and cast doubts on the pertinency of employing the surface tension to compare cohesive energy densities of polar solvents with important chemical differences.

Technological hurdles to the application of intercalated graphite fibers

NASA Technical Reports Server (NTRS)

Gaier, James R.

1988-01-01

Before intercalated graphite fibers can be developed as an effective power material, there are several technological hurdles which must be overcome. These include the environmental stability, homogeneity and bulk properties, connection procedures, and costs. Strides were made within the last several years in stability and homogeneity of intercalated graphite fibers. Bulk properties and connection procedures are areas of active research now. Costs are still prohibitive for all but the most demanding applications. None of these problems, however, appear to be unsolvable, and their solution may result in wide spread GOC application. The development of a relatively simple technology application, such as EMI shielding, would stimulate the solution of scale-up problems. Once this technology is developed, then more demanding applications, such as power bus bars, may be possible.

Influence of isotopic disorder on solid state amorphization and polyamorphism in solid H2O -D2O solutions

NASA Astrophysics Data System (ADS)

Gromnitskaya, E. L.; Danilov, I. V.; Lyapin, A. G.; Brazhkin, V. V.

2015-10-01

We present a low-temperature and high-pressure ultrasonic study of elastic properties of isotopic H2O-D2O solid solutions, comparing their properties with those of the isotopically pure H2O and D2O ices. Measurements were carried out for solid state amorphization (SSA) from 1h to high-density amorphous (HDA) ice upon compression up to 1.8 GPa at 77 K and for the temperature-induced (77 -190 K ) u-HDA (unrelaxed HDA) → e-HDA (expanded HDA) → low-density amorphous (LDA )→1 c cascade of ice transformations near room pressure. There are many similarities in the elasticity behaviour of H2O ,D2O , and H2O-D2O solid solutions, including the softening of the shear elastic modulus as a precursor of SSA and the HDA →LDA transition. We have found significant isotopic effects during H/D substitution, including elastic softening of H2O -D2O solid solutions with respect to the isotopically pure ices in the case of the bulk moduli of ices 1c and 1h and for both bulk and shear elastic moduli of HDA ice at high pressures (>1 GPa ) . This softening is related to the configurational isotopic disorder in the solid solutions. At low pressures, the isotope concentration dependence of the elastic moduli of u-HDA ice changes remarkably and becomes monotonic with pronounced change of the bulk modulus (≈20 %) .

Aqueous pathways dominate permeation of solutes across Pisum sativum seed coats and mediate solute transport via diffusion and bulk flow of water.

PubMed

Niemann, Sylvia; Burghardt, Markus; Popp, Christian; Riederer, Markus

2013-05-01

The permeability of seed coats to solutes either of biological or anthropogenic origin plays a major role in germination, seedling growth and seed treatment by pesticides. An experimental set-up was designed for investigating the mechanisms of seed coat permeation, which allows steady-state experiments with isolated seed coats of Pisum sativum. Permeances were measured for a set of organic model compounds with different physicochemical properties and sizes. The results show that narrow aqueous pathways dominate the diffusion of solutes across pea seed coats, as indicated by a correlation of permeances with the molecular sizes of the compounds instead of their lipophilicity. Further indicators for an aqueous pathway are small size selectivity and a small effect of temperature on permeation. The application of an osmotic water potential gradient across isolated seed coats leads to an increase in solute transfer, indicating that the aqueous pathways form a water-filled continuum across the seed coat allowing the bulk flow of water. Thus, the uptake of organic solutes across pea testae has two components: (1) by diffusion and (2) by bulk water inflow, which, however, is relevant only during imbibition. © 2012 Blackwell Publishing Ltd.

Aggregation of concentrated monoclonal antibody solutions studied by rheology and neutron scattering

NASA Astrophysics Data System (ADS)

Castellanos, Maria Monica; Pathak, Jai; Colby, Ralph

2013-03-01

Protein solutions are studied using rheology and scattering techniques to investigate aggregation. Here we present a monoclonal antibody (mAb) that aggregates after incubation at 40 °C (below its unfolding temperature), with a decrease in monomer purity of 6% in 10 days. The mAb solution contains surfactant and behaves as a Newtonian fluid when reconstituted into solution from the lyophilized form (before incubation at 40 °C). In contrast, mAb solutions incubated at 40 °C for 1 month exhibit shear yielding in torsional bulk rheometers. Interfacial rheology reveals that interfacial properties are controlled by the surfactant, producing a negligible surface contribution to the bulk yield stress. These results provide evidence that protein aggregates formed in the bulk are responsible for the yield stress. Small-angle neutron scattering (SANS) measurements show an increase in intensity at low wavevectors (q < 4*10-2 nm-1) that we attribute to protein aggregation, and is not observed in solutions stored at 4 °C for 3 days before the measurement. This work suggests a correlation between the aggregated state of the protein (stability) and the yield stress from rheology. Research funded by MedImmune

Ab initio investigation of Ti2Al(C,N) solid solutions

NASA Astrophysics Data System (ADS)

Arróyave, Raymundo; Radovic, Miladin

2011-10-01

Mn+1AXn phases (M: early transition metal, A: IIIA- or IVA-group element, X: carbon or nitrogen) are layered ternary compounds that possess both metal- and ceramic-like properties with numerous potential applications in bulk and thin film forms, particularly under high-temperature conditions. In this work, we use the cluster expansion formalism to investigate the energetics of C-N interactions across the entire Ti2AlC-Ti2AlN composition range. It is shown that there is a definite tendency for ordering in the C,N sublattice. However, the molar volume and bulk modulus of the ordered structures found along the Ti2AlC-Ti2AlN composition range show small deviations from the (linear) rule of mixing, indicating that despite the ordering tendencies, the C-N interactions are not strong and the solution becomes disordered at relatively low temperatures. Random solid solutions of Ti2AlC1-xNx are simulated using special quasirandom structures (SQS) with x=0.25, 0.50, and 0.75. The thermodynamic properties of these structures are compared to those of the structures found to belong to the ground state through the cluster expansion approach. It is found that the structural properties of these approximations to random alloys do not deviate significantly from Vegard's law. The trend in the structural parameters of these SQS are found to agree well with available experimental data and the predictions of the bulk modulus suggest a very weak alloying effect—with respect to Vegard's law—on the elastic properties of Ti2AlC1-xNx.

Effect of composition on physical properties of food powders

NASA Astrophysics Data System (ADS)

Szulc, Karolina; Lenart, Andrzej

2016-04-01

The paper presents an influence of raw material composition and technological process applied on selected physical properties of food powders. Powdered multi-component nutrients were subjected to the process of mixing, agglomeration, coating, and drying. Wetting liquids ie water and a 15% water lactose solution, were used in agglomeration and coating. The analyzed food powders were characterized by differentiated physical properties, including especially: particle size, bulk density, wettability, and dispersibility. The raw material composition of the studied nutrients exerted a statistically significant influence on their physical properties. Agglomeration as well as coating of food powders caused a significant increase in particle size, decreased bulk density, increased apparent density and porosity, and deterioration in flowability in comparison with non-agglomerated nutrients.

Theoretical and Simulations-Based Modeling of Micellization in Linear and Branched Surfactant Systems

NASA Astrophysics Data System (ADS)

Mendenhall, Jonathan D.

Surfactants are chemically-heterogeneous molecules possessing hydrophilic (head) and hydrophobic (tail) moieties. This dual nature of surfactants leads to interesting phase behavior in aqueous solution as a function of surfactant concentration, including: (i) formation of surfactant monolayers at surfaces and interfaces, and (ii) self-assembly into finite aggregates (micelles) in the bulk solution beyond the critical micelle concentration (cmc). This concentration-dependent phase behavior induces changes in solution properties. For example, the surface activity of surfactants can decrease the surface tension, and self-assembly in bulk solution can lead to changes in viscosity, equivalent conductivity, solubilization capacity, and other bulk properties. These effects make surfactants quite attractive and unique for use in product formulations, where they are utilized as detergents, dispersants, emulsifiers, solubilizers, surface and interfacial tension modifiers, and in other contexts. The specific chemical structure of the surfactant head and tail is essential in determining the overall performance properties of a surfactant in aqueous media. The surfactant tail drives the self-assembly process through the hydrophobic effect, while the surfactant head imparts a certain extent of solubility to the surfactant in aqueous solution through preferential interactions with the hydrogen-bonding network of water. The interplay between these two effects gives rise to the particular phase diagram of a surfactant, including the specific cmc at which micelles begin to form. In addition to serving as a quantitative indicator of micelle formation, the cmc represents a limit to surface monolayer formation, and hence to surface and interfacial tension reduction, because surfactant adsorption at interfaces remains approximately constant beyond the cmc. In addition, the cmc represents the onset of changes in bulk solution properties. This Thesis is concerned with the prediction of cmc's and other micellization properties for a variety of linear and branched surfactant chemical architectures which are commonly encountered in practice. Single-component surfactant solutions are investigated, in order to clarify the specific contributions of the surfactant head and tail to the free energy of micellization, a quantity which determines the cmc and all other aspects of micellization. First, a molecular-thermodynamic (MT) theory is presented which makes use of bulk-phase thermodynamics and a phenomenological thought process to describe the energetics related to the formation of a micelle from its constituent surfactant monomers. Second, a combined computer-simulation/molecular-thermodynamic (CSMT) framework is discussed which provides a more detailed quantification of the hydrophobic effect using molecular dynamics simulations. A novel computational strategy to identify surfactant head and tail using an iterative dividing surface approach, along with simulated micelle results, is proposed. Force-field development for novel surfactant structures is also discussed. Third, a statistical-thermodynamic, single-chain, mean-field theory for linear and branched tail packing is formulated, which enables quantification of the specific energetic penalties related to confinement and constraint of surfactant tails within micelles. Finally, these theoretical and simulations-based strategies are used to predict the micellization behavior of 55 linear surfactants and 28 branched surfactants. Critical micelle concentration and optimal micelle properties are reported and compared with experiment, demonstrating good agreement across a range of surfactant head and tail types. In particular, the CSMT framework is found to provide improved agreement with experimental cmc's for the branched surfactants considered. (Copies available exclusively from MIT Libraries, libraries.mit.edu/docs - docs mit.edu)

Thermal emission property of solid solution Gd{sub 1-x}Nd{sub x}B{sub 6} (x=0, 0.6, 0.8)

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

Xing Zhang, Jiu; Hong Bao, Li; Lin Zhou, Shen, E-mail: zjiuxing@bjut.edu.cn, E-mail: Baolihong_10@yahoo.com.cn, E-mail: zhoushenlin@emails.bjut.edu.cn

2011-07-01

In this paper, to further explore the excellent emission properties of rare earth boride cathode, herein we present the synthesis, characterization and properties of polycrystalline Nd{sub 1-x}Gd{sub x}B{sub 6} (x = 0, 0.6, 0.8) bulk via arc plasma and reactive SPS. (author)

EFFECTIVE POROSITY IMPLIES EFFECTIVE BULK DENSITY IN SORBING SOLUTE TRANSPORT

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

Flach, G.

2012-02-27

The concept of an effective porosity is widely used in solute transport modeling to account for the presence of a fraction of the medium that effectively does not influence solute migration, apart from taking up space. This non-participating volume or ineffective porosity plays the same role as the gas phase in single-phase liquid unsaturated transport: it increases pore velocity, which is useful towards reproducing observed solute travel times. The prevalent use of the effective porosity concept is reflected by its prominent inclusion in popular texts, e.g., de Marsily (1986), Fetter (1988, 1993) and Zheng and Bennett (2002). The purpose ofmore » this commentary is to point out that proper application of the concept for sorbing solutes requires more than simply reducing porosity while leaving other material properties unchanged. More specifically, effective porosity implies the corresponding need for an effective bulk density in a conventional single-porosity model. The reason is that the designated non-participating volume is composed of both solid and fluid phases, both of which must be neglected for consistency. Said another way, if solute does not enter the ineffective porosity then it also cannot contact the adjoining solid. Conceptually neglecting the fluid portion of the non-participating volume leads to a lower (effective) porosity. Likewise, discarding the solid portion of the non-participating volume inherently leads to a lower or effective bulk density. In the author's experience, practitioners virtually never adjust bulk density when adopting the effective porosity approach.« less

Solvent effect on redox properties of hexanethiolate monolayer-protected gold nanoclusters.

PubMed

Su, Bin; Zhang, Meiqin; Shao, Yuanhua; Girault, Hubert H

2006-11-02

The capacitance of monolayer-protected gold nanoclusters (MPCs), C(MPC), in solution has been theoretically reconsidered from an electrostatic viewpoint, in which an MPC is considered as an isolated charged sphere within two dielectric layers, the intrinsic coating monolayer, and the bulk solvent. The model predicts that the bulk solvent provides an important contribution to C(MPC) and influences the redox properties of MPCs. This theoretical prediction is then examined experimentally by comparing the redox properties of MPCs in four organic solvents: 1,2-dichloroethane (DCE), dichloromethane (DCM), chlorobenzene (CB), and toluene (TOL), in all of which MPCs have excellent solubility. Furthermore, this set of organic solvents features a dielectric constant in a range from 10.37 (DCE) to 2.38 (TOL), which is wide enough to probe the solvent effect. In these organic solvents, tetrahexylammonium bis(trifluoromethylsulfonyl)imide (THATf2N) is used as the supporting electrolyte. Cyclic and differential pulse voltammetric results provide concrete evidence that, despite the monolayer protection, the solvent plays a significant effect on the properties of MPCs in solution.

Boron Arsenide and Boron Phosphide for High Temperature and Luminescent Devices. [semiconductor devices - crystal growth/crystal structure

NASA Technical Reports Server (NTRS)

Chu, T. L.

1975-01-01

The crystal growth of boron arsenide and boron phosphide in the form of bulk crystals and epitaxial layers on suitable substrates is discussed. The physical, chemical, and electrical properties of the crystals and epitaxial layers are examined. Bulk crystals of boron arsenide were prepared by the chemical transport technique, and their carrier concentration and Hall mobility were measured. The growth of boron arsenide crystals from high temperature solutions was attempted without success. Bulk crystals of boron phosphide were also prepared by chemical transport and solution growth techniques. Techniques required for the fabrication of boron phosphide devices such as junction shaping, diffusion, and contact formation were investigated. Alloying techniques were developed for the formation of low-resistance ohmic contacts to boron phosphide. Four types of boron phosphide devices were fabricated: (1) metal-insulator-boron phosphide structures, (2) Schottky barriers; (3) boron phosphide-silicon carbide heterojunctions; and (4) p-n homojunctions. Easily visible red electroluminescence was observed from both epitaxial and solution grown p-n junctions.

The spatial range of protein hydration

NASA Astrophysics Data System (ADS)

Persson, Filip; Söderhjelm, Pär; Halle, Bertil

2018-06-01

Proteins interact with their aqueous surroundings, thereby modifying the physical properties of the solvent. The extent of this perturbation has been investigated by numerous methods in the past half-century, but a consensus has still not emerged regarding the spatial range of the perturbation. To a large extent, the disparate views found in the current literature can be traced to the lack of a rigorous definition of the perturbation range. Stating that a particular solvent property differs from its bulk value at a certain distance from the protein is not particularly helpful since such findings depend on the sensitivity and precision of the technique used to probe the system. What is needed is a well-defined decay length, an intrinsic property of the protein in a dilute aqueous solution, that specifies the length scale on which a given physical property approaches its bulk-water value. Based on molecular dynamics simulations of four small globular proteins, we present such an analysis of the structural and dynamic properties of the hydrogen-bonded solvent network. The results demonstrate unequivocally that the solvent perturbation is short-ranged, with all investigated properties having exponential decay lengths of less than one hydration shell. The short range of the perturbation is a consequence of the high energy density of bulk water, rendering this solvent highly resistant to structural perturbations. The electric field from the protein, which under certain conditions can be long-ranged, induces a weak alignment of water dipoles, which, however, is merely the linear dielectric response of bulk water and, therefore, should not be thought of as a structural perturbation. By decomposing the first hydration shell into polarity-based subsets, we find that the hydration structure of the nonpolar parts of the protein surface is similar to that of small nonpolar solutes. For all four examined proteins, the mean number of water-water hydrogen bonds in the nonpolar subset is within 1% of the value in bulk water, suggesting that the fragmentation and topography of the nonpolar protein-water interface has evolved to minimize the propensity for protein aggregation by reducing the unfavorable free energy of hydrophobic hydration.

Electrochemically induced annealing of stainless-steel surfaces.

PubMed

Burstein, G T; Hutchings, I M; Sasaki, K

2000-10-19

Modification of the surface properties of metals without affecting their bulk properties is of technological interest in demanding applications where surface stability and hardness are important. When austenitic stainless steel is heavily plastically deformed by grinding or rolling, a martensitic phase transformation occurs that causes significant changes in the bulk and surface mechanical properties of the alloy. This martensitic phase can also be generated in stainless-steel surfaces by cathodic charging, as a consequence of lattice strain generated by absorbed hydrogen. Heat treatment of the steel to temperatures of several hundred degrees can result in loss of the martensitic structure, but this alters the bulk properties of the alloy. Here we show that martensitic structures in stainless steel can be removed by appropriate electrochemical treatment in aqueous solutions at much lower temperature than conventional annealing treatments. This electrochemically induced annealing process allows the hardness of cold-worked stainless steels to be maintained, while eliminating the brittle martensitic phase from the surface. Using this approach, we are able to anneal the surface and near-surface regions of specimens that contain rolling-induced martensite throughout their bulk, as well as those containing surface martensite induced by grinding. Although the origin of the electrochemical annealing process still needs further clarification, we expect that this treatment will lead to further development in enhancing the surface properties of metals.

Communication: Contrasting effects of glycerol and DMSO on lipid membrane surface hydration dynamics and forces

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

Schrader, Alex M.; Cheng, Chi-Yuan; Israelachvili, Jacob N.

2016-07-28

Glycerol and dimethyl sulfoxide (DMSO) are commonly used cryoprotectants in cellular systems, but due to the challenges of measuring the properties of surface-bound solvent, fundamental questions remain regarding the concentration, interactions, and conformation of these solutes at lipid membrane surfaces. We measured the surface water diffusivity at gel-phase dipalmitoylphosphatidylcholine (DPPC) bilayer surfaces in aqueous solutions containing ≤7.5 mol. % of DMSO or glycerol using Overhauser dynamic nuclear polarization. We found that glycerol similarly affects the diffusivity of water near the bilayer surface and that in the bulk solution (within 20%), while DMSO substantially increases the diffusivity of surface water relativemore » to bulk water. We compare these measurements of water dynamics with those of equilibrium forces between DPPC bilayers in the same solvent mixtures. DMSO greatly decreases the range and magnitude of the repulsive forces between the bilayers, whereas glycerol increases it. We propose that the differences in hydrogen bonding capability of the two solutes leads DMSO to dehydrate the lipid head groups, while glycerol affects surface hydration only as much as it affects the bulk water properties. The results suggest that the mechanism of the two most common cryoprotectants must be fundamentally different: in the case of DMSO by decoupling the solvent from the lipid surface, and in the case of glycerol by altering the hydrogen bond structure and intermolecular cohesion of the global solvent, as manifested by increased solvent viscosity.« less

Thermodynamic and Structural Properties of Methanol-Water Solutions Using Non-Additive Interaction Models

PubMed Central

Zhong, Yang; Warren, G. Lee; Patel, Sandeep

2014-01-01

We study bulk structural and thermodynamic properties of methanol-water solutions via molecular dynamics simulations using novel interaction potentials based on the charge equilibration (fluctuating charge) formalism to explicitly account for molecular polarization at the atomic level. The study uses the TIP4P-FQ potential for water-water interactions, and the CHARMM-based (Chemistry at HARvard Molecular Mechanics) fluctuating charge potential for methanol-methanol and methanol-water interactions. In terms of bulk solution properties, we discuss liquid densities, enthalpies of mixing, dielectric constants, self-diffusion constants, as well as structural properties related to local hydrogen bonding structure as manifested in radial distribution functions and cluster analysis. We further explore the electronic response of water and methanol in the differing local environments established by the interaction of each species predominantly with molecules of the other species. The current force field for the alcohol-water interaction performs reasonably well for most properties, with the greatest deviation from experiment observed for the excess mixing enthalpies, which are predicted to be too favorable. This is qualitatively consistent with the overestimation of the methanol-water gas-phase interaction energy for the lowest-energy conformer (methanol as proton donor). Hydration free energies for methanol in TIP4P-FQ water are predicted to be −5.6±0.2 kcal/mole, in respectable agreement with the experimental value of −5.1 kcal/mole. With respect to solution micro-structure, the present cluster analysis suggests that the micro-scale environment for concentrations where select thermodynamic quantities reach extremal values is described by a bi-percolating network structure. PMID:18074339

Optical characteristics of novel bulk and nanoengineered laser host materials

NASA Astrophysics Data System (ADS)

Prasad, Narasimha S.; Sova, Stacey; Kelly, Lisa; Bevan, Talon; Arnold, Bradley; Cooper, Christopher; Choa, Fow-Sen; Singh, N. B.

2018-02-01

The hexagonal apatite single crystals have been investigated for their applications as laser host materials. Czochralksi and flux growth methods have been utilized to obtain single crystals. For low temperature processing (<100 0C), several techniques for crystal growth have been developed. The hexagonal apatite structure (space group P63/m) is characteristic of several compounds, some of which have extremely interesting and useful properties as laser hosts and bone materials. Calcium lanthanum silicate (Nd-doped) and lanthanum aluminate material systems were studied in detail. Nanoengineered calcium and lanthanum based silicates were synthesized by a solution method and their optical and morphological characteristics were compared with Czochralski grown bulk hydroxyapatite single crystals. Materials were evaluated by absorbance, fluorescence and Raman characteristics. Neodymium, iron and chromium doped crystals grown by a solution method showed weak but similar optical properties to that of Czochralski grown single crystals.

Microwave Dielectric Constant Dependence on Soil Tension.

DTIC Science & Technology

1983-10-01

water to be only a single monolayer thick .1 (OA) with Ice-like dielectric properties EWS = (3.15, JO). The first approach apportions the soil solution Into...mixing model that accounts explicitly for the presence of a hydrationU layer of bound water adjacent to hydrophilic soil particle surfaces. The soil ... solution is differentiated Into (1) a bound, ice-like component and (2) a bulk solution component, by a physical soil model dependent upon either soil

Solution based approach for the fabrication of photonic devices in chalcogenide glasses

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

Prince,, E-mail: princevish2@gmail.com; Raman, Swati; Dwivedi, Prabhat K.

2015-06-24

In this report, we describe the solution preparation conditions of various chalcogenide glasses. The dissolution mechanism of (As{sub 2}S{sub 3}){sub 60}Ge{sub 40}, (As{sub 2}S{sub 3}){sub 60}Se{sub 40} in ethanolamine is studied. Dynamic light scattering (DLS)measurements confirms that the particles in suspension are <10 nm in all the solutions.Prepared solutions are shown to possess similar molecular structure to the parent bulk glasses. Optical properties of the prepared solution are also discussed.

Anisotropic Bianchi Type-I and Type-II Bulk Viscous String Cosmological Models Coupled with Zero Mass Scalar Field

NASA Astrophysics Data System (ADS)

Venkateswarlu, R.; Sreenivas, K.

2014-06-01

The LRS Bianchi type-I and type-II string cosmological models are studied when the source for the energy momentum tensor is a bulk viscous stiff fluid containing one dimensional strings together with zero-mass scalar field. We have obtained the solutions of the field equations assuming a functional relationship between metric coefficients when the metric is Bianchi type-I and constant deceleration parameter in case of Bianchi type-II metric. The physical and kinematical properties of the models are discussed in each case. The effects of Viscosity on the physical and kinematical properties are also studied.

Dynamic analysis of bulk-fill composites: Effect of food-simulating liquids.

PubMed

Eweis, Ahmed Hesham; Yap, Adrian U-Jin; Yahya, Noor Azlin

2017-10-01

This study investigated the effect of food simulating liquids on visco-elastic properties of bulk-fill restoratives using dynamic mechanical analysis. One conventional composite (Filtek Z350 [FZ]), two bulk-fill composites (Filtek Bulk-fill [FB] and Tetric N Ceram [TN]) and a bulk-fill giomer (Beautifil-Bulk Restorative [BB]) were evaluated. Specimens (12 × 2 × 2mm) were fabricated using customized stainless steel molds. The specimens were light-cured, removed from their molds, finished, measured and randomly divided into six groups. The groups (n = 10) were conditioned in the following mediums for 7 days at 37°C: air (control), artificial saliva (SAGF), distilled water, 0.02N citric acid, heptane, 50% ethanol-water solution. Specimens were assessed using dynamic mechanical testing in flexural three-point bending mode and their respective mediums at 37°C and a frequency range of 0.1-10Hz. The distance between the supports were fixed at 10mm and an axial load of 5N was employed. Data for elastic modulus, viscous modulus and loss tangent were subjected to ANOVA/Tukey's tests at significance level p < 0.05. Significant differences in visco-elastic properties were observed between materials and mediums. Apart from bulk-fill giomer, elastic modulus was the highest after conditioning in heptane. No apparent trends were noted for viscous modulus. Generally, loss tangent was the highest after conditioning in ethanol. The effect of food-simulating liquids on the visco-elastic properties of bulk-fill composites was material and medium dependent. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sliding Wear Characteristics and Corrosion Behaviour of Selective Laser Melted 316L Stainless Steel

NASA Astrophysics Data System (ADS)

Sun, Y.; Moroz, A.; Alrbaey, K.

2014-02-01

Stainless steel is one of the most popular materials used for selective laser melting (SLM) processing to produce nearly fully dense components from 3D CAD models. The tribological and corrosion properties of stainless steel components are important in many engineering applications. In this work, the wear behaviour of SLM 316L stainless steel was investigated under dry sliding conditions, and the corrosion properties were measured electrochemically in a chloride containing solution. The results show that as compared to the standard bulk 316L steel, the SLM 316L steel exhibits deteriorated dry sliding wear resistance. The wear rate of SLM steel is dependent on the vol.% porosity in the steel and by obtaining full density it is possible achieve wear resistance similar to that of the standard bulk 316L steel. In the tested chloride containing solution, the general corrosion behaviour of the SLM steel is similar to that of the standard bulk 316L steel, but the SLM steel suffers from a reduced breakdown potential and is more susceptible to pitting corrosion. Efforts have been made to correlate the obtained results with porosity in the SLM steel.

Closed string tachyon driving f(R) cosmology

NASA Astrophysics Data System (ADS)

Wang, Peng; Wu, Houwen; Yang, Haitang

2018-05-01

To study quantum effects on the bulk tachyon dynamics, we replace R with f(R) in the low-energy effective action that couples gravity, the dilaton, and the bulk closed string tachyon of bosonic closed string theory and study properties of their classical solutions. The α' corrections of the graviton-dilaton-tachyon system are implemented in the f(R). We obtain the tachyon-induced rolling solutions and show that the string metric does not need to remain fixed in some cases. In the case with H( t=‑∞ ) = , only the R and R2 terms in f(R) play a role in obtaining the rolling solutions with nontrivial metric. The singular behavior of more classical solutions are investigated and found to be modified by quantum effects. In particular, there could exist some classical solutions, in which the tachyon field rolls down from a maximum of the tachyon potential while the dilaton expectation value is always bounded from above during the rolling process.

Inflationary solutions in the brane world and their geometrical interpretation

NASA Astrophysics Data System (ADS)

Khoury, Justin; Steinhardt, Paul J.; Waldram, Daniel

2001-05-01

We consider the cosmology of a pair of domain walls bounding a five-dimensional bulk space-time with a negative cosmological constant, in which the distance between the branes is not fixed in time. Although there are strong arguments to suggest that this distance should be stabilized in the present epoch, no such constraints exist for the early universe and thus non-static solutions might provide relevant inflationary scenarios. We find the general solution for the standard ansatz where the bulk is foliated by planar-symmetric hypersurfaces. We show that in all cases the bulk geometry is that of anti-de Sitter (AdS5) space. We then present a geometrical interpretation for the solutions as embeddings of two de Sitter (dS4) surfaces in AdS5, which provide a simple interpretation of the physical properties of the solutions. A notable feature explained in the analysis is that two-way communication between branes expanding away from one another is possible for a finite amount of time, after which communication can proceed in one direction only. The geometrical picture also shows that our class of solutions (and related solutions in the literature) is not completely general, contrary to some claims. We then derive the most general solution for two walls in AdS5. This includes novel cosmologies where the brane tensions are not constrained to have opposite signs. The construction naturally generalizes to arbitrary FRW cosmologies on the branes.

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

Leaching of Conductive Species: Implications to Measurements of Electrical Resistivity

PubMed Central

Spragg, R; Jones, S; Bu, Y; Lu, Y; Bentz, D; Snyder, K; Weiss, J

2017-01-01

Electrical tests have been used to characterize the microstructure of porous materials, the measured electrical response being determined by the contribution of the microstructure (porosity and tortuosity) and the electrical properties of the solution (conductivity of the pore solution) inside the pores of the material. This study has shown how differences in concentration between the pore solution (i.e., the solution in the pores) and the storage solution surrounding the test specimen leads to significant transport (leaching) of the conductive ionic species between the pore solution and the storage solution. Leaching influences the resistivity of the pore solution, thereby influencing electrical measurements on the bulk material from either a surface or uniaxial bulk resistance test. This paper has three main conclusions: 1.) Leaching of conductive species does occur with concentration gradients and that a diffusion based approach can be used to estimate the time scale associated with this change. 2.) Leaching of ions in the pore solution can influence resistivity measurements, and the ratio of surface to uniaxial resistivity can be used as a method to assess the presence of leaching and 3.) An estimation of the magnitude of leaching for standardized tests of cementitious materials. PMID:28584407

Leaching of Conductive Species: Implications to Measurements of Electrical Resistivity.

PubMed

Spragg, R; Jones, S; Bu, Y; Lu, Y; Bentz, D; Snyder, K; Weiss, J

2017-05-01

Electrical tests have been used to characterize the microstructure of porous materials, the measured electrical response being determined by the contribution of the microstructure (porosity and tortuosity) and the electrical properties of the solution (conductivity of the pore solution) inside the pores of the material. This study has shown how differences in concentration between the pore solution (i.e., the solution in the pores) and the storage solution surrounding the test specimen leads to significant transport (leaching) of the conductive ionic species between the pore solution and the storage solution. Leaching influences the resistivity of the pore solution, thereby influencing electrical measurements on the bulk material from either a surface or uniaxial bulk resistance test. This paper has three main conclusions: 1.) Leaching of conductive species does occur with concentration gradients and that a diffusion based approach can be used to estimate the time scale associated with this change. 2.) Leaching of ions in the pore solution can influence resistivity measurements, and the ratio of surface to uniaxial resistivity can be used as a method to assess the presence of leaching and 3.) An estimation of the magnitude of leaching for standardized tests of cementitious materials.

Synthesis and properties of the compound: LiNi 3/5Cu 2/5VO 4

NASA Astrophysics Data System (ADS)

Ram, Moti

2009-12-01

The LiNi 3/5Cu 2/5VO 4 is synthesized by solution-based chemical method and its formation has been checked by X-ray diffraction (XRD) study. XRD study shows a tetragonal unit cell structure with lattice parameters of a = 11.6475 (18) Å, c = 2.4855 (18) Å and c/ a = 0.2134 Å. Electrical properties are verified using complex impedance spectroscopy (CIS) technique. Complex impedance analysis reveals following points: (i) the bulk contribution to electrical properties up to 200 °C, (ii) the bulk and grain boundary contribution at T ≥ 225 °C, (iii) the presence of temperature dependent electrical relaxation phenomena in the material. D.c. conductivity study indicates that electrical conduction in the material is a thermally activated process.

Biocompatible Zr-Al-Fe bulk metallic glasses with large plasticity

NASA Astrophysics Data System (ADS)

Hua, NengBin; Li, Ran; Wang, JianFeng; Zhang, Tao

2012-09-01

In the present study, high-zirconium ternary Zr-Al-Fe bulk metallic glasses (BMGs) with low Young's modulus and good plasticity were developed. Zr75Al7.5Fe17.5 BMG exhibits a low Young's modulus of 70 GPa and high Poisson's ratio of 0.403. Pronounced plasticity was demonstrated under both compression and bending conditions for the BMGs. Furthermore, the alloys show high corrosion resistance in phosphate buffered solution. The combination of desirable mechanical and chemical properties implies potential for biomedical applications.

On the electron affinity of cytosine in bulk water and at hydrophobic aqueous interfaces.

PubMed

Vöhringer-Martinez, Esteban; Dörner, Ciro; Abel, Bernd

2014-10-01

In the past one possible mechanism of DNA damage in bulk water has been attributed to the presence of hydrated electrons in water. Recently, one important property of hydrated electrons, namely their binding energy, was reported to be smaller at hydrophobic interfaces than in bulk aqueous solution. This possibly opens up new reaction possibilities with different solutes such as the DNA at hydrophobic, aqueous interfaces. Here, we use QM/MM molecular dynamics simulation to study how the molecular environment at the vacuum-water interface and in the bulk alters the electron affinity of cytosine being a characteristic part of the DNA. The electron affinity at the interface is closer to the corresponding binding energy of the partially hydrated electron. The increased energy resonance makes the electron capture process more probable and suggests that hydrated electrons at hydrophobic interfaces may be more reactive than the fully hydrated ones. Additionally, we found that the relaxation of the anionic form after electron attachment also induces a proton transfer from the surrounding solvent that was confirmed by comparison with the experimental reduction potential.

Geochemical heterogeneity in a sand and gravel aquifer: Effect of sediment mineralogy and particle size on the sorption of chlorobenzenes

USGS Publications Warehouse

Barber, L.B.; Thurman, E.M.; Runnells, D.R.; ,

1992-01-01

The effect of particle size, mineralogy and sediment organic carbon (SOC) on solution of tetrachlorobenzene and pentachlorobenzene was evaluated using batch-isotherm experiments on sediment particle-size and mineralogical fractions from a sand and gravel aquifer, Cape Cod, Massachusetts. Concentration of SOC and sorption of chlorobenzenes increase with decreasing particle size. For a given particle size, the magnetic fraction has a higher SOC content and sorption capacity than the bulk or non-magnetic fractions. Sorption appears to be controlled by the magnetic minerals, which comprise only 5-25% of the bulk sediment. Although SOC content of the bulk sediment is < 0.1%, the observed sorption of chlorobenzenes is consistent with a partition mechanism and is adequately predicted by models relating sorption to the octanol/water partition coefficient of the solute and SOC content. A conceptual model based on preferential association of dissolved organic matter with positively-charged mineral surfaces is proposed to describe micro-scale, intergranular variability in sorption properties of the aquifer sediments.The effect of particle size, mineralogy and sediment organic carbon (SOC) on sorption of tetrachlorobenzene and pentachlorobenzene was evaluated using batch-isotherm experiments on sediment particle-size and mineralogical fractions from a sand and gravel aquifer, Cape Cod, Massachusetts. Concentration of SOC and sorption of chlorobenzenes increase with decreasing particle size. For a given particle size, the magnetic fraction has a higher SOC content and sorption capacity than the bulk or non-magnetic fractions. Sorption appears to be controlled by the magnetic minerals, which comprise only 5-25% of the bulk sediment. Although SOC content of the bulk sediment is <0.1%, the observed sorption of chlorobenzenes is consistent with a partition mechanism and is adequately predicted by models relating sorption to the octanol/water partition coefficient of the solute and SOC content. A conceptual model based on preferential association of dissolved organic matter with positively-charged mineral surfaces is proposed to describe micro-scale, intergranular variability in sorption properties of the aquifer sediments.

Changes in apparent molar water volume and DKP solubility yield insights on the Hofmeister effect.

PubMed

Payumo, Alexander Y; Huijon, R Michael; Mansfield, Deauna D; Belk, Laurel M; Bui, Annie K; Knight, Anne E; Eggers, Daryl K

2011-12-15

This study examines the properties of a 4 × 2 matrix of aqueous cations and anions at concentrations up to 8.0 M. The apparent molar water volume, as calculated by subtracting the mass and volume of the ions from the corresponding solution density, was found to exceed the molar volume of ice in many concentrated electrolyte solutions, underscoring the nonideal behavior of these systems. The solvent properties of water were also analyzed by measuring the solubility of diketopiperazine (DKP) in 2.000 M salt solutions prepared from the same ion combinations. Solution rankings for DKP solubility were found to parallel the Hofmeister series for both cations and anions, whereas molar water volume concurred with the cation series only. The results are discussed within the framework of a desolvation energy model that attributes solute-specific changes in equilibria to solute-dependent changes in the free energy of bulk water.

Changes in Apparent Molar Water Volume and DKP Solubility Yield Insights on the Hofmeister Effect

PubMed Central

Payumo, Alexander Y.; Huijon, R. Michael; Mansfield, Deauna D.; Belk, Laurel M.; Bui, Annie K.; Knight, Anne E.; Eggers, Daryl K.

2011-01-01

This study examines the properties of a 4 × 2 matrix of aqueous cations and anions at concentrations up to 8.0 M. The apparent molar water volume, as calculated by subtracting the mass and volume of the ions from the corresponding solution density, was found to exceed the molar volume of ice in many concentrated electrolyte solutions, underscoring the non-ideal behavior of these systems. The solvent properties of water were also analyzed by measuring the solubility of diketopiperazine (DKP) in 2.000 M salt solutions prepared from the same ion combinations. Solution rankings for DKP solubility were found to parallel the Hofmeister series for both cations and anions, whereas molar water volume concurred with the cation series only. The results are discussed within the framework of a desolvation energy model that attributes solute-specific changes in equilibria to solute-dependent changes in the free energy of bulk water. PMID:22029390

Toxicity of silver and copper to Cucurbita pepo: differential effects of nano and bulk-size particles.

PubMed

Musante, Craig; White, Jason C

2012-09-01

The phytotoxicity of bulk and nanoparticle Cu and Ag was directly compared. NP Ag reduced biomass and transpiration by 66-84% when compared with bulk Ag. The Ag ion concentration was 4.4-10-times greater in NP than bulk particle solutions. The Cu ion concentration was 1.4-4.4-times greater in bulk than NP amended solutions. Humic acid (50 mg/L) decreased the ion content of bulk Cu solution by 38-42% but increased ion Cu content of NP solutions by 1.4-2.9 times. Bulk and NP Cu were highly phytotoxic; growth and transpiration were reduced by 60-70% relative to untreated controls. NP Cu phytotoxicity was unaffected by solution type, but humic acid (50 mg/L) completely alleviated phytotoxicity caused by bulk Cu. The data demonstrate differential toxicity of Ag NP relative to bulk Ag. The finding that humic acid and solution chemistry differentially impact bulk and NP behavior highlights the importance of evaluating nanoparticles under environmentally relevant conditions. Copyright © 2010 Wiley Periodicals, Inc.

Phthalocyanine Blends Improve Bulk Heterojunction Solar Cells

PubMed Central

Varotto, Alessandro; Nam, Chang-Yong; Radivojevic, Ivana; Tomé, Joao; Cavaleiro, José A.S.; Black, Charles T.; Drain, Charles Michael

2010-01-01

A core phthalocyanine platform allows engineering the solubility properties the band gap; shifting the maximum absorption toward the red. A simple method to increase the efficiency of heterojunction solar cells uses a self-organized blend of the phthalocyanine chromophores fabricated by solution processing. PMID:20136126

Synthesis and properties of mecoprop-intercalated layered double hydroxide

NASA Astrophysics Data System (ADS)

Ahmed Khan, Modabber; Choi, Choong-Lyeal; Lee, Dong-Hoon; Park, Man; Lim, Bu-Kug; Lee, Jong-Yoon; Choi, Jyung

2007-08-01

This study carried out to elucidate the synthesis of MCPP LDH hybrid, release pattern of MCPP from MCPP LDH hybrid and their properties. MCPP LDH hybrid was synthesized from MCPP and Mg Al complex. Release pattern of MCPP from MCPP LDH hybrid was slower in distilled water and soil solution but it was slower in distilled water than soil solution. MCPP LDH hybrid has shown more stable condition than CO32- form of LDH in thermal and acidic condition. Therefore, MCPP LDH hybrid would lead as functional and benign pesticide to minimize the harmful effects on soil environment by bulk herbicides.

Synthesis and supramolecular assembly of biomimetic polymers

NASA Astrophysics Data System (ADS)

Marciel, Amanda Brittany

A grand challenge in materials chemistry is the synthesis of macromolecules and polymers with precise shapes and architectures. Polymer microstructure and architecture strongly affect the resulting functionality of advanced materials, yet understanding the static and dynamic properties of these complex macromolecules in bulk has been difficult due to their inherit polydispersity. Single molecule studies have provided a wealth of information on linear flexible and semi-flexible polymers in dilute solutions. However, few investigations have focused on industrially relevant complex topologies (e.g., star, comb, hyperbranched polymers) in industrially relevant solution conditions (e.g., semi-dilute, concentrated). Therefore, from this perspective there is a strong need to synthesize precision complex architectures for bulk studies as well as complex architectures compatible with current single molecule techniques to study static and dynamic polymer properties. In this way, we developed a hybrid synthetic strategy to produce branched polymer architectures based on chemically modified DNA. Overall, this approach enables control of backbone length and flexibility, as well as branch grafting density and chemical identity. We utilized a two-step scheme based on enzymatic incorporation of non-natural nucleotides containing bioorthogonal dibenzocyclooctyne (DBCO) functional groups along the main polymer backbone, followed by copper-free "click" chemistry to graft synthetic polymer branches or oligonucleotide branches to the DNA backbone, thereby allowing for the synthesis of a variety of polymer architectures, including three-arm stars, H-polymers, graft block copolymers, and comb polymers for materials assembly and single molecule studies. Bulk materials properties are also affected by industrial processing conditions that alter polymer morphology. Therefore, in an alternative strategy we developed a microfluidic-based approach to assemble highly aligned synthetic oligopeptides nanostructures using microscale extensional flows. This strategy enabled reproducible, reliable fabrication of aligned hierarchical constructs that do not form spontaneously in solution. In this way, fluidic-directed assembly of supramolecular structures allows for unprecedented manipulation at the nano- and mesoscale, which has the potential to provide rapid and efficient control of functional materials properties.

Poly(imide-siloxane) segmented copolymer structural adhesives prepared by bulk and solution thermal imidization

NASA Technical Reports Server (NTRS)

Bott, R. H.; Summers, J. D.; Arnold, C. A.; Blankenship, C. P., Jr.; Taylor, L. T.

1988-01-01

The improved properties that have been demonstrated through thermal solution imidization in the case of polyimides and poly(imide-siloxane) segmented copolymers suggests significant potential for application of these new materials. Specifically, the enhancement in solubility, moisture reduction, and processability observed through this solution technique is quite dramatic. Previous work has shown that the presence of low amounts of siloxane does not detract significantly from the lap shear strength of these materials to titanium in the case of bulk thermal imidization synthesis. In addition, the siloxane incorporation results in the added advantage of resistance to hot, wet environments. This added durability is presumably due to the hydrophobic siloxane segments preventing the uptake of water at the critical interphase between the adhesive and the adherend. This paper discusses the extension of this work to the solution imidization synthesis technique recently developed in our laboratory. Results dealing with the absolute bond strengths as well as durability and failure surface analysis will be presented.

Raoult's Law: A General Chemistry Experiment.

ERIC Educational Resources Information Center

Steffel, Margaret J.

1983-01-01

To make material on Raoult's law more meaningful, students complete exercises on paper, in the laboratory, and with molecular models. Paper exercises give practice using the law; laboratory work illustrates behavior of real solutions; and models show relationships between properties of individual molecules and of matter in bulk. (JN)

Molecular conformation of linear alkane molecules: From gas phase to bulk water through the interface

NASA Astrophysics Data System (ADS)

Murina, Ezequiel L.; Fernández-Prini, Roberto; Pastorino, Claudio

2017-08-01

We studied the behavior of long chain alkanes (LCAs) as they were transferred from gas to bulk water, through the liquid-vapor interface. These systems were studied using umbrella sampling molecular dynamics simulation and we have calculated properties like free energy profiles, molecular orientation, and radius of gyration of the LCA molecules. The results show changes in conformation of the solutes along the path. LCAs adopt pronounced molecular orientations and the larger ones extend appreciably when partially immersed in the interface. In bulk water, their conformations up to dodecane are mainly extended. However, larger alkanes like eicosane present a more stable collapsed conformation as they approach bulk water. We have characterized the more probable configurations in all interface and bulk regions. The results obtained are of interest for the study of biomatter processes requiring the transfer of hydrophobic matter, especially chain-like molecules like LCAs, from gas to bulk aqueous systems through the interface.

Enhancement of the inverted polymer solar cells via ZnO doped with CTAB

NASA Astrophysics Data System (ADS)

Sivashnamugan, Kundan; Guo, Tzung-Fang; Hsu, Yao-Jane; Wen, Ten-Chin

2018-02-01

A facile approach enhancing electron extraction in zinc oxide (ZnO) electron transfer interlayer and improving performance of bulk-heterojunction (BHJ) polymer solar cells (PSCs) by adding cetyltrimethylammonium bromide (CTAB) into sol-gel ZnO precursor solution was demonstrated in this work. The power conversion efficiency (PCE) has a 24.1% increment after modification. Our results show that CTAB can dramatically influence optical, electrical and morphological properties of ZnO electron transfer layer, and work as effective additive to enhance the performance of bulk- heterojunction polymer solar cells.

Development of property-transfer models for estimating the hydraulic properties of deep sediments at the Idaho National Engineering and Environmental Laboratory, Idaho

USGS Publications Warehouse

Winfield, Kari A.

2005-01-01

Because characterizing the unsaturated hydraulic properties of sediments over large areas or depths is costly and time consuming, development of models that predict these properties from more easily measured bulk-physical properties is desirable. At the Idaho National Engineering and Environmental Laboratory, the unsaturated zone is composed of thick basalt flow sequences interbedded with thinner sedimentary layers. Determining the unsaturated hydraulic properties of sedimentary layers is one step in understanding water flow and solute transport processes through this complex unsaturated system. Multiple linear regression was used to construct simple property-transfer models for estimating the water-retention curve and saturated hydraulic conductivity of deep sediments at the Idaho National Engineering and Environmental Laboratory. The regression models were developed from 109 core sample subsets with laboratory measurements of hydraulic and bulk-physical properties. The core samples were collected at depths of 9 to 175 meters at two facilities within the southwestern portion of the Idaho National Engineering and Environmental Laboratory-the Radioactive Waste Management Complex, and the Vadose Zone Research Park southwest of the Idaho Nuclear Technology and Engineering Center. Four regression models were developed using bulk-physical property measurements (bulk density, particle density, and particle size) as the potential explanatory variables. Three representations of the particle-size distribution were compared: (1) textural-class percentages (gravel, sand, silt, and clay), (2) geometric statistics (mean and standard deviation), and (3) graphical statistics (median and uniformity coefficient). The four response variables, estimated from linear combinations of the bulk-physical properties, included saturated hydraulic conductivity and three parameters that define the water-retention curve. For each core sample,values of each water-retention parameter were estimated from the appropriate regression equation and used to calculate an estimated water-retention curve. The degree to which the estimated curve approximated the measured curve was quantified using a goodness-of-fit indicator, the root-mean-square error. Comparison of the root-mean-square-error distributions for each alternative particle-size model showed that the estimated water-retention curves were insensitive to the way the particle-size distribution was represented. Bulk density, the median particle diameter, and the uniformity coefficient were chosen as input parameters for the final models. The property-transfer models developed in this study allow easy determination of hydraulic properties without need for their direct measurement. Additionally, the models provide the basis for development of theoretical models that rely on physical relationships between the pore-size distribution and the bulk-physical properties of the media. With this adaptation, the property-transfer models should have greater application throughout the Idaho National Engineering and Environmental Laboratory and other geographic locations.

Polythiophene Derivative with a Side Chain Chromophore as Photovoltaic and Photorefractive Materials

DTIC Science & Technology

1993-11-17

the desired bulk property in the polymer such as water solubility,1 8 optical activity,19 ionic conductivity 20 or liquid crystalline properties. 2 1...photoexcitation, which is similar to photoinduced polarization observed in the Langmuir - Blodgett (L-B) films of donor-acceptor molecules. 23 But due to...Maximum 200 Words) A new, solution processable, thiophene copolymer with a side chain nonlinear optical (NLO) chromophore namely Poly (3-octylthiophene

Stress Wave Interactions with Tunnels Buried in Well-Characterized Jointed Media.

DTIC Science & Technology

1980-06-01

27 14 Particle Velocity and Principal Stress Fields at 62 jisec for the Elastic- Plastic Media Model (Case 1, 0.8 kbar...is used; the basic formulation is similar to the HEMP code (Ref. 3) . Tn numerical solutions and material properties are luscriben in Section 3. 3...media is 16A rock simulant. The elastic- plastic properties are modeled with the following parameters: Bulk Modulus K = .131 Mbar Shear Modulus G

Creation of Novel Solid-Solution Alloy Nanoparticles on the Basis of Density-of-States Engineering by Interelement Fusion.

PubMed

Kobayashi, Hirokazu; Kusada, Kohei; Kitagawa, Hiroshi

2015-06-16

Currently 118 known elements are represented in the periodic table. Of these 118 elements, only about 80 elements are stable, nonradioactive, and widely available for our society. From the viewpoint of the "elements strategy", we need to make full use of the 80 elements to bring out their latent ability and create innovative materials. Furthermore, there is a strong demand that the use of rare or toxic elements be reduced or replaced while their important properties are retained. Advanced science and technology could create higher-performance materials even while replacing or reducing minor or harmful elements through the combination of more abundant elements. The properties of elements are correlated directly with their electronic states. In a solid, the magnitude of the density of states (DOS) at the Fermi level affects the physical and chemical properties. In the present age, more attention has been paid to improving the properties of materials by means of alloying elements. In particular, the solid-solution-type alloy is advantageous because the properties can be continuously controlled by tuning the compositions and/or combinations of the constituent elements. However, the majority of bulk alloys are of the phase-separated type under ambient conditions, where constituent elements are immiscible with each other. To overcome the challenge of the bulk-phase metallurgical aspects, we have focused on the nanosize effect and developed methods involving "nonequilibrium synthesis" or "a process of hydrogen absorption/desorption". We propose a new concept of "density-of-states engineering" for the design of materials having the most desirable and suitable properties by means of "interelement fusion". In this Account, we describe novel solid-solution alloys of Pd-Pt, Ag-Rh, and Pd-Ru systems in which the constituent elements are immiscible in the bulk state. The homogeneous solid-solution alloys of Pd and Pt were created from Pd core/Pt shell nanoparticles using a hydrogen absorption/desorption process as a trigger. Several atom percent replacements of Pd with Pt atoms resulted in a significantly enhanced hydrogen absorption capacity compared with Pd nanoparticles. AgxRh1-x and PdxRu1-x solid-solution alloy nanoparticles were also developed by nonequilibrium synthesis based on a polyol method. The AgxRh1-x nanoparticles demonstrated hydrogen storage properties, although pure metal nanoparticles of each constituent element do not adsorb hydrogen. AgxRh1-x is therefore considered to possess a similar electronic structure to Pd as a synthetic pseudo-palladium. The PdxRu1-x nanoparticles showed enhanced catalytic activity for CO oxidation, with the highest catalytic activity found using the equimolar Pd0.5Ru0.5 nanoparticles. The catalytic activity of the Pd0.5Ru0.5 nanoparticles exceeds that of the widely used and best-performing Ru catalysts for CO oxidation and is also higher than that of neighboring Rh on the periodic table. Our present work provides a guiding principle for the design of a suitable DOS shape according to the intended physical and/or chemical properties and a method for the development of novel solid-solution alloys.

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.

Detecting the Biopolymer Behavior of Graphene Nanoribbons in Aqueous Solution

NASA Astrophysics Data System (ADS)

Wijeratne, Sithara S.; Penev, Evgeni S.; Lu, Wei; Li, Jingqiang; Duque, Amanda L.; Yakobson, Boris I.; Tour, James M.; Kiang, Ching-Hwa

2016-08-01

Graphene nanoribbons (GNR), can be prepared in bulk quantities for large-area applications by reducing the product from the lengthwise oxidative unzipping of multiwalled carbon nanotubes (MWNT). Recently, the biomaterials application of GNR has been explored, for example, in the pore to be used for DNA sequencing. Therefore, understanding the polymer behavior of GNR in solution is essential in predicting GNR interaction with biomaterials. Here, we report experimental studies of the solution-based mechanical properties of GNR and their parent products, graphene oxide nanoribbons (GONR). We used atomic force microscopy (AFM) to study their mechanical properties in solution and showed that GNR and GONR have similar force-extension behavior as in biopolymers such as proteins and DNA. The rigidity increases with reducing chemical functionalities. The similarities in rigidity and tunability between nanoribbons and biomolecules might enable the design and fabrication of GNR-biomimetic interfaces.

Detecting the Biopolymer Behavior of Graphene Nanoribbons in Aqueous Solution

PubMed Central

Wijeratne, Sithara S.; Penev, Evgeni S.; Lu, Wei; Li, Jingqiang; Duque, Amanda L.; Yakobson, Boris I.; Tour, James M.; Kiang, Ching-Hwa

2016-01-01

Graphene nanoribbons (GNR), can be prepared in bulk quantities for large-area applications by reducing the product from the lengthwise oxidative unzipping of multiwalled carbon nanotubes (MWNT). Recently, the biomaterials application of GNR has been explored, for example, in the pore to be used for DNA sequencing. Therefore, understanding the polymer behavior of GNR in solution is essential in predicting GNR interaction with biomaterials. Here, we report experimental studies of the solution-based mechanical properties of GNR and their parent products, graphene oxide nanoribbons (GONR). We used atomic force microscopy (AFM) to study their mechanical properties in solution and showed that GNR and GONR have similar force-extension behavior as in biopolymers such as proteins and DNA. The rigidity increases with reducing chemical functionalities. The similarities in rigidity and tunability between nanoribbons and biomolecules might enable the design and fabrication of GNR-biomimetic interfaces. PMID:27503635

Influence of growth temperature on bulk and surface defects in hybrid lead halide perovskite films

NASA Astrophysics Data System (ADS)

Peng, Weina; Anand, Benoy; Liu, Lihong; Sampat, Siddharth; Bearden, Brandon E.; Malko, Anton V.; Chabal, Yves J.

2016-01-01

The rapid development of perovskite solar cells has focused its attention on defects in perovskites, which are gradually realized to strongly control the device performance. A fundamental understanding is therefore needed for further improvement in this field. Recent efforts have mainly focused on minimizing the surface defects and grain boundaries in thin films. Using time-resolved photoluminescence spectroscopy, we show that bulk defects in perovskite samples prepared using vapor assisted solution process (VASP) play a key role in addition to surface and grain boundary defects. The defect state density of samples prepared at 150 °C (~1017 cm-3) increases by 5 fold at 175 °C even though the average grains size increases slightly, ruling out grain boundary defects as the main mechanism for the observed differences in PL properties upon annealing. Upon surface passivation using water molecules, the PL intensity and lifetime of samples prepared at 200 °C are only partially improved, remaining significantly lower than those prepared at 150 °C. Thus, the present study indicates that the majority of these defect states observed at elevated growth temperatures originates from bulk defects and underscores the importance to control the formation of bulk defects together with grain boundary and surface defects to further improve the optoelectronic properties of perovskites.The rapid development of perovskite solar cells has focused its attention on defects in perovskites, which are gradually realized to strongly control the device performance. A fundamental understanding is therefore needed for further improvement in this field. Recent efforts have mainly focused on minimizing the surface defects and grain boundaries in thin films. Using time-resolved photoluminescence spectroscopy, we show that bulk defects in perovskite samples prepared using vapor assisted solution process (VASP) play a key role in addition to surface and grain boundary defects. The defect state density of samples prepared at 150 °C (~1017 cm-3) increases by 5 fold at 175 °C even though the average grains size increases slightly, ruling out grain boundary defects as the main mechanism for the observed differences in PL properties upon annealing. Upon surface passivation using water molecules, the PL intensity and lifetime of samples prepared at 200 °C are only partially improved, remaining significantly lower than those prepared at 150 °C. Thus, the present study indicates that the majority of these defect states observed at elevated growth temperatures originates from bulk defects and underscores the importance to control the formation of bulk defects together with grain boundary and surface defects to further improve the optoelectronic properties of perovskites. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06222e

Probing Chemical Properties of Interstitial Micro-fluids in Ice

NASA Astrophysics Data System (ADS)

Cheng, J.; Colussi, A. J.; Hoffmann, M. R.

2007-12-01

Liquid is present as microscopic channels in polycrystalline ice at sub-freezing and even sub-eutectic temperatures. Not only do chemicals tend to concentrate substantially in this microscopic liquid phase, but local physicochemical properties may also differ widely from the bulk counterparts, therefore critically affecting the thermodynamics and kinetics of chemical processes occurring in frozen media such as snow, frost, and frost- flowers. This phenomenon has important implications in atmospheric chemistry such as affecting the composition of the atmospheric boundary layer in snow-covered regions. A method using con-focal laser scanning microscope equipped with a cryostat has been developed to measure physicochemical properties of the microscopic liquid phase in ice that are not readily extrapolated from the bulk data. The experimental setup allows for monitoring the freezing process of an aqueous solution with a sub- second time resolution and a submicron 3D spatial resolution. The physicochemical properties (e.g. viscosity, polarity, and acidity) can, in theory, be deduced from features of the fluorescence spectra of particular fluorescent indicators. For example, the acidity change during the freezing and melting process of electrolyte solutions has been monitored in real time by a pH-dependent dual emission fluorescent probe C-SNARF-1. The effects of temperature, freezing rate, and added electrolytes such as ammonium sulfate, sodium chloride and zwitterions are also examined. The findings complement the theory and previous experimental evidence of freezing hydrolysis.

Electroactive microorganisms in bulk solution contribute significantly to methane production in bioelectrochemical anaerobic reactor.

PubMed

Feng, Qing; Song, Young-Chae; Ahn, Yongtae

2018-07-01

The role of anaerobic microorganisms suspended in the bulk solution on methane production was investigated in a bioelectrochemical anaerobic reactor with the electrode polarized at 0.5 V. The electron transfer from substrate to methane and hydrogen were 25% and 7.5%, respectively, in the absence of the anaerobic microorganisms in the bulk solution. As the anaerobic microorganisms increased to 4400 mg/L, the electrons transferred to methane increased to 83.3% but decreased to 0.3% in hydrogen. The electroactive microorganisms (EAM), including exoelectrogens and electrotrophs, enriched in the bulk solution that confirmed by the redox peaks in the cyclic voltammogram was proportional to the anaerobic microorganism. The methane yield based on COD removal was dependent on the anaerobic microorganisms in the bulk solution rather than on the bioelectrode surface. The EAM suspended in the bulk solution are enriched by the polarized electrode, and significantly improve methane production in bioelectrochemical anaerobic reactor. Copyright © 2018 Elsevier Ltd. All rights reserved.

Bulk Moisture and Salinity Sensor

NASA Technical Reports Server (NTRS)

Nurge, Mark; Monje, Oscar; Prenger, Jessica; Catechis, John

2013-01-01

Measurement and feedback control of nutrient solutions in plant root zones is critical to the development of healthy plants in both terrestrial and reduced-gravity environments. In addition to the water content, the amount of fertilizer in the nutrient solution is important to plant health. This typically requires a separate set of sensors to accomplish. A combination bulk moisture and salinity sensor has been designed, built, and tested with different nutrient solutions in several substrates. The substrates include glass beads, a clay-like substrate, and a nutrient-enriched substrate with the presence of plant roots. By measuring two key parameters, the sensor is able to monitor both the volumetric water content and salinity of the nutrient solution in bulk media. Many commercially available moisture sensors are point sensors, making localized measurements over a small volume at the point of insertion. Consequently, they are more prone to suffer from interferences with air bubbles, contact area of media, and root growth. This makes it difficult to get an accurate representation of true moisture content and distribution in the bulk media. Additionally, a network of point sensors is required, increasing the cabling, data acquisition, and calibration requirements. measure the dielectric properties of a material in the annular space of the vessel. Because the pore water in the media often has high salinity, a method to measure the media moisture content and salinity simultaneously was devised. Characterization of the frequency response for capacitance and conductance across the electrodes was completed for 2-mm glass bead media, 1- to 2-mm Turface (a clay like media), and 1- to 2-mm fertilized Turface with the presence of root mass. These measurements were then used to find empirical relationships among capacitance (C), the dissipation factor (D), the volumetric water content, and the pore water salinity.

Mechanical properties of bulk graphene oxide/poly(acrylic acid)/poly(ethylenimine) ternary polyelectrolyte complex.

PubMed

Duan, Yipin; Wang, Chao; Zhao, Mengmeng; Vogt, Bryan D; Zacharia, Nicole S

2018-05-30

Ternary complexes formed in a single pot process through the mixing of cationic (branched polyethylenimine, BPEI) and anionic (graphene oxide, GO, and poly(acrylic acid), PAA) aqueous solutions exhibit superior mechanical performance in comparison to their binary analogs. The composition of the ternary complex can be simply tuned through the composition of the anionic solution, which influences the water content and mechanical properties of the complex. Increasing the PAA content in the complex decreases the overall water content due to improved charge compensation with the BPEI, but this change also significantly improves the toughness of the complex. Ternary complexes containing ≤32 wt% PAA were too brittle to generate samples for tensile measurements, while extension in excess of 250% could be reached with 57 wt% PAA. From this work, the influence of GO and PAA on the mechanical properties of GO/PAA/BPEI complexes were elucidated with GO sheets acting to restrain the viscous flow and improve the mechanical strength at low loading (<12.6 wt%) and PAA more efficiently complexes with BPEI than GO to generate a less swollen and stronger network. This combination overcomes the brittle nature of GO-BPEI complexes and viscous creep of PAA-BPEI complexes. Ternary nanocomposite complexes appear to provide an effective route to toughen and strengthen bulk polyelectrolyte complexes.

Chemical and physical properties affecting strontium distribution coefficients of surficial-sediment samples at the Idaho National Engineering and Environmental Laboratory, Idaho

USGS Publications Warehouse

Liszewski, M.J.; Rosentreter, J.J.; Miller, Karl E.; Bartholomay, R.C.

2000-01-01

The U.S. Geological Survey and Idaho State University, in cooperation with the U.S. Department of Energy, conducted a study to determine strontium distribution coefficients (K(d)s) of surficial sediments at the Idaho National Engineering and Environmental Laboratory (INEEL). Batch experiments using synthesized aqueous solutions were used to determine K(d)s, which describe the distribution of a solute between the solution and solid phase, of 20 surficial-sediment samples from the INEEL. The K(d)s for the 20 surficial-sediment samples ranged from 36 to 275 ml/g. Many properties of both the synthesized aqueous solutions and sediments used in the experiments also were determined. Solution properties determined were initial and equilibrium concentrations of calcium, magnesium, and strontium, pH and specific conductance, and initial concentrations of potassium and sodium. Sediment properties determined were grain-size distribution, bulk mineralogy, whole-rock major-oxide and strontium and barium concentrations, and Brunauer-Emmett-Teller (BET) surface area. Solution and sediment properties were correlated with strontium K(d)s of the 20 surficial sediments using Pearson correlation coefficients. Solution properties with the strongest correlations with strontium K(d)s were equilibrium pH and equilibrium calcium concentration correlation coefficients, 0.6598 and -0.6518, respectively. Sediment properties with the strongest correlations with strontium K(d)s were manganese oxide (MnO), BET surface area, and the >4.75-mm-grain-size fraction correlation coefficients, 0.7054, 0.7022, and -0.6660, respectively. Effects of solution properties on strontium K(d)s were interpreted as being due to competition among similarly charged and sized cations in solution for strontium-sorption sites; effects of sediment properties on strontium K(d)s were interpreted as being surface-area related. Multivariate analyses of these solution and sediment properties resulted in r2 values of 0.8071 when all five properties were used and 0.8043 when three properties, equilibrium pH, MnO, and BET surface area, were used.

Electrochemical Induced Calcium Phosphate Precipitation: Importance of Local pH

PubMed Central

2017-01-01

Phosphorus (P) is an essential nutrient for living organisms and cannot be replaced or substituted. In this paper, we present a simple yet efficient membrane free electrochemical system for P removal and recovery as calcium phosphate (CaP). This method relies on in situ formation of hydroxide ions by electro mediated water reduction at a titanium cathode surface. The in situ raised pH at the cathode provides a local environment where CaP will become highly supersaturated. Therefore, homogeneous and heterogeneous nucleation of CaP occurs near and at the cathode surface. Because of the local high pH, the P removal behavior is not sensitive to bulk solution pH and therefore, efficient P removal was observed in three studied bulk solutions with pH of 4.0 (56.1%), 8.2 (57.4%), and 10.0 (48.4%) after 24 h of reaction time. While P removal efficiencies are not generally affected by bulk solution pH, the chemical-physical properties of CaP solids collected on the cathode are still related to bulk solution pH, as confirmed by structure characterizations. High initial solution pH promotes the formation of more crystalline products with relatively high Ca/P molar ratio. The Ca/P molar ratio increases from 1.30 (pH 4.0) to 1.38 (pH 8.2) and further increases to 1.55 (pH 10.0). The formation of CaP precipitates was a typical crystallization process, with an amorphous phase formed at the initial stage which then transforms to the most stable crystal phase, hydroxyapatite, which is inferred from the increased Ca/P molar ratio from 1.38 (day 1) to the theoretical 1.76 (day 11) and by the formation of needle-like crystals. Finally, we demonstrated the efficiency of this system for real wastewater. This, together with the fact that the electrochemical method can work at low bulk pH, without dosing chemicals and a need for a separation process, highlights the potential application of the electrochemical method for P removal and recovery. PMID:28872838

Measurements of thermodynamic and optical properties of selected aqueous organic and organic-inorganic mixtures of atmospheric relevance.

PubMed

Lienhard, Daniel M; Bones, David L; Zuend, Andreas; Krieger, Ulrich K; Reid, Jonathan P; Peter, Thomas

2012-10-11

Atmospheric aerosol particles can exhibit liquid solution concentrations supersaturated with respect to the dissolved organic and inorganic species and supercooled with respect to ice. In this study, thermodynamic and optical properties of sub- and supersaturated aqueous solutions of atmospheric interest are presented. The density, refractive index, water activity, ice melting temperatures, and homogeneous ice freezing temperatures of binary aqueous solutions containing L(+)-tartaric acid, tannic acid, and levoglucosan and ternary aqueous solutions containing levoglucosan and one of the salts NH(4)HSO(4), (NH(4))(2)SO(4), and NH(4)NO(3) have been measured in the supersaturated concentration range for the first time. In addition, the density and refractive index of binary aqueous citric acid and raffinose solutions and the glass transition temperatures of binary aqueous L(+)-tartaric acid and levoglucosan solutions have been measured. The data presented here are derived from experiments on single levitated microdroplets and bulk solutions and should find application in thermodynamic and atmospheric aerosol models as well as in food science applications.

Crystal growth and optical properties of 4-aminobenzophenone (ABP)

NASA Astrophysics Data System (ADS)

Li, Zhengdong; Wu, Baichang; Su, Genbo; Huang, Gongfan

1997-02-01

Bulk crystals of 4-aminobenzophenone (ABP) were grown from organic solution. The crystal structure was determined by X-ray analysis. The refractive indices were determined by the method of prism minimum deviation. Some effective nonlinear-optical coefficients deff were measured. A blue second-harmonic emission with wavelengths of 433 and 460 nm were observed during laser diode pumping.

Thermal conductive heating in fractured bedrock: Screening calculations to assess the effect of groundwater influx

NASA Astrophysics Data System (ADS)

Baston, Daniel P.; Kueper, Bernard H.

2009-02-01

A two-dimensional semi-analytical heat transfer solution is developed and a parameter sensitivity analysis performed to determine the relative importance of rock material properties (density, thermal conductivity and heat capacity) and hydrogeological properties (hydraulic gradient, fracture aperture, fracture spacing) on the ability to heat fractured rock using thermal conductive heating (TCH). The solution is developed using a Green's function approach in which an integral equation is constructed for the temperature in the fracture. Subsurface temperature distributions are far more sensitive to hydrogeological properties than material properties. The bulk ground water influx ( q) can provide a good estimate of the extent of influx cooling when influx is low to moderate, allowing the prediction of temperatures during heating without specific knowledge of the aperture and spacing of fractures. Target temperatures may not be reached or may be significantly delayed when the groundwater influx is large.

Controlled uptake and release of imatinib from ultrasound nanoparticles Cu3(BTC)2 metal-organic framework in comparison with bulk structure.

PubMed

Abbasi, Amir Reza; Rizvandi, Maryam; Azadbakht, Azadeh; Rostamnia, Sadegh

2016-06-01

The porosity of metal-organic frameworks (MOFs) is an important point concerning the possible use of such functional materials for different purposes. In this work, we study uptake and release properties of imatinib (IM) from nano Cu(II)-MOF in comparison with bulk Cu(II)-MOF. To explore the absorption ability of the Cu(II)-MOF to IM, fresh sample of Cu3(BTC)2 was immersed in an aqueous solution of IM and were monitored in real time with UV/vis spectroscopy. Results show that the adsorbed quantity of IM over nano Cu3(BTC)2 (I) is much higher than those over a bulk Cu3(BTC)2 (II). Copyright © 2016. Published by Elsevier Inc.

Bulk Heterojunction versus Diffused Bilayer: The Role of Device Geometry in Solution p-Doped Polymer-Based Solar Cells.

PubMed

Loiudice, Anna; Rizzo, Aurora; Biasiucci, Mariano; Gigli, Giuseppe

2012-07-19

We exploit the effect of molecular p-type doping of P3HT in diffused bilayer (DB) polymer solar cells. In this alternative device geometry, the p-doping is accomplished in solution by blending the F4-TCNQ with P3HT. The p-doping both increases the film conductivity and reduces the potential barrier at the interface with the electrode. This results in an excellent power conversion efficiency of 4.02%, which is an improvement of ∼48% over the p-doped standard bulk heterojunction (BHJ) device. Combined VOC-light intensity dependence measurements and Kelvin probe force microscopy reveal that the DB device configuration is particularly advantageous, if compared to the conventional BHJ, because it enables optimization of the donor and acceptor layers independently to minimize the effect of trapping and to fully exploit the improved transport properties.

Microphase separation and the formation of ion conductivity channels in poly(ionic liquid)s: A coarse-grained molecular dynamics study

NASA Astrophysics Data System (ADS)

Weyman, Alexander; Bier, Markus; Holm, Christian; Smiatek, Jens

2018-05-01

We study generic properties of poly(ionic liquid)s (PILs) via coarse-grained molecular dynamics simulations in bulk solution and under confinement. The influence of different side chain lengths on the spatial properties of the PIL systems and on the ionic transport mechanism is investigated in detail. Our results reveal the formation of apolar and polar nanodomains with increasing side chain length in good agreement with previous results for molecular ionic liquids. The ion transport numbers are unaffected by the occurrence of these domains, and the corresponding values highlight the potential role of PILs as single-ion conductors in electrochemical devices. In contrast to bulk behavior, a pronounced formation of ion conductivity channels in confined systems is initiated in close vicinity to the boundaries. We observe higher ion conductivities in these channels for increasing PIL side chain lengths in comparison with bulk values and provide an explanation for this effect. The appearance of these domains points to an improved application of PILs in modern polymer electrolyte batteries.

Possible existence of convective currents in surfactant bulk solution in experimental pendant-bubble dynamic surface tension measurements.

PubMed

Moorkanikkara, Srinivas Nageswaran; Blankschtein, Daniel

2009-02-03

Traditionally, surfactant bulk solutions in which dynamic surface tension (DST) measurements are conducted using the pendant-bubble apparatus are assumed to be quiescent. Consequently, the transport of surfactant molecules in the bulk solution is often modeled as being purely diffusive when analyzing the experimental pendant-bubble DST data. In this Article, we analyze the experimental pendant-bubble DST data of the alkyl poly (ethylene oxide) nonionic surfactants, C12E4 and C12E6, and demonstrate that both surfactants exhibit "superdiffusive" adsorption kinetics behavior with characteristics that challenge the traditional assumption of a quiescent surfactant bulk solution. In other words, the observed superdiffusive adsorption behavior points to the possible existence of convection currents in the surfactant bulk solution. The analysis presented here involves the following steps: (1) constructing an adsorption kinetics model that corresponds to the fastest rate at which surfactant molecules adsorb onto the actual pendant-bubble surface from a quiescent solution, (2) predicting the DST behaviors of C12E4 and C12E6 at several surfactant bulk solution concentrations using the model constructed in step 1, and (3) comparing the predicted DST profiles with the experimental DST profiles. This comparison reveals systematic deviations for both C12E4 and C12E6 with the following characteristics: (a) the experimental DST profiles exhibit adsorption kinetics behavior, which is faster than the predicted fastest rate of surfactant adsorption from a quiescent surfactant bulk solution at time scales greater than 100 s, and (b) the experimental DST profiles and the predicted DST behaviors approach the same equilibrium surface tension values. Characteristic (b) indicates that the cause of the observed systematic deviations may be associated with the adsorption kinetics mechanism adopted in the model used rather than with the equilibrium behavior. Characteristic (a) indicates that the actual surfactant bulk solution in which the DST measurement was conducted, most likely, cannot be considered to be quiescent at time scales greater than 100 s. Accordingly, the observed superdiffusive adsorption behavior is interpreted as resulting from convection currents present in a nonquiescent surfactant bulk solution. Convection currents accelerate the surfactant adsorption process by increasing the rate of surfactant transport in the bulk solution. The systematic nature of the deviations observed between the predicted DST profiles and the experimental DST behavior for C12E4 and C12E6 suggests that the nonquiescent nature of the surfactant bulk solution may be intrinsic to the experimental pendant-bubble DST measurement approach. To validate this possibility, we identified generic features in the experimental DST data when DST measurements are conducted in a nonquiescent surfactant bulk solution, and the DST measurements are analyzed assuming that the surfactant bulk solution is quiescent. An examination of the DST literature reveals that these identified generic features are quite general and are observed in the experimental DST data of several other surfactants (decanol, nonanol, C10E8, C14E8, C12E8, and C10E4) measured using the pendant-bubble apparatus.

Accuracy limit of rigid 3-point water models

NASA Astrophysics Data System (ADS)

Izadi, Saeed; Onufriev, Alexey V.

2016-08-01

Classical 3-point rigid water models are most widely used due to their computational efficiency. Recently, we introduced a new approach to constructing classical rigid water models [S. Izadi et al., J. Phys. Chem. Lett. 5, 3863 (2014)], which permits a virtually exhaustive search for globally optimal model parameters in the sub-space that is most relevant to the electrostatic properties of the water molecule in liquid phase. Here we apply the approach to develop a 3-point Optimal Point Charge (OPC3) water model. OPC3 is significantly more accurate than the commonly used water models of same class (TIP3P and SPCE) in reproducing a comprehensive set of liquid bulk properties, over a wide range of temperatures. Beyond bulk properties, we show that OPC3 predicts the intrinsic charge hydration asymmetry (CHA) of water — a characteristic dependence of hydration free energy on the sign of the solute charge — in very close agreement with experiment. Two other recent 3-point rigid water models, TIP3PFB and H2ODC, each developed by its own, completely different optimization method, approach the global accuracy optimum represented by OPC3 in both the parameter space and accuracy of bulk properties. Thus, we argue that an accuracy limit of practical 3-point rigid non-polarizable models has effectively been reached; remaining accuracy issues are discussed.

Rheology and hydrodynamic properties of Tolypocladium inflatum fermentation broth and its simulation.

PubMed

Benchapattarapong, N; Anderson, W A; Bai, F; Moo-Young, M

2005-07-01

A physico-chemical, two phase simulated pseudoplastic fermentation (SPF) broth was investigated in which Solka Floc cellulose fibre was used to simulate the filamentous biomass, and a mixture of 0.1% (w/v) carboxymethyl cellulose (CMC) and 0.15 M aqueous sodium chloride was used to simulate the liquid fraction of the fermentation broth. An investigation of the rheological behaviour and hydrodynamic properties of the SPF broth was carried out, and compared to both a fungal Tolypocladium inflatum fermentation broth and a CMC solution in a 50 L stirred tank bioreactor equipped with conventional Rushton turbines. The experimental data confirmed the ability of the two phase SPF broth to mimic both the T. inflatum broth bulk rheology as well as the mixing and mass transfer behaviour. In contrast, using a homogeneous CMC solution with a similar bulk rheology to simulate the fermentation resulted in a significant underestimation of the mass transfer and mixing times. The presence of the solid phase and its microstructure in the SPF broth appear to play a significant role in gas holdup and bubble size, thus leading to the different behaviours. The SPF broth seems to be a more accurate simulation fluid that can be used to predict the bioreactor mixing and mass transfer performance in filamentous fermentations, in comparison with CMC solutions used in some previous studies.

Passivation of high temperature superconductors

NASA Technical Reports Server (NTRS)

Vasquez, Richard P. (Inventor)

1991-01-01

The surface of high temperature superconductors such as YBa2Cu3O(7-x) are passivated by reacting the native Y, Ba and Cu metal ions with an anion such as sulfate or oxalate to form a surface film that is impervious to water and has a solubility in water of no more than 10(exp -3) M. The passivating treatment is preferably conducted by immersing the surface in dilute aqueous acid solution since more soluble species dissolve into the solution. The treatment does not degrade the superconducting properties of the bulk material.

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

Not Available

This volume contains the interim change notice for physical testing. Covered are: properties of solutions, slurries, and sludges; rheological measurement with cone/plate viscometer; % solids determination; particle size distribution by laser scanning; penetration resistance of radioactive waste; operation of differential scanning calorimeter, thermogravimetric analyzer, and high temperature DTA and DSC; sodium rod for sodium bonded fuel; filling SP-100 fuel capsules; sodium filling of BEATRIX-II type capsules; removal of alkali metals with ammonia; specific gravity of highly radioactive solutions; bulk density of radioactive granular solids; purification of Li by hot gettering/filtration; and Li filling of MOTA capsules.

Role of Spatial Ionic Distribution on the Energetics of Hydrophobic Assembly and Properties of the Water/Hydrophobe Interface†

PubMed Central

Bauer, Brad A.; Ou, Shuching; Patel, Sandeep

2014-01-01

We present results from all-atom molecular dynamics simulations of large-scale hydrophobic plates solvated in NaCl and NaI salt solutions. As observed in studies of ions at the air-water interface, the density of iodide near the water-plate interface is significantly enhanced relative to chloride and in the bulk. This allows for the partial hydration of iodide while chloride remains more fully hydrated. In 1M solutions, iodide directly pushes the hydrophobes together (contributing −2.51 kcal/mol) to the PMF. Chloride, however, strengthens the water-induced contribution to the PMF by ~ −2.84 kcal/mol. These observations are enhanced in 3M solutions, consistent with the increased ion density in the vicinity of the hydrophobes. The different salt solutions influence changes in the critical hydrophobe separation distance and characteristic wetting/dewetting transitions. These differences are largely influenced by the ion-specific expulsion of iodide from bulk water. Results of this study are of general interest to the study of ions at interfaces and may lend insight to the mechanisms underlying the Hofmeister series. PMID:22231014

Influence of growth temperature on bulk and surface defects in hybrid lead halide perovskite films.

PubMed

Peng, Weina; Anand, Benoy; Liu, Lihong; Sampat, Siddharth; Bearden, Brandon E; Malko, Anton V; Chabal, Yves J

2016-01-21

The rapid development of perovskite solar cells has focused its attention on defects in perovskites, which are gradually realized to strongly control the device performance. A fundamental understanding is therefore needed for further improvement in this field. Recent efforts have mainly focused on minimizing the surface defects and grain boundaries in thin films. Using time-resolved photoluminescence spectroscopy, we show that bulk defects in perovskite samples prepared using vapor assisted solution process (VASP) play a key role in addition to surface and grain boundary defects. The defect state density of samples prepared at 150 °C (∼10(17) cm(-3)) increases by 5 fold at 175 °C even though the average grains size increases slightly, ruling out grain boundary defects as the main mechanism for the observed differences in PL properties upon annealing. Upon surface passivation using water molecules, the PL intensity and lifetime of samples prepared at 200 °C are only partially improved, remaining significantly lower than those prepared at 150 °C. Thus, the present study indicates that the majority of these defect states observed at elevated growth temperatures originates from bulk defects and underscores the importance to control the formation of bulk defects together with grain boundary and surface defects to further improve the optoelectronic properties of perovskites.

Use of LANDSAT images of vegetation cover to estimate effective hydraulic properties of soils

NASA Technical Reports Server (NTRS)

Eagleson, Peter S.; Jasinski, Michael F.

1988-01-01

The estimation of the spatially variable surface moisture and heat fluxes of natural, semivegetated landscapes is difficult due to the highly random nature of the vegetation (e.g., plant species, density, and stress) and the soil (e.g., moisture content, and soil hydraulic conductivity). The solution to that problem lies, in part, in the use of satellite remotely sensed data, and in the preparation of those data in terms of the physical properties of the plant and soil. The work was focused on the development and testing of a stochastic geometric canopy-soil reflectance model, which can be applied to the physically-based interpretation of LANDSAT images. The model conceptualizes the landscape as a stochastic surface with bulk plant and soil reflective properties. The model is particularly suited for regional scale investigations where the quantification of the bulk landscape properties, such as fractional vegetation cover, is important on a pixel by pixel basis. A summary of the theoretical analysis and the preliminary testing of the model with actual aerial radiometric data is provided.

Impact of helical organization on the photovoltaic properties of oligothiophene supramolecular polymers† †Electronic supplementary information (ESI) available: Synthesis and characterization of 3 and 4, UV-vis spectra, solar cell device properties and AFM images. See DOI: 10.1039/c7sc05093c

PubMed Central

Ouchi, Hayato; Kizaki, Takahiro; Yamato, Masaki; Lin, Xu; Hoshi, Nagahiro; Silly, Fabien; Kajitani, Takashi; Fukushima, Takanori

2018-01-01

Helical self-assembly of functional π-conjugated molecules offers unique photochemical and electronic properties in the spectroscopic level, but there are only a few examples that demonstrate their positive impact on the optoelectronic device level. Here, we demonstrate that hydrogen-bonded tapelike supramolecular polymers of a barbiturated oligo(alkylthiophene) show notable improvement in their photovoltaic properties upon organizing into helical nanofibers. A tapelike hydrogen-bonded supramolecular array of barbiturated oligo(butylthiophene) molecules was directly visualized by STM at a liquid–solid interface. TEM, AFM and XRD revealed that the tapelike supramolecular polymers further organize into helical nanofibers in solution and bulk states. Bulk heterojunction solar cells of the helical nanofibers and soluble fullerene showed a power conversion efficiency of 4.5%, which is markedly high compared to that of the regioisomer of butyl chains organizing into 3D lamellar agglomerates. PMID:29780493

Copper Oxide Nanomaterials Prepared by Solution Methods, Some Properties, and Potential Applications: A Brief Review

PubMed Central

Tran, Thi Ha; Nguyen, Viet Tuyen

2014-01-01

Cupric oxide (CuO), having a narrow bandgap of 1.2 eV and a variety of chemophysical properties, is recently attractive in many fields such as energy conversion, optoelectronic devices, and catalyst. Compared with bulk material, the advanced properties of CuO nanostructures have been demonstrated; however, the fact that these materials cannot yet be produced in large scale is an obstacle to realize the potential applications of this material. In this respect, chemical methods seem to be efficient synthesis processes which yield not only large quantities but also high quality and advanced material properties. In this paper, the effect of some general factors on the morphology and properties of CuO nanomaterials prepared by solution methods will be overviewed. In terms of advanced nanostructure synthesis, microwave method in which copper hydroxide nanostructures are produced in the precursor solution and sequentially transformed by microwave into CuO may be considered as a promising method to explore in the near future. This method produces not only large quantities of nanoproducts in a short reaction time of several minutes, but also high quality materials with advanced properties. A brief review on some unique properties and applications of CuO nanostructures will be also presented. PMID:27437488

Strongly nonlinear composite dielectrics: A perturbation method for finding the potential field and bulk effective properties

NASA Astrophysics Data System (ADS)

Blumenfeld, Raphael; Bergman, David J.

1991-10-01

A class of strongly nonlinear composite dielectrics is studied. We develop a general method to reduce the scalar-potential-field problem to the solution of a set of linear Poisson-type equations in rescaled coordinates. The method is applicable for a large variety of nonlinear materials. For a power-law relation between the displacement and the electric fields, it is used to solve explicitly for the value of the bulk effective dielectric constant ɛe to second order in the fluctuations of its local value. A simlar procedure for the vector potential, whose curl is the displacement field, yields a quantity analogous to the inverse dielectric constant in linear dielectrics. The bulk effective dielectric constant is given by a set of linear integral expressions in the rescaled coordinates and exact bounds for it are derived.

Synthesis of formamidinium lead iodide perovskite bulk single crystal and its optical properties

NASA Astrophysics Data System (ADS)

Zheng, Hongge; Duan, Junjie; Dai, Jun

2017-07-01

Formamidinium lead iodide (FAPbI3) is a promising hybrid perovskite material for optoelectronic devices. We synthesized bulk single crystal FAPbI3 by a rapid solution crystallization method. X-ray diffraction (XRD) was performed to characterize the crystal structure. Temperature-dependent photoluminescence (PL) spectra of the bulk single crystal FAPbI3 were measured from 10 to 300 K to explain PL recombination mechanism. It shows that near band edge emission blueshifts with the temperature increasing from 10 to 120 K and from 140 K to room temperature, a sudden emission band redshift demonstrates near 140 K because of the phase transition from orthorhombic phase to cubic phase. From the temperature-dependent PL spectra, the temperature coefficients of the bandgap and thermal activation energies of FAPbI3 perovskite are fitted.

Controlled Bulk Properties of Composite Polymeric Solutions for Extensive Structural Order of Honeycomb Polysulfone Membranes

PubMed Central

Gugliuzza, Annarosa; Perrotta, Maria Luisa; Drioli, Enrico

2016-01-01

This work provides additional insights into the identification of operating conditions necessary to overcome a current limitation to the scale-up of the breath figure method, which is regarded as an outstanding manufacturing approach for structurally ordered porous films. The major restriction concerns, indeed, uncontrolled touching droplets at the boundary. Herein, the bulk of polymeric solutions are properly managed to generate honeycomb membranes with a long-range structurally ordered texture. Water uptake and dynamics are explored as chemical environments are changed with the intent to modify the hydrophilic/hydrophobic balance and local water floatation. In this context, a model surfactant such as the polyoxyethylene sorbitan monolaurate is used in combination with alcohols at different chain length extents and a traditional polymer such as the polyethersufone. Changes in the interfacial tension and kinematic viscosity taking place in the bulk of composite solutions are explored and examined in relation to competitive droplet nucleation and growth rate. As a result, extensive structurally ordered honeycomb textures are obtained with the rising content of the surfactant while a broad range of well-sized pores is targeted as a function of the hydrophilic-hydrophobic balance and viscosity of the composite polymeric mixture. The experimental findings confirm the consistency of the approach and are expected to give propulsion to the commercially production of breath figures films shortly. PMID:27196938

Controlled Bulk Properties of Composite Polymeric Solutions for Extensive Structural Order of Honeycomb Polysulfone Membranes.

PubMed

Gugliuzza, Annarosa; Perrotta, Maria Luisa; Drioli, Enrico

2016-05-16

This work provides additional insights into the identification of operating conditions necessary to overcome a current limitation to the scale-up of the breath figure method, which is regarded as an outstanding manufacturing approach for structurally ordered porous films. The major restriction concerns, indeed, uncontrolled touching droplets at the boundary. Herein, the bulk of polymeric solutions are properly managed to generate honeycomb membranes with a long-range structurally ordered texture. Water uptake and dynamics are explored as chemical environments are changed with the intent to modify the hydrophilic/hydrophobic balance and local water floatation. In this context, a model surfactant such as the polyoxyethylene sorbitan monolaurate is used in combination with alcohols at different chain length extents and a traditional polymer such as the polyethersufone. Changes in the interfacial tension and kinematic viscosity taking place in the bulk of composite solutions are explored and examined in relation to competitive droplet nucleation and growth rate. As a result, extensive structurally ordered honeycomb textures are obtained with the rising content of the surfactant while a broad range of well-sized pores is targeted as a function of the hydrophilic-hydrophobic balance and viscosity of the composite polymeric mixture. The experimental findings confirm the consistency of the approach and are expected to give propulsion to the commercially production of breath figures films shortly.

Detecting the Biopolymer Behavior of Graphene Nanoribbons in Aqueous Solution

NASA Astrophysics Data System (ADS)

Li, Jingqiang; Wijeratne, Sithara; Penev, Evgeni; Lu, Wei; Duque, Amanda; Yakobson, Boris; Tour, James; Kiang, Ching-Hwa; Boris I. Yakobson Group Team; James M. Tour Group Team; Ching-Hwa Kiang Group Team

Graphene nanoribbons (GNR), can be prepared in bulk quantities for large-area applications by reducing the product from the lengthwise oxidative unzipping of multiwalled carbon nanotubes (MWNT). Recently, the biomaterials application of GNR has been explored, for example, in the pore to be used for DNA sequencing. Therefore, understanding the polymer behavior of GNR in solution is essential in predicting GNR interaction with biomaterials. Here, we report experimental studies of the solutionbased mechanical properties of GNR and their parent products, graphene oxide nanoribbons (GONR). We used atomic force microscopy (AFM) to study their mechanical properties in solution and showed that GNR and GONR have similar force-extension behavior as in biopolymers such as proteins and DNA. The rigidity increases with reducing chemical functionalities. The similarities in rigidity and tunability between nanoribbons and biomolecules might enable the design and fabrication of GNR-biomimetic interfaces.

Counting ions and other nucleophiles at surfaces by chemical trapping.

PubMed

Cuccovia, Iolanda Midea; da Silva Lima, Filipe; Chaimovich, Hernan

2017-10-01

The interfaces of membranes and other aggregates are determined by the polarity, electrical charge, molecular volume, degrees of motional freedom and packing density of the head groups of the amphiphiles. These properties also determine the type of bound ion (ion selectivity) and its local density, i.e. concentration defined by choosing an appropriate volume element at the aggregate interface. Bulk and local ion concentrations can differ by orders of magnitude. The relationships between ion (or other compound) concentrations in the bulk solvent and in the interface are complex but, in some cases, well established. As the local ion concentration, rather than that in the bulk, controls a variety of properties of membranes, micelles, vesicles and other objects of theoretical and applied interests, measurement of local (interfacial, bound) ion concentrations is of relevance for understanding and characterizing such aggregates. Many experimental methods for estimating ion distributions between the bulk solution and the interface provide indirect estimates because they are based on concentration-dependent properties, rather than concentration measurements. Dediazoniation, i.e. the loss of N 2 , of a substituted diazophenyl derivative provides a tool for determining the number of nucleophiles (including neutral or negatively charged ions) surrounding the diazophenyl derivative prior to the dediazoniation event. This reaction, defined as chemical trapping, and the appropriate reference points obtained in bulk solution allow direct measurements of local concentrations of a variety of nucleophiles at the surface of membranes and other aggregates. Here we review our contributions of our research group to the use, and understanding, of this method and applications of chemical trapping to the description of local concentrations of ions and other nucleophiles in micelles, reverse micelles, vesicles and solvent mixtures. Among other results, we have shown that interfacial water determines micellar shape, zwitterionic vesicle-forming amphiphiles display ion selectivity and urea does not accumulate at micellar interfaces. We have also shown that reaction products can be predicted from the composition of the initial state, even in non-ideal solvent mixtures, supporting the usefulness of chemical trapping as a method to determine local concentrations. In addition, we have analysed the mechanism of dediazoniation, both on theoretical and experimental basis, and concluded that the formation of a free phenyl cation is not a necessary part of the reaction pathway.

Study of a Novel Method for the Thermolysis of Solutes in Aqueous Solution Using a Low Temperature Bubble Column Evaporator.

PubMed

Shahid, Muhammad; Xue, Xinkai; Fan, Chao; Ninham, Barry W; Pashley, Richard M

2015-06-25

An enhanced thermal decomposition of chemical compounds in aqueous solution has been achieved at reduced solution temperatures. The technique exploits hitherto unrecognized properties of a bubble column evaporator (BCE). It offers better heat transfer efficiency than conventional heat transfer equipment. This is obtained via a continuous flow of hot, dry air bubbles of optimal (1-3 mm) size. Optimal bubble size is maintained by using the bubble coalescence inhibition property of some salts. This novel method is illustrated by a study of thermal decomposition of ammonium bicarbonate (NH4HCO3) and potassium persulfate (K2S2O8) in aqueous solutions. The decomposition occurs at significantly lower temperatures than those needed in bulk solution. The process appears to work via the continuous production of hot (e.g., 150 °C) dry air bubbles, which do not heat the solution significantly but produce a transient hot surface layer around each rising bubble. This causes the thermal decomposition of the solute. The decomposition occurs due to the effective collision of the solute with the surface of the hot bubbles. The new process could, for example, be applied to the regeneration of the ammonium bicarbonate draw solution used in forward osmosis.

The Role of Solvent-Solute Interactions on The Behavior of Low Molecular Mass Organo-Gelators

NASA Astrophysics Data System (ADS)

Cavicchi, Kevin; Feng, Li

2012-02-01

Low molecular mass organo-gelators (LMOGs) are a class of small molecules that can self-assemble in organic solvents to form three-dimensional fibrillar networks. This has a profound effect on the viscoelastic properties of the solution causing physical gelation. These gels have uses in a range of industries including cosmetics, foodstuffs, plastics, petroleum and pharmaceuticals. A fundamental question in this field is: What makes a good LMOG? This talk will discuss the relationships between the viscoelastic properties and thermodynamic phase behavior of LMOG/solvent solutions. The regular solution model was used to fit the liquidus line and sol/gel transition temperature vs. concentration in different solvents to determine LMOG-solvent interaction parameters (χ = A/T). This parameter A was found to scale with the solubility parameter of the solvent, especially for non-polar solvents. This demonstrates that gelation is strongly linked to LMOG solubility and indicates that the bulk thermodynamic parameters of the LMOG (solubility parameter and melting temperature) are useful to predict the solution behavior of LMOGs.

Self-assembly of cationic multidomain peptide hydrogels: supramolecular nanostructure and rheological properties dictate antimicrobial activity

NASA Astrophysics Data System (ADS)

Jiang, Linhai; Xu, Dawei; Sellati, Timothy J.; Dong, He

2015-11-01

Hydrogels are an important class of biomaterials that have been widely utilized for a variety of biomedical/medical applications. The biological performance of hydrogels, particularly those used as wound dressing could be greatly advanced if imbued with inherent antimicrobial activity capable of staving off colonization of the wound site by opportunistic bacterial pathogens. Possessing such antimicrobial properties would also protect the hydrogel itself from being adversely affected by microbial attachment to its surface. We have previously demonstrated the broad-spectrum antimicrobial activity of supramolecular assemblies of cationic multi-domain peptides (MDPs) in solution. Here, we extend the 1-D soluble supramolecular assembly to 3-D hydrogels to investigate the effect of the supramolecular nanostructure and its rheological properties on the antimicrobial activity of self-assembled hydrogels. Among designed MDPs, the bactericidal activity of peptide hydrogels was found to follow an opposite trend to that in solution. Improved antimicrobial activity of self-assembled peptide hydrogels is dictated by the combined effect of supramolecular surface chemistry and storage modulus of the bulk materials, rather than the ability of individual peptides/peptide assemblies to penetrate bacterial cell membrane as observed in solution. The structure-property-activity relationship developed through this study will provide important guidelines for designing biocompatible peptide hydrogels with built-in antimicrobial activity for various biomedical applications.Hydrogels are an important class of biomaterials that have been widely utilized for a variety of biomedical/medical applications. The biological performance of hydrogels, particularly those used as wound dressing could be greatly advanced if imbued with inherent antimicrobial activity capable of staving off colonization of the wound site by opportunistic bacterial pathogens. Possessing such antimicrobial properties would also protect the hydrogel itself from being adversely affected by microbial attachment to its surface. We have previously demonstrated the broad-spectrum antimicrobial activity of supramolecular assemblies of cationic multi-domain peptides (MDPs) in solution. Here, we extend the 1-D soluble supramolecular assembly to 3-D hydrogels to investigate the effect of the supramolecular nanostructure and its rheological properties on the antimicrobial activity of self-assembled hydrogels. Among designed MDPs, the bactericidal activity of peptide hydrogels was found to follow an opposite trend to that in solution. Improved antimicrobial activity of self-assembled peptide hydrogels is dictated by the combined effect of supramolecular surface chemistry and storage modulus of the bulk materials, rather than the ability of individual peptides/peptide assemblies to penetrate bacterial cell membrane as observed in solution. The structure-property-activity relationship developed through this study will provide important guidelines for designing biocompatible peptide hydrogels with built-in antimicrobial activity for various biomedical applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr05233e

Comparison of Methods for Predicting the Compositional Dependence of the Density and Refractive Index of Organic-Aqueous Aerosols.

PubMed

Cai, Chen; Miles, Rachael E H; Cotterell, Michael I; Marsh, Aleksandra; Rovelli, Grazia; Rickards, Andrew M J; Zhang, Yun-Hong; Reid, Jonathan P

2016-08-25

Representing the physicochemical properties of aerosol particles of complex composition is of crucial importance for understanding and predicting aerosol thermodynamic, kinetic, and optical properties and processes and for interpreting and comparing analysis methods. Here, we consider the representations of the density and refractive index of aqueous-organic aerosol with a particular focus on the dependence of these properties on relative humidity and water content, including an examination of the properties of solution aerosol droplets existing at supersaturated solute concentrations. Using bulk phase measurements of density and refractive index for typical organic aerosol components, we provide robust approaches for the estimation of these properties for aerosol at any intermediate composition between pure water and pure solute. Approximately 70 compounds are considered, including mono-, di- and tricarboxylic acids, alcohols, diols, nitriles, sulfoxides, amides, ethers, sugars, amino acids, aminium sulfates, and polyols. We conclude that the molar refraction mixing rule should be used to predict the refractive index of the solution using a density treatment that assumes ideal mixing or, preferably, a polynomial dependence on the square root of the mass fraction of solute, depending on the solubility limit of the organic component. Although the uncertainties in the density and refractive index predictions depend on the range of subsaturated compositional data available for each compound, typical errors for estimating the solution density and refractive index are less than ±0.1% and ±0.05%, respectively. Owing to the direct connection between molar refraction and the molecular polarizability, along with the availability of group contribution models for predicting molecular polarizability for organic species, our rigorous testing of the molar refraction mixing rule provides a route to predicting refractive indices for aqueous solutions containing organic molecules of arbitrary structure.

Bulk viscous cosmology with causal transport theory

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

Piattella, Oliver F.; Fabris, Júlio C.; Zimdahl, Winfried, E-mail: oliver.piattella@gmail.com, E-mail: fabris@pq.cnpq.br, E-mail: winfried.zimdahl@pq.cnpq.br

2011-05-01

We consider cosmological scenarios originating from a single imperfect fluid with bulk viscosity and apply Eckart's and both the full and the truncated Müller-Israel-Stewart's theories as descriptions of the non-equilibrium processes. Our principal objective is to investigate if the dynamical properties of Dark Matter and Dark Energy can be described by a single viscous fluid and how such description changes when a causal theory (Müller-Israel-Stewart's, both in its full and truncated forms) is taken into account instead of Eckart's non-causal one. To this purpose, we find numerical solutions for the gravitational potential and compare its behaviour with the corresponding ΛCDMmore » case. Eckart's and the full causal theory seem to be disfavoured, whereas the truncated theory leads to results similar to those of the ΛCDM model for a bulk viscous speed in the interval 10{sup −11} || cb{sup 2} ∼< 10{sup −8}.« less

Coupling between magnetic and optical properties of stable Au-Fe solid solution nanoparticles

NASA Astrophysics Data System (ADS)

de Julián Fernández, C.; Mattei, G.; Paz, E.; Novak, R. L.; Cavigli, L.; Bogani, L.; Palomares, F. J.; Mazzoldi, P.; Caneschi, A.

2010-04-01

Au-Fe nanoparticles constitute one of the simplest prototypes of a multifunctional nanomaterial that can exhibit both magnetic and optical (plasmonic) properties. This solid solution, not feasible in the bulk phase diagram in thermal equilibrium, can be formed as a nanostructure by out-of-equilibrium processes. Here, the novel magnetic, optical and magneto-optical properties of ion-implanted Au-Fe solid solution nanoparticles dispersed in a SiO2 matrix are investigated and correlated. The surface plasmon resonance of the Au-Fe nanoparticles with almost equicomposition is strongly damped when compared to pure Au and to Au-rich Au-Fe nanoparticles. In all cases, the Au atoms are magnetically polarized, as measured by x-ray magnetic circular dichroism, and ferromagnetically coupled with Fe atoms. Although the chemical stability of Au-Fe nanoparticles is larger than that of Fe nanoparticles, both the magnetic moment per Fe atom and the order temperature are smaller. These results suggest that electronic and magnetic properties are more influenced by the hybridization of the electronic bands in the Au-Fe solid solution than by size effects. On the other hand, the magneto-optical transitions allowed in the vis-nIR spectral regions are very similar. In addition, we also observe, after studying the properties of thermally treated samples, that the Au-Fe alloy is stabilized, not by surface effects, but by the combination of the out-of-equilibrium nature of the ion implantation technique and by changes in the properties due to size effects.

Coupling between magnetic and optical properties of stable Au-Fe solid solution nanoparticles.

PubMed

de Julián Fernández, C; Mattei, G; Paz, E; Novak, R L; Cavigli, L; Bogani, L; Palomares, F J; Mazzoldi, P; Caneschi, A

2010-04-23

Au-Fe nanoparticles constitute one of the simplest prototypes of a multifunctional nanomaterial that can exhibit both magnetic and optical (plasmonic) properties. This solid solution, not feasible in the bulk phase diagram in thermal equilibrium, can be formed as a nanostructure by out-of-equilibrium processes. Here, the novel magnetic, optical and magneto-optical properties of ion-implanted Au-Fe solid solution nanoparticles dispersed in a SiO(2) matrix are investigated and correlated. The surface plasmon resonance of the Au-Fe nanoparticles with almost equicomposition is strongly damped when compared to pure Au and to Au-rich Au-Fe nanoparticles. In all cases, the Au atoms are magnetically polarized, as measured by x-ray magnetic circular dichroism, and ferromagnetically coupled with Fe atoms. Although the chemical stability of Au-Fe nanoparticles is larger than that of Fe nanoparticles, both the magnetic moment per Fe atom and the order temperature are smaller. These results suggest that electronic and magnetic properties are more influenced by the hybridization of the electronic bands in the Au-Fe solid solution than by size effects. On the other hand, the magneto-optical transitions allowed in the vis-nIR spectral regions are very similar. In addition, we also observe, after studying the properties of thermally treated samples, that the Au-Fe alloy is stabilized, not by surface effects, but by the combination of the out-of-equilibrium nature of the ion implantation technique and by changes in the properties due to size effects.

Changes in mechanical properties and morphology of elastomer coatings after immersion in salt solutions

NASA Astrophysics Data System (ADS)

Terán Arce, Fernando; Avci, Recep; Beech, Iwona; Cooksey, Keith; Wigglesworth-Cooksey, Barbara

2004-03-01

RTV11 (^TM GE Silicones) and Intersleek (^TM International Paints) are two elastomers of considerable significance to the navy and maritime industry for their application as fouling release coatings. Both materials are composed of polymeric matrices with embedded filler particles, which provide increased strength and durability to the elastomer. Using Atomic force microscopy (AFM), surface and bulk analysis techniques, we have found surface regions with microelastic properties, which correlate with the locations of filler particles inside the coatings. These particles are able to undergo elastic displacements of hundreds of nm inside the polymeric matrix during compression by the AFM tip. While elastic properties of Intersleek remain largely unchanged after immersion in salt solutions, roughening, embrittlement and stiffening occurs in RTV11 coatings depending on the amount of curing agent and humidity used during preparation and curing, respectively. Interestingly, such transformations are absent after immersion in pure water. In particle free regions, elastic moduli of RTV11 take values of 2 - 3 MPa before immersion in salt solutions. After immersion, those values increase 5 - 10 times.

A de Sitter tachyonic braneworld revisited

NASA Astrophysics Data System (ADS)

Barbosa-Cendejas, Nandinii; Cartas-Fuentevilla, Roberto; Herrera-Aguilar, Alfredo; Rigel Mora-Luna, Refugio; da Rocha, Roldão

2018-01-01

Within the framework of braneworlds, several interesting physical effects can be described in a wide range of energy scales, starting from high-energy physics to cosmology and low-energy physics. An usual way to generate a thick braneworld model relies in coupling a bulk scalar field to higher dimensional warped gravity. Quite recently, a novel braneworld was generated with the aid of a tachyonic bulk scalar field, having several remarkable properties. It comprises a regular and stable solution that contains a relevant 3-brane with de Sitter induced metric, arising as an exact solution to the 5D field equations, describing the inflationary eras of our Universe. Besides, it is asymptotically flat, despite of the presence of a negative 5D cosmological constant, which is an interesting feature that contrasts with most of the known, asymptotically either dS or AdS models. Moreover, it encompasses a graviton spectrum with a single massless bound state, accounting for 4D gravity localized on the brane, separated from the continuum of Kaluza-Klein massive graviton modes by a mass gap that makes the 5D corrections to Newton's law to decay exponentially. Finally, gauge, scalar and fermion fields are also shown to be localized on this braneworld. In this work, we show that this tachyonic braneworld allows for a nontrivial solution with a vanishing 5D cosmological constant that preserves all the above mentioned remarkable properties with a less amount of parameters, constituting an important contribution to the construction of a realistic cosmological braneworld model.

Processing of high performance (LRE)-Ba Cu O large, single-grain bulk superconductors in air

NASA Astrophysics Data System (ADS)

Hari Babu, N.; Iida, K.; Shi, Y.; Cardwell, D. A.

2006-10-01

We report the fabrication of large (LRE)BCO single-grains with improved superconducting properties for LRE = Nd, Sm and Gd using a practical process via both conventional top seeded melt growth (TSMG) and seeded infiltration-growth (SIG). This process uses a new generic seed crystal that promotes heterogeneous grain nucleation in the required orientation and suppresses the formation of solid solution in a controlled manner within individual grains by the addition of excess BaO2 to the precursor powder. The spatial distribution of the superconducting properties of LRE bulk superconductors as a function of BaO2 addition for large (LRE)BCO grains fabricated in air by TSMG and SIG for LRE = Gd, Sm and Nd are compared. The optimum BaO2 content required to fabricate single-grain (LRE)BCO with high and homogeneous Tc is determined from these experiments for each LRE system. The irreversibility fields of (LRE)BCO bulk superconductors processed in air are as high as those processed in reduced PO2. Critical current densities in excess of 105 A/cm2 at 77 K and higher trapped fields have been achieved in optimized (LRE)BCO superconductors fabricated in air for the first time.

How Does Boiling in the Earth's Crust Influence Metal Speciation and Transport?

NASA Astrophysics Data System (ADS)

Kam, K.; Lemke, K.

2014-12-01

The presence of large quantities of precious metals, such as gold and copper, near the Earth's surface (upper crust) is commonly attributed to transport in aqueous solution and precipitation upon variations in temperature and pressure. As a consequence, gold exploration is closely linked to solution chemistry, i.e. hydrothermal processes involving aqueous fluids with densities of around unity. However, as crustal fluids buoyantly ascend, boiling produces a coexisting low-density aqueous liquid with fundamentally different physical and chemical properties, and a, most importantly, a high affinity for coinage metals (Heinrich et al., Econ Geol., 1992, 87, 1566). From recent experimental studies of Au (Hurtig and Williams-Jones, 2014, Geochim. Cosmochim. Acta,, 127, 304), we know that metal speciation in this low-density phase differs fundamentally from that observed in bulk solution, clearly, with important implications for Au, and metal speciation in general, transport and ore concentrations processes (these processes would also be operable in industrial geothermal plants given the quite special solvent properties of steam). In brief, this study focuses on the speciation of select metal halides in bulk solution as well as in water vapor, and is driven by our need to understand the solvent properties of around 2.0x109 cubic kilometers of free water (or 2,500 times as much water as stored in all lakes and rivers) present in the Earth's crust. The scope of this study has particular applications in the geothermal and oil industries, as both deal with high temperature low-density aqueous fluids. Understanding how metal halide species behave upon boiling can also provide insight into how metals, such as copper and silver, coat turbine equipment and steam piping in geothermal plants, ultimately rendering these components inoperable. This study will also provide preliminary results from mass spectrometric experiments of transition metal halides, and will be augmented with results from molecular simulations of metal halides that are aimed at characterizing the nature (i.e. relativistic structures and energies) of metal clusters in water vapor.

Recent advances in bulk metallic glasses for biomedical applications.

PubMed

Li, H F; Zheng, Y F

2016-05-01

With a continuously increasing aging population and the improvement of living standards, large demands of biomaterials are expected for a long time to come. Further development of novel biomaterials, that are much safer and of much higher quality, in terms of both biomedical and mechanical properties, are therefore of great interest for both the research scientists and clinical surgeons. Compared with the conventional crystalline metallic counterparts, bulk metallic glasses have unique amorphous structures, and thus exhibit higher strength, lower Young's modulus, improved wear resistance, good fatigue endurance, and excellent corrosion resistance. For this purpose, bulk metallic glasses (BMGs) have recently attracted much attention for biomedical applications. This review discusses and summarizes the recent developments and advances of bulk metallic glasses, including Ti-based, Zr-based, Fe-based, Mg-based, Zn-based, Ca-based and Sr-based alloying systems for biomedical applications. Future research directions will move towards overcoming the brittleness, increasing the glass forming ability (GFA) thus obtaining corresponding bulk metallic glasses with larger sizes, removing/reducing toxic elements, and surface modifications. Bulk metallic glasses (BMGs), also known as amorphous alloys or liquid metals, are relative newcomers in the field of biomaterials. They have gained increasing attention during the past decades, as they exhibit an excellent combination of properties and processing capabilities desired for versatile biomedical implant applications. The present work reviewed the recent developments and advances of biomedical BMGs, including Ti-based, Zr-based, Fe-based, Mg-based, Zn-based, Ca-based and Sr-based BMG alloying systems. Besides, the critical analysis and in-depth discussion on the current status, challenge and future development of biomedical BMGs are included. The possible solution to the BMG size limitation, the brittleness of BMGs has been proposed. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Photoluminescence and lasing properties of MAPbBr3 single crystals grown from solution

NASA Astrophysics Data System (ADS)

Aryal, Sandip; Lafalce, Evan; Zhang, Chuang; Zhai, Yaxin; Vardeny, Z. Valy

Recent studies of solution-grown single crystals of inorganic-organic hybrid lead-trihalide perovskites have suggested that surface traps may play a significant role in their photophysics. We study electron-hole recombination in single crystal MAPbBr3 through such trap states using cw photoluminescence (PL) and ps transient photoinduced absorption (PA) spectroscopies. By varying the depth of the collecting optics we examined the contributions from surface and bulk radiative recombination. We found a surface dominated PL band at the band-edge that is similar to that observed from polycrystalline thin films, as well as a weaker red-shifted emission band that originates from the bulk crystal. The two PL bands are distinguished in their temperature, excitation intensity and polarization dependencies, as well as their ps dynamics. Additionally, amplified spontaneous emission and crystal-related cavity lasing modes were observed in the same spectral range as the PL band assigned to the surface recombination. This work was funded by AFOSR through MURI Grant RA 9550-14-1-0037.

Microstructure and mechanical properties of bulk yttria-partially-stabilized zirconia

NASA Technical Reports Server (NTRS)

Valentine, P. G.; Maier, R. D.; Mitchell, T. E.

1981-01-01

A commercially available bulk 4.5 mole percent yttria-Y2O3)-partially-stabilized zirconia (PSZ) was studied by light microscopy, X-ray analysis, microhardness measurement, and fracture toughness testing. The growth of the precipitates and the phase transformations were studied as a function of aging in air at 1500 C. Aging cuves were constructed for both the as-received and the solution-annealed-and-quenched materials; the curves showed hardness peaks at 1397 and 1517 kg/sq mm, respectively. A total of twelve different types of tetragonal precipitates were found. The rectangular plate-shaped tetragonal precipitates were found to have a (110) habit plane. Grinding of the Y2O3 PSZ into powder did not cause a significant amount of metastable tetragonal precipitates to transform into the monoclinic phase, thus indicating that transformation toughening is not a significant mechanism for the material. The fracture toughness of the aged and of the unaged solution-annealed-and-quenched PSZ was found to be between 2 and 3 MN/cu m/2.

Solutions for the diurnally forced advection-diffusion equation to estimate bulk fluid velocity and diffusivity in streambeds from temperature time series

Treesearch

Charles H. Luce; Daniele Tonina; Frank Gariglio; Ralph Applebee

2013-01-01

Work over the last decade has documented methods for estimating fluxes between streams and streambeds from time series of temperature at two depths in the streambed. We present substantial extension to the existing theory and practice of using temperature time series to estimate streambed water fluxes and thermal properties, including (1) a new explicit analytical...

Particle characterization of poorly water-soluble drugs using a spray freeze drying technique.

PubMed

Kondo, Masahiro; Niwa, Toshiyuki; Okamoto, Hirokazu; Danjo, Kazumi

2009-07-01

A spray freeze drying (SFD) method was developed to prepare the composite particles of poorly water-soluble drug. The aqueous solution dissolved drug and the functional polymer was sprayed directly into liquid nitrogen. Then, the iced droplets were lyophilized with freeze-dryer to prepare solid particles. Tolbutamide (TBM) and hydroxypropylmethylcellulose (HPMC) were used as a model drug and water-soluble polymeric carrier in this study, respectively. The morphological observation of particles revealed that the spherical particles having porous structure could be obtained by optimizing the loading amount of drug and polymer in the spray solution. Especially, SFD method was characterized that the prepared particles had significantly larger specific surface area comparing with those prepared by the standard spray drying technique. The physicochemical properties of the resultant particles were found to be dependent on the concentration of spray solution. When the solution with high content of drug and polymer was used, the particle size of the resulting composite particles increased and they became spherical. The specific surface area of the particles also increased as a result of higher concentration of solution. The evaluation of spray solution indicated that these results were dependent on the viscosity of spray solution. In addition, when composite particles of TBM were prepared using the SFD method with HPMC as a carrier, the crystallinity of TBM decreased as the proportion of HPMC increased. When the TBM : HPMC ratio reached 1 : 5, the crystallinity of the particles completely disappeared. The dissolution tests showed that the release profiles of poorly water-soluble TBM from SFD composite particles were drastically improved compared to bulk TBM. The 70% release time T(70) of composite particles prepared by the SFD method in a solution of pH 1.2 was quite smaller than that of bulk TBM, while in a solution of pH 6.8, it was slightly lower. In addition, the release rates were faster than those of standard spray dried (SD) composite particles for solutions of pH 1.2 and 6.8, respectively. When composite particles were prepared from mixtures with various composition ratios, T(70) was found to decrease as the proportion of HPMC increased; the release rate was faster than that of bulk TBM in a solution of pH 6.8, as well as solution of pH 1.2.

Linearized Israel matching conditions for cosmological perturbations in a moving brane background

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

Bucher, Martin; DAMTP, University of Cambridge, Cambridge CB3 0WA; Carvalho, Carla

2005-04-15

In the Randall-Sundrum cosmological models, a (3+1)-dimensional brane subject to a Z{sub 2} orbifold symmetry is embedded in a (4+1)-dimensional bulk spacetime empty except for a negative cosmological constant. The unperturbed braneworld cosmological solutions, subject to homogeneity and isotropy in the three transverse spatial dimensions, are most simply presented by means of a moving brane description. Owing to a generalization of Birkhoff's theorem, as long as there are no perturbations violating the three-dimensional spatial homogeneity and isotropy, the bulk spacetime remains stationary and trivial. For the spatially flat case, the bulk spacetime is described by one of three bulk solutions:more » a pure AdS{sup 5} solution, an AdS{sup 5}-Schwarzschild black hole solution, or an AdS{sup 5}-Schwarzschild naked singularity solution. The brane moves on the boundary of one of these simple bulk spacetimes, its trajectory determined by the evolution of the stress-energy localized on the brane. We derive here the form of the Israel matching conditions for the linearized cosmological perturbations in this moving brane picture. These Israel matching conditions must be satisfied in any gauge. However, they are not sufficient to determine how to describe in a specific gauge the reflection of the bulk gravitational waves off the brane boundary. In this paper we adopt a fully covariant Lorentz gauge condition in the bulk and find the supplementary gauge conditions that must be imposed on the boundary to ensure that the reflected waves do not violate the Lorentz gauge condition. Compared to the form obtained from Gaussian normal coordinates, the form of the Israel matching conditions obtained here is more complex. However, the propagation of the bulk gravitons is simpler because the coordinates used for the background exploit fully the symmetry of the bulk background solution.« less

Spatial and Temporal Control of Surfactant Systems

PubMed Central

Liu, Xiaoyang; Abbott, Nicholas L.

2011-01-01

This paper reviews some recent progress on approaches leading to spatial and temporal control of surfactant systems. The approaches revolve around the use of redox-active and light-sensitive surfactants. Perspectives are presented on experiments that have realized approaches for active control of interfacial properties of aqueous surfactant systems, reversible control of microstructures and nanostructures formed within bulk solutions, and in situ manipulation of the interactions of surfactants with polymers, DNA and proteins. A particular focus of this review is devoted to studies of amphiphiles that contain the redox-active group ferrocene – reversible control of the oxidation state of ferrocene leads to changes in the charge/hydrophobicity of these amphiphiles, resulting in substantial changes in their self-assembly. Light-sensitive surfactants containing azobenzene, which undergo changes in shape/polarity upon illumination with light, are a second focus of this review. Examples of both redox-active and light-sensitive surfactants that lead to large (> 20mN/m) and spatially localized (~mm) changes in surface tensions on a time scale of seconds are presented. Systems that permit reversible transformations of bulk solution nanostructures – such as micelle-to-vesicle transitions or monomer-to-micelle transitions – are also described. The broad potential utility of these emerging classes of amphiphiles are illustrated by the ability to drive changes in functional properties of surfactant systems, such as rheological properties and reversible solubilization of oils, as well as the ability to control interactions of surfactants with biomolecules to modulate their transport into cells. PMID:19665723

Impact of Backbone Tether Length and Structure on the Electrochemical Performance of Viologen Redox Active Polymers

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

Burgess, Mark; Chénard, Etienne; Hernández-Burgos, Kenneth

The design of chemically stable and electrochemically reversible redox active polymers (RAPs) is of great interest for energy storage technologies. Particularly, RAPs are new players for flow batteries relying on a size-exclusion based mechanism of electrolyte separation, but few studies have provided detailed molecular understanding of redox polymers in solution. Here, we use a systematic molecular design approach to investigate the impact of linker and redox-pendant electronic interactions on the performance of viologen RAPs. We used scanning electrochemical microscopy, cyclic voltammetry, bulk electrolysis, temperature-dependent absorbance, and spectroelectrochemistry to study the redox properties, charge transfer kinetics, and self-exchange of electrons throughmore » redox active dimers and their equivalent polymers. Stark contrast was observed between the electrochemical properties of viologen dimers and their corresponding polymers. Electron self-exchange kinetics in redox active dimers that only differ by their tether length and rigidity influences their charge transfer properties. Predictions from the Marcus Hush theory were consistent with observations in redox active dimers, but they failed to fully capture the behavior of macromolecular systems. For example, polymer bound viologen pendants, if too close in proximity, do not retain chemical reversibility. In contrast to polymer films, small modifications to the backbone structure decisively impact the bulk electrolysis of polymer solutions. This first comprehensive study highlights the careful balance between electronic interactions and backbone rigidity required to design RAPs with superior electrochemical performance.« less

First evidence on phloem transport of nanoscale calcium oxide in groundnut using solution culture technique

NASA Astrophysics Data System (ADS)

Deepa, Manchala; Sudhakar, Palagiri; Nagamadhuri, Kandula Venkata; Balakrishna Reddy, Kota; Giridhara Krishna, Thimmavajjula; Prasad, Tollamadugu Naga Venkata Krishna Vara

2015-06-01

Nanoscale materials, whose size typically falls below 100 nm, exhibit novel chemical, physical and biological properties which are different from their bulk counterparts. In the present investigation, we demonstrated that nanoscale calcium oxide particles (n-CaO) could transport through phloem tissue of groundnut unlike the corresponding bulk materials. n-CaO particles are prepared using sol-gel method. The size of the as prepared n-CaO measured (69.9 nm) using transmission electron microscopic technique (TEM). Results of the hydroponics experiment using solution culture technique revealed that foliar application of n-CaO at different concentrations (10, 50, 100, 500, 1,000 ppm) on groundnut plants confirmed the entry of calcium into leaves and stems through phloem compared to bulk source of calcium sprayed (CaO and CaNO3). After spraying of n-CaO, calcium content in roots, shoots and leaves significantly increased. Based on visual scoring of calcium deficiency correction and calcium content in plant parts, we may establish the fact that nanoscale calcium oxide particles (size 69.9 nm) could move through phloem tissue in groundnut. This is the first report on phloem transport of nanoscale calcium oxide particles in plants and this result points to the use of nanoscale calcium oxide particles as calcium source to the plants through foliar application, agricultural crops in particular, as bulk calcium application through foliar nutrition is restricted due to its non-mobility in phloem.

Evolution of the electrical resistivity anisotropy during saline tracer tests: insights from geoelectrical milli-fluidic experiments

NASA Astrophysics Data System (ADS)

Jougnot, D.; Jimenez-Martinez, J.; Legendre, R.; Le Borgne, T.; Meheust, Y.; Linde, N.

2017-12-01

The use of time-lapse electrical resistivity tomography has been largely developed in environmental studies to remotely monitor water saturation and contaminant plumes migration. However, subsurface heterogeneities, and corresponding preferential transport paths, yield a potentially large anisotropy in the electrical properties of the subsurface. In order to study this effect, we have used a newly developed geoelectrical milli-fluidic experimental set-up with a flow cell that contains a 2D porous medium consisting of a single layer of cylindrical solid grains. We performed saline tracer tests under full and partial water saturations in that cell by jointly injecting air and aqueous solutions with different salinities. The flow cell is equipped with four electrodes to measure the bulk electrical resistivity at the cell's scale. The spatial distribution of the water/air phases and the saline solute concentration field in the water phase are captured simultaneously with a high-resolution camera by combining a fluorescent tracer with the saline solute. These data are used to compute the longitudinal and transverse effective electrical resistivity numerically from the measured spatial distributions of the fluid phases and the salinity field. This approach is validated as the computed longitudinal effective resistivities are in good agreement with the laboratory measurements. The anisotropy in electrical resistivity is then inferred from the computed longitudinal and transverse effective resistivities. We find that the spatial distribution of saline tracer, and potentially air phase, drive temporal changes in the effective resistivity through preferential paths or barriers for electrical current at the pore scale. The resulting heterogeneities in the solute concentrations lead to strong anisotropy of the effective bulk electrical resistivity, especially for partially saturated conditions. Therefore, considering the electrical resistivity as a tensor could improve our understanding of transport properties from field-scale time-lapse ERT.

DEM Solutions Develops Answers to Modeling Lunar Dust and Regolith

NASA Technical Reports Server (NTRS)

Dunn, Carol Anne; Calle, Carlos; LaRoche, Richard D.

2010-01-01

With the proposed return to the Moon, scientists like NASA-KSC's Dr. Calle are concerned for a number of reasons. We will be staying longer on the planet's surface, future missions may include dust-raising activities, such as excavation and handling of lunar soil and rock, and we will be sending robotic instruments to do much of the work for us. Understanding more about the chemical and physical properties of lunar dust, how dust particles interact with each other and with equipment surfaces and the role of static electricity build-up on dust particles in the low-humidity lunar environment is imperative to the development of technologies for removing and preventing dust accumulation, and successfully handling lunar regolith. Dr. Calle is currently working on the problems of the electrostatic phenomena of granular and bulk materials as they apply to planetary surfaces, particularly to those of Mars and the Moon, and is heavily involved in developing instrumentation for future planetary missions. With this end in view, the NASA Kennedy Space Center's Innovative Partnerships Program Office partnered with OEM Solutions, Inc. OEM Solutions is a global leader in particle dynamics simulation software, providing custom solutions for use in tackling tough design and process problems related to bulk solids handling. Customers in industries such as pharmaceutical, chemical, mineral, and materials processing as well as oil and gas production, agricultural and construction, and geo-technical engineering use OEM Solutions' EDEM(TradeMark) software to improve the design and operation of their equipment while reducing development costs, time-to-market and operational risk. EDEM is the world's first general-purpose computer-aided engineering (CAE) tool to use state-of-the-art discrete element modeling technology for the simulation and analysis of particle handling and manufacturing operations. With EDEM you'can quickly and easily create a parameterized model of your granular solids system. Computer-aided design (CAD) models of real particles can be imported to obtain an accurate representation of their shape. EDEM(TradeMark) uses particle-scale behavior models to simulate bulk solids behavior. In addition to particle size and shape, the models can account for physical properties of particles along with interaction between particles and with equipment surfaces and surrounding media, as needed to define the physics of a particular process.

Atomistic Modeling of Surface and Bulk Properties of Cu, Pd and the Cu-Pd System

NASA Technical Reports Server (NTRS)

Bozzolo, Guillermo; Garces, Jorge E.; Noebe, Ronald D.; Abel, Phillip; Mosca, Hugo O.; Gray, Hugh R. (Technical Monitor)

2002-01-01

The BFS (Bozzolo-Ferrante-Smith) method for alloys is applied to the study of the Cu-Pd system. A variety of issues are analyzed and discussed, including the properties of pure Cu or Pd crystals (surface energies, surface relaxations), Pd/Cu and Cu/Pd surface alloys, segregation of Pd (or Cu) in Cu (or Pd), concentration dependence of the lattice parameter of the high temperature fcc CuPd solid solution, the formation and properties of low temperature ordered phases, and order-disorder transition temperatures. Emphasis is made on the ability of the method to describe these properties on the basis of a minimum set of BFS universal parameters that uniquely characterize the Cu-Pd system.

Passive non-linear microrheology for determining extensional viscosity

NASA Astrophysics Data System (ADS)

Hsiao, Kai-Wen; Dinic, Jelena; Ren, Yi; Sharma, Vivek; Schroeder, Charles M.

2017-12-01

Extensional viscosity is a key property of complex fluids that greatly influences the non-equilibrium behavior and processing of polymer solutions, melts, and colloidal suspensions. In this work, we use microfluidics to determine steady extensional viscosity for polymer solutions by directly observing particle migration in planar extensional flow. Tracer particles are suspended in semi-dilute solutions of DNA and polyethylene oxide, and a Stokes trap is used to confine single particles in extensional flows of polymer solutions in a cross-slot device. Particles are observed to migrate in the direction transverse to flow due to normal stresses, and particle migration is tracked and quantified using a piezo-nanopositioning stage during the microfluidic flow experiment. Particle migration trajectories are then analyzed using a second-order fluid model that accurately predicts that migration arises due to normal stress differences. Using this analytical framework, extensional viscosities can be determined from particle migration experiments, and the results are in reasonable agreement with bulk rheological measurements of extensional viscosity based on a dripping-onto-substrate method. Overall, this work demonstrates that non-equilibrium properties of complex fluids can be determined by passive yet non-linear microrheology.

Propensity of bond exchange as a window into the mechanical properties of metallic glasses

NASA Astrophysics Data System (ADS)

Jiao, W.; Wang, X. L.; Lan, S.; Pan, S. P.; Lu, Z. P.

2015-02-01

We investigated the mechanical properties of Zr-Cu-Al bulk metallic glasses, by compression experiment and molecular dynamics simulations. From the simulation, we found that the large, solvent atom, Zr, has high propensity of bond exchange compared to those of the smaller solute atoms. The difference in bond exchange is consistent with the observed disparity in mechanical behaviors: Zr-rich metallic glass exhibits low elastic modulus and large plastic strain. X-ray photoelectron spectroscopy measurements suggest that the increased propensity in bond exchange is related to the softening of Zr bonds with increasing Zr content.

Microwave properties of film Ba x Sr1 - x TiO3 ferroelectric variconds with a magnesium-containing additive

NASA Astrophysics Data System (ADS)

Tumarkin, A. V.; Tepina, E. R.; Nenasheva, E. A.; Kartenko, N. F.; Kozyrev, A. B.

2012-06-01

The electrophysical properties of bulk ceramics based on Ba x Sr1 - x TiO3 solid solutions with a Mg-containing additive and planar variconds based on ferroelectric films obtained by the ion-plasma sputtering of targets with different elemental compositions are studied. Controllability n( U) = C(0)/ C( U) and the dielectric loss tangent (tanδ) of ferroelectric variconds are measured as functions of the elemental composition of the ferroelectric. The figure of merit of the variconds is estimated, and the film composition providing the best electrophysical parameters is determined.

46 CFR Table 2 to Part 153 - Cargoes Not Regulated Under Subchapters D or O of This Chapter When Carried in Bulk on Non...

Code of Federal Regulations, 2010 CFR

2010-10-01

... polyacrylate solution III Tetrasodium salt of Ethylenediaminetetraaacetic acid solution, see... 46 Shipping 5 2010-10-01 2010-10-01 false Cargoes Not Regulated Under Subchapters D or O of This..., DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES SHIPS CARRYING BULK LIQUID...

The behaviour of water and sodium chloride solution confined into asbestos nanotube

NASA Astrophysics Data System (ADS)

Fomin, Yu. D.; Ryzhov, V. N.; Tsiok, E. N.

2016-08-01

We present the molecular simulation study of the behaviour of water and sodium chloride solution confined in lizardite asbestos nanotube which is a typical example of hydrophilic confinement. The local structure and orientational and dynamic properties are studied. It is shown that at low enough temperatures there is a well-defined orientational ordering of the water molecules. At high local densities corresponding to the maxima of the density distribution function, the water molecules are oriented parallel to the axis of the tube. It is also shown that the diffusion coefficient drops about two orders of magnitude comparing to the bulk case. The behaviour of sodium chloride solutions is also considered and the formation of double layer is observed.

46 CFR 151.50-75 - Ferric chloride solution.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 46 Shipping 5 2010-10-01 2010-10-01 false Ferric chloride solution. 151.50-75 Section 151.50-75 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES BARGES CARRYING BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-75 Ferric chloride solution...

The Effect of Valinomycin on the Electrical Properties of Solutions of Red Cell Lipids in n-Decane

PubMed Central

Andreoli, Thomas E.; Tosteson, Daniel C.

1971-01-01

This paper reports the electrical properties of thick lipid membranes in the absence and presence of valinomycin. The thick lipid membranes were formed by placing a solution of sheep red cell lipids in decane between two cellophane partitions which formed the interfaces between the membrane and the two aqueous bathing solutions. The DC electrical resistance of these structures was found to be directly proportional to the reciprocal of the concentration of lipids in the decane (CL). The limiting resistance, as (CL -1) approached zero, was 3 x 108 ohm-cm2. Resistance was also found to be linearly related to membrane thickness. The limiting resistance at zero thickness was again 1–3 x 108 ohm-cm2. These data are interpreted to indicate that the DC resistance of thick lipid membranes comprises two surface resistances (RS) at each interface with the aqueous bathing solutions, and a bulk resistance (RB) of the lipid-decane solution, arranged in series. Measurements of the effect of variations of area on resistance were consistent with this interpretation. Valinomycin reduced RS but had no effect on RB. Under certain conditions, thick lipid membranes containing valinomycin behaved like highly selective K+ electrodes. PMID:5553100

Multistep building of a soft plant protein film at the air-water interface.

PubMed

Poirier, Alexandre; Banc, Amélie; Stocco, Antonio; In, Martin; Ramos, Laurence

2018-09-15

Gliadins are edible wheat storage proteins well known for their surface active properties. In this paper, we present experimental results on the interfacial properties of acidic solutions of gliadin studied over 5 decades of concentrations, from 0.001 to 110 g/L. Dynamic pendant drop tensiometry reveals that the surface pressure Π of gliadin solutions builds up in a multistep process. The series of curves of the time evolution of Π collected at different bulk protein concentrations C can be merged onto a single master curve when Π is plotted as a function of αt where t is the time elapsed since the formation of the air/water interface and α is a shift parameter that varies with C as a power law with an exponent 2. The existence of such time-concentration superposition, which we evidence for the first time, indicates that the same mechanisms govern the surface tension evolution at all concentrations and are accelerated by an increase of the bulk concentration. The scaling of α with C is consistent with a kinetic of adsorption controlled by the diffusion of the proteins in the bulk. Moreover, we show that the proteins adsorption at the air/water interface is kinetically irreversible. Correlated evolutions of the optical and elastic properties of the interfaces, as probed by ellipsometry and surface dilatational rheology respectively, provide a consistent physical picture of the building up of the protein interfacial layer. A progressive coverage of the interface by the proteins occurs at low Π. This stage is followed, at higher Π, by conformational rearrangements of the protein film, which are identified by a strong increase of the dissipative viscoelastic properties of the film concomitantly with a peculiar evolution of its optical profile that we have rationalized. In the last stage, at even higher surface pressure, the adsorption is arrested; the optical profile is not modified while the elasticity of the interfacial layer dramatically increases with the surface pressure, presumably due to the film ageing. Copyright © 2018 Elsevier Inc. All rights reserved.

Influence of Molecular Conformations and Microstructure on the Optoelectronic Properties of Conjugated Polymers

PubMed Central

Botiz, Ioan; Stingelin, Natalie

2014-01-01

It is increasingly obvious that the molecular conformations and the long-range arrangement that conjugated polymers can adopt under various experimental conditions in bulk, solutions or thin films, significantly impact their resulting optoelectronic properties. As a consequence, the functionalities and efficiencies of resulting organic devices, such as field-effect transistors, light-emitting diodes, or photovoltaic cells, also dramatically change due to the close structure/property relationship. A range of structure/optoelectronic properties relationships have been investigated over the last few years using various experimental and theoretical methods, and, further, interesting correlations are continuously revealed by the scientific community. In this review, we discuss the latest findings related to the structure/optoelectronic properties interrelationships that exist in organic devices fabricated with conjugated polymers in terms of charge mobility, absorption, photoluminescence, as well as photovoltaic properties. PMID:28788568

Interaction of pepsin-[C16mim]Br system: interfacial dilational rheology and conformational studies.

PubMed

Huang, Tian; Cao, Chong; Liu, Zi-lin; Li, Yang; Du, Feng-pei

2014-09-21

The interfacial rheological property is closely related to the stabilities of foams and emulsions, yet there have been limited studies on the interaction between proteins with ionic liquid-type imidazolium surfactants at the decane-water interface as well as in the bulk. Herein, we investigated the interfacial and bulk properties of pepsin (PEP) and an ionic liquid (IL), 1-hexadecyl-3-methylimidazolium bromide, [C(16)mim]Br. The interfacial pressure and dilational rheology studies were performed to describe the formation of [C(16)mim]Br-pepsin complexes. The influence of the oscillating frequency and the bulk concentration of [C(16)mim]Br on the dilational properties were explored. The conformational changes were studied by monitoring the fluorescence and far UV-CD spectra. The results reveal that the globular structure of pepsin is one of the decisive factors controlling the nature of the interfacial film. The monotonous increase in the dilational elastic modulus of pepsin-[C(16)mim]Br solutions with the surface age indicates that no loops and tails had formed. Interestingly, with an increase in the concentration of [C(16)mim]Br, the εd-c curve first passes through a plateau value due to steric hindrance and the electrostatic barrier of already absorbed tenacious pepsin-[C(16)mim]Br complexes. With the further addition of [C(16)mim]Br, the remarkable decrease in dilational elastic modulus indicates that the compact structure is destroyed gradually. The results of the fluorescence spectra and far UV-CD spectra confirm that [C(16)mim]Br did not produce perceptible changes in pepsin at the concentrations studied in the dilational experiment. Possible schematic programs of the pepsin-[C(16)mim]Br interaction model at the interface and in bulk phase are proposed.

Superconducting Thin Films for the Enhancement of Superconducting Radio Frequency Accelerator Cavities

NASA Astrophysics Data System (ADS)

Burton, Matthew C.

Bulk niobium (Nb) superconducting radio frequency (SRF) cavities are currently the preferred method for acceleration of charged particles at accelerating facilities around the world. However, bulk Nb cavities have poor thermal conductance, impose material and design restrictions on other components of a particle accelerator, have low reproducibility and are approaching the fundamental material-dependent accelerating field limit of approximately 50MV/m. Since the SRF phenomena occurs at surfaces within a shallow depth of ˜1 microm, a proposed solution to this problem has been to utilize thin film technology to deposit superconducting thin films on the interior of cavities to engineer the active SRF surface in order to achieve cavities with enhanced properties and performance. Two proposed thin film applications for SRF cavities are: 1) Nb thin films coated on bulk cavities made of suitable castable metals (such as copper or aluminum) and 2) multilayer films designed to increase the accelerating gradient and performance of SRF cavities. While Nb thin films on copper (Cu) cavities have been attempted in the past using DC magnetron sputtering (DCMS), such cavities have never performed at the bulk Nb level. However, new energetic condensation techniques for film deposition, such as High Power Impulse Magnetron Sputtering (HiPIMS), offer the opportunity to create suitably thick Nb films with improved density, microstructure and adhesion compared to traditional DCMS. Clearly use of such novel technique requires fundamental studies to assess surface evolution and growth modes during deposition and resulting microstructure and surface morphology and the correlation with RF superconducting properties. Here we present detailed structure-property correlative research studies done on Nb/Cu thin films and NbN- and NbTiN-based multilayers made using HiPIMS and DCMS, respectively.

Influence of the ultrasound-assisted synthesis of Cu-BTC metal-organic frameworks nanoparticles on uptake and release properties of rifampicin.

PubMed

Abbasi, Amir Reza; Rizvandi, Maryam

2018-01-01

In this work, we study uptake and release properties of rifampicin (denoted henceforth as Rif) from ultrasound-assisted synthesis Cu-BTC nanoparticles in comparison with bulk Cu-BTC and activated carbon. To explore the absorption ability of the Cu-BTC to Rif, fresh sample of Cu-BTC was immersed in an aqueous solution of Rif and were monitored in real time with UV/vis spectroscopy. Results show that the adsorbed quantity of Rif over nano Cu-BTC (denoted henceforth as I) is much higher than those over a bulk Cu-BTC (denoted henceforth as II) and activated carbon. In compound I and all of the nano-MOFs the channel length is decreased so that the amount of adsorption is increased a little. The samples were characterized with X-ray powder diffraction (XRD), Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), and UV/vis spectroscopy. Copyright © 2017 Elsevier B.V. All rights reserved.

Holographic cosmology and phase transitions of SYM theory

NASA Astrophysics Data System (ADS)

Ghoroku, Kazuo; Meyer, René; Toyoda, Fumihiko

2017-10-01

We study the time development of strongly coupled N =4 supersymmetric Yang Mills (SYM) theory on cosmological Friedmann-Robertson-Walker (FRW) backgrounds via the AdS/CFT correspondence. We implement the cosmological background as a boundary metric fulfilling the Friedmann equation with a four-dimensional cosmological constant and a dark radiation term. We analyze the dual bulk solution of the type IIB supergravity and find that the time dependence of the FRW background strongly influences the dynamical properties of the SYM theory. We in particular find a phase transition between a confined and a deconfined phase. We also argue that some cosmological solutions could be related to the inflationary scenario.

Structural and optical properties of novel surfactant-coated Yb@TiO2 nanoparticles

NASA Astrophysics Data System (ADS)

Calandra, P.; Lombardo, D.; Pistone, A.; Turco Liveri, V.; Trusso, S.

2011-11-01

In this paper a novel hybrid approach to synthesise composite nanoparticles is presented. It is based on the laser ablation of a bulk target (Yb) immersed in a reversed micellar solution which contains nanoparticles of a different host material (TiO2 nanoparticles) previously synthesised by chemical method. This approach thus exploits the advantages of the chemical synthesis through reversed micellar solution (size control, nanoparticle stabilisation), and of the laser ablation ("clean" synthesis, no side reactions). Central role is played by the microscopic processes controlling the deposition of the ablated Yb atoms onto the surface of TiO2 nanoparticles which actually behave as nucleation seeds. The structural features of the resulting Yb@TiO2 composite nanoparticles have been studied by Transmission Electron Microscopy, whereas their peculiar optical properties have been explored by UV-Vis spectroscopy and steady-state fluorescence. Results consistently show the formation of Yb and TiO2 glued nanodomains to form nearly spherical and non-interacting nanoparticles with enhanced photophysical properties.

A homogenization approach for the effective drained viscoelastic properties of 2D porous media and an application for cortical bone.

PubMed

Nguyen, Sy-Tuan; Vu, Mai-Ba; Vu, Minh-Ngoc; To, Quy-Dong

2018-02-01

Closed-form solutions for the effective rheological properties of a 2D viscoelastic drained porous medium made of a Generalized Maxwell viscoelastic matrix and pore inclusions are developed and applied for cortical bone. The in-plane (transverse) effective viscoelastic bulk and shear moduli of the Generalized Maxwell rheology of the homogenized medium are expressed as functions of the porosity and the viscoelastic properties of the solid phase. When deriving these functions, the classical inverse Laplace-Carson transformation technique is avoided, due to its complexity, by considering the short and long term approximations. The approximated results are validated against exact solutions obtained from the inverse Laplace-Carson transform for a simple configuration when the later is available. An application for cortical bone with assumption of circular pore in the transverse plane shows that the proposed approximation fit very well with experimental data. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sugar replacers: from technological challenges to consequences on health.

PubMed

Lê, Kim-Anne; Robin, Frédéric; Roger, Olivier

2016-07-01

Dietary sugars play a role in noncommunicable diseases and represent a clear target for reduction. In this context, product reformulation can have a positive impact on health. Several technological solutions are available to replace sugar, all with benefits and limitations. The goal of this review is to describe the main sugar replacement alternatives and discuss their impact on health and product physicochemical properties. Although high intensity sweeteners and polyols have been used for a long time to replace sucrose and despite no clear evidence of harm, the trend is today to look for alternatives such as sweet enhancers or alternative sugars such as allulose or tagatose, which are both low caloric. To replace the physical properties of sugars, new trends are to substitute widely used maltodextrins by dietary fibres to confer added health benefits. A wide range of solutions is currently available to replace dietary sugars and compensate for the impact on bulking properties and sweetness profile of food products.

Effect of pH adjustment, homogenization and diafiltration on physicochemical, reconstitution, functional and rheological properties of medium protein milk protein concentrates (MPC70).

PubMed

Meena, Ganga Sahay; Singh, Ashish Kumar; Gupta, Vijay Kumar; Borad, Sanket; Arora, Sumit; Tomar, Sudhir Kumar

2018-04-01

Poor solubility is the major limiting factor in commercial applications of milk protein concentrates (MPC) powders. Retentate treatments such as pH adjustment using disodium phosphate (Na 2 HPO 4 ), also responsible for calcium chelation with homogenization and; its diafiltration with 150 mM NaCl solution were hypothesized to improve the functional properties of treated MPC70 powders. These treatments significantly improved the solubility, heat stability, water binding, dispersibility, bulk density, flowability, buffer index, foaming and emulsifying capacity of treated powders over control. Rheological behaviour of reconstituted MPC solutions was best explained by Herschel Bulkley model. Compared to rough, large globular structures with dents in control; majorly intact, separate, smaller particles of smooth surface, without any aggregation were observed in SEM micrograph of treated powders. Applied treatments are easy, cost-effective and capable to improve functional properties of treated powders that could replace control MPC70 powder in various food applications where protein functionality is of prime importance.

Surface properties of anatase TiO2 nanowire films grown from a fluoride-containing solution.

PubMed

Berger, Thomas; Anta, Juan A; Morales-Flórez, Víctor

2013-06-03

Controlling the surface chemistry of nucleating seeds during wet-chemical synthesis allows for the preparation of morphologically well-defined nanostructures. Synthesis conditions play a key role in the surface properties, which directly affect the functional properties of the material. Therefore, it is important to establish post-synthesis treatments to facilitate the optimization of surface properties with respect to a specific application, without losing the morphological peculiarity of the nanostructure. We studied the surface properties of highly crystalline and porous anatase TiO2 nanowire (NW) electrodes, grown by chemical-bath deposition in fluoride-containing solutions, using a combined electrochemical and spectroscopic approach. As-deposited films showed low capacity for catechol adsorption and a poor photoelectrocatalytic activity for water oxidation. Mild thermal annealing at 200 °C resulted in a significant improvement of the electrode photoelectrocatalytic activity, whereas the bulk properties of the NWs (crystal structure, band-gap energy) remained unchanged. Enhancement of the functional properties of the material is discussed on the basis of adsorption capacity and electronic properties. The temperature-induced decrease of recombination centers, along with the concomitant increase of adsorption and reaction sites upon thermal annealing are called to be responsible for such improved performance. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solute rotational dynamics at the water liquid/vapor interface.

PubMed

Benjamin, Ilan

2007-11-28

The rotational dynamics of a number of diatomic molecules adsorbed at different locations at the interface between water and its own vapors are studied using classical molecular dynamics computer simulations. Both equilibrium orientational and energy correlations and nonequilibrium orientational and energy relaxation correlations are calculated. By varying the dipole moment of the molecule and its location, and by comparing the results with those in bulk water, the effects of dielectric and mechanical frictions on reorientation dynamics and on rotational energy relaxation can be studied. It is shown that for nonpolar and weekly polar solutes, the equilibrium orientational relaxation is much slower in the bulk than at the interface. As the solute becomes more polar, the rotation slows down and the surface and bulk dynamics become similar. The energy relaxation (both equilibrium and nonequilibrium) has the opposite trend with the solute dipole (larger dipoles relax faster), but here again the bulk and surface results converge as the solute dipole is increased. It is shown that these behaviors correlate with the peak value of the solvent-solute radial distribution function, which demonstrates the importance of the first hydration shell structure in determining the rotational dynamics and dependence of these dynamics on the solute dipole and location.

Hyporheic less-mobile porosity and solute transport in porous media

NASA Astrophysics Data System (ADS)

MahmoodPoorDehkordy, F.; Briggs, M. A.; Day-Lewis, F. D.; Scruggs, C.; Singha, K.; Zarnetske, J. P.; Lane, J. W., Jr.; Bagtzoglou, A. C.

2017-12-01

Solute transport and reactive processes are strongly influenced by hydrodynamic exchange with the hyporheic zone. Contaminant transport and redox zonation in the hyporheic zone and near-stream aquifer can be impacted by the exchange between mobile and less-mobile porosity zones in heterogeneous porous media. Less-mobile porosity zones can be created by fine materials with tight pore throats (e.g. clay, organics) and in larger, well-connected pores down gradient of flow obstructions (e.g. sand behind cobbles). Whereas fluid sampling is primarily responsive to the more-mobile domain, tracking solute tracer dynamics by geoelectrical methods provides direct information about both more- and less-mobile zones. During tracer injection through porous media of varied pore connectivity, a lag between fluid and bulk electrical conductivity is observed, creating a hysteresis loop when plotted in conductivity space. Thus, the combination of simultaneous fluid and bulk electrical conductivity measurements enables a much improved quantification of less-mobile solute dynamics compared to traditional fluid-only sampling approaches. We have demonstrated the less-mobile porosity exchange in laboratory-scale column experiments verified by simulation models. The experimental approach has also been applied to streambed sediments in column and reach-scale field experiments and verified using numerical simulation. Properties of the resultant hysteresis loops can be used to estimate exchange parameters of less-mobile porosity. Our integrated approach combining field experiments, laboratory experiments, and numerical modeling provides new insights into the effect of less-mobile porosity on solute transport in the hyporheic zone.

The influence of excipients commonly used in freeze drying on whole blood coagulation dynamics assessed by rotational thromboelastometry.

PubMed

Erber, Matthias; Lee, Geoffrey

2015-09-01

Lyophilized reagents are used on a daily basis in coagulation diagnostics. They often contain a number of excipients in addition to the active compound. Some of these excipients may, however, influence coagulation dynamics. Besides from plasmatic coagulation bulking agents may influence platelet properties. We therefore studied the influence of a variety of bulking agents (glycine, mannitol, sucrose and trehalose) as well as a surfactant (Tween® 80) on whole blood coagulation using thromboelastometry (ROTEM®) and platelet function analysis (ROTEM® platelet). Both disaccharides as well as Tween® 80 did not influence whole blood coagulation in the concentration range investigated. The addition of glycine and mannitol solutions to the ROTEM® measurement leads to an impaired clot formation as well as overall clot strength while clotting initiation remained barely influenced. Hypertonic glycine and mannitol solutions exhibit different clot formation impairment when correlated to their osmolar concentration and compared to equally osmolar NaCl-solutions. The effect of glycine was assigned to fibrin formation impairment identified with the FIBTEM assay. Platelet function analysis revealed that hypertonic glycine solutions do not alter platelet function but hypertonic mannitol and NaCl solutions do. While the influence observed for glycine may be due to fibrinogen precipitation, the mechanism of mannitol appears to be more complex as platelet function as well as fibrin-based clot formation are influenced. This study therefore demonstrates the necessity to check for coagulation impairment due to compounds contained in lyophilized reagents.

Coupled metal partitioning dynamics and toxicodynamics at biointerfaces: a theory beyond the biotic ligand model framework.

PubMed

Duval, Jérôme F L

2016-04-14

A mechanistic understanding of the processes governing metal toxicity to microorganisms (bacteria, algae) calls for an adequate formulation of metal partitioning at biointerfaces during cell exposure. This includes the account of metal transport dynamics from bulk solution to biomembrane and the kinetics of metal internalisation, both potentially controlling the intracellular and surface metal fractions that originate cell growth inhibition. A theoretical rationale is developed here for such coupled toxicodynamics and interfacial metal partitioning dynamics under non-complexing medium conditions with integration of the defining cell electrostatic properties. The formalism explicitly considers intertwined metal adsorption at the biointerface, intracellular metal excretion, cell growth and metal depletion from bulk solution. The theory is derived under relevant steady-state metal transport conditions on the basis of coupled Nernst-Planck equation and continuous logistic equation modified to include metal-induced cell growth inhibition and cell size changes. Computational examples are discussed to identify limitations of the classical Biotic Ligand Model (BLM) in evaluating metal toxicity over time. In particular, BLM is shown to severely underestimate metal toxicity depending on cell exposure time, metal internalisation kinetics, cell surface electrostatics and initial cell density. Analytical expressions are provided for the interfacial metal concentration profiles in the limit where cell-growth is completely inhibited. A rigorous relationship between time-dependent cell density and metal concentrations at the biosurface and in bulk solution is further provided, which unifies previous equations formulated by Best and Duval under constant cell density and cell size conditions. The theory is sufficiently flexible to adapt to toxicity scenarios with involved cell survival-death processes.

Surface-enhanced Raman scattering studies of the reduction of p-nitroaniline catalyzed by a nanonized Ag porous-glass hybrid composite.

PubMed

Huang, Genin Gary; Sou, Nga-Lai; Hung, Mei-Jou

2016-09-05

Nanonized noble metal composites have been known for their excellent catalytic properties. However, the mechanism and intermediates formed on the surfaces of nanocatalysts during catalysis are speculated with mostly insufficient evidence. In this study, to obtain further understanding of the roles of noble metal nanocatalysts in a catalytic reaction, surface-enhanced Raman scattering (SERS) was used to monitor the surfaces of silver (Ag) nanocatalysts. Furthermore, UV-Vis spectrometry was used to trace the concentration variations of reactants and products in bulk solutions, thereby correlating the variations of the Ag nanocatalyst surfaces with those in the bulk solutions. Nanonized Ag porous-glass hybrid composites were prepared by reducing naked Ag nanoparticles on porous-glass filter plates and were used as catalysts for nitroanilines reduction. The complete process was monitored using SERS and UV-Vis spectrometry simultaneously. The results indicated that the reactant and product molecules adsorbed on the Ag nanocatalysts can reach equilibrium, and the equilibrium is affected by the reaction conditions, including reducing agent concentration, pH of the reaction system, and temperature. In addition, the reduction of reactants in the bulk solutions is also related to the behavior of Ag nanocatalyst surfaces. Furthermore, Ag nanocatalysts can act as electron relays even if their surfaces are occupied by reactants and products. Analyzing the collected SERS and UV-Vis spectra can provide a new insight into Ag nanoparticle catalysis, and the role of Ag nanocatalysts can be further comprehended. Copyright © 2016 Elsevier B.V. All rights reserved.

Evaluating the Role of the Air-Solution Interface on the Mechanism of Subvisible Particle Formation Caused by Mechanical Agitation for an IgG1 mAb.

PubMed

Ghazvini, Saba; Kalonia, Cavan; Volkin, David B; Dhar, Prajnaparamita

2016-05-01

Mechanical agitation of monoclonal antibody (mAb) solutions often leads to protein particle formation. In this study, various formulations of an immunoglobulin G (IgG) 1 mAb were subjected to different controlled interfacial stresses using a Langmuir trough, and protein particles formed at the interface and measured in bulk solution were characterized using atomic force microscopy and flow digital imaging. Results were compared to mAb solutions agitated in glass vials and unstressed controls. At lower pH, mAb solutions exhibited larger hysteresis in their surface pressure versus area isotherms and increased number of particles in bulk solution, when subjected to interfacial stresses. mAb samples subjected to 750-1000 interfacial compression-expansion cycles in 6 h contained high particle numbers in bulk solution, and displayed similar particulation trends when agitated in vials. At compression rates of 50 cycles in 6 h, however, particle levels in mAb solutions were comparable to unstressed controls, despite protein aggregates being present at the air-solution interface. These results suggest that while the air-solution interface serves as a nucleation site for initiating protein aggregation, the number of protein particles measured in bulk mAb solutions depends on the total number of compression cycles that proteins at the air-solution interface are subjected to within a fixed time. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

STUDIES ON THE ANOMALOUS VISCOSITY AND FLOW-BIREFRINGENCE OF PROTEIN SOLUTIONS

PubMed Central

Lawrence, A. S. C.; Miall, Margaret; Needham, Joseph; Shen, Shih-Chang

1944-01-01

1. An extensive investigation has been made of protein particle shape using the methods of flow-birefringence and anomalous viscosity measurement in the coaxial cell. 2. As a result of investigations on a number of proteins, it is concluded that they may be divided into four groups. Group A consists of those which show flow-anomaly both in the bulk phase and in the surface film. These also show flow-birefringence in the bulk phase. Examples: tobacco mosaic disease virus nucleoprotein; myosin. Though corpuscular proteins, they have elongated particles before denaturation. Group B consists of those which show flow-anomaly only (in the first instance) in the surface film, and no flow-birefringence in the bulk phase. They are probably close to spherical in shape in solution, but form elongated particles as they denature in the surface film. After this process has been completed, they may show flow-anomaly also in the bulk phase. Some proteins show flow-anomaly in the surface film immediately it forms, others only show it after a certain time has elapsed for the building up of the film. We designate the former as group B1 and the latter as group B2. Group B1, immediate surface film flow-anomaly. Examples: serum euglobulin, amphibian embryo euglobulin b. Group B2, slowly appearing surface film flow-anomaly. After the film has once been fully formed and then dispersed by shaking, the solution may have the properties of that of a protein in group B1; i.e., anomalous flow in the film may occur immediately on testing in the viscosimeter. Examples: avian ovalbumin, amphibian embryo pseudoglobulin. Group C consists of those proteins which show flow-anomaly neither in the bulk phase nor in the surface film, under the conditions used by us. They are probably close to spherical in shape. Examples: insulin, methaemoglobin, amphibian embryo euglobulin c, mucoproteins. 3. The theoretical significance of protein fibre molecules, whether native or formed by denaturation in the living cell, is discussed, especially in relation to experimental morphology and cytology. PMID:19873385

One-dimensional organic lead halide perovskites with efficient bluish white-light emission

NASA Astrophysics Data System (ADS)

Yuan, Zhao; Zhou, Chenkun; Tian, Yu; Shu, Yu; Messier, Joshua; Wang, Jamie C.; van de Burgt, Lambertus J.; Kountouriotis, Konstantinos; Xin, Yan; Holt, Ethan; Schanze, Kirk; Clark, Ronald; Siegrist, Theo; Ma, Biwu

2017-01-01

Organic-inorganic hybrid metal halide perovskites, an emerging class of solution processable photoactive materials, welcome a new member with a one-dimensional structure. Herein we report the synthesis, crystal structure and photophysical properties of one-dimensional organic lead bromide perovskites, C4N2H14PbBr4, in which the edge sharing octahedral lead bromide chains [PbBr4 2-]∞ are surrounded by the organic cations C4N2H14 2+ to form the bulk assembly of core-shell quantum wires. This unique one-dimensional structure enables strong quantum confinement with the formation of self-trapped excited states that give efficient bluish white-light emissions with photoluminescence quantum efficiencies of approximately 20% for the bulk single crystals and 12% for the microscale crystals. This work verifies once again that one-dimensional systems are favourable for exciton self-trapping to produce highly efficient below-gap broadband luminescence, and opens up a new route towards superior light emitters based on bulk quantum materials.

One-dimensional organic lead halide perovskites with efficient bluish white-light emission

PubMed Central

Yuan, Zhao; Zhou, Chenkun; Tian, Yu; Shu, Yu; Messier, Joshua; Wang, Jamie C.; van de Burgt, Lambertus J.; Kountouriotis, Konstantinos; Xin, Yan; Holt, Ethan; Schanze, Kirk; Clark, Ronald; Siegrist, Theo; Ma, Biwu

2017-01-01

Organic-inorganic hybrid metal halide perovskites, an emerging class of solution processable photoactive materials, welcome a new member with a one-dimensional structure. Herein we report the synthesis, crystal structure and photophysical properties of one-dimensional organic lead bromide perovskites, C4N2H14PbBr4, in which the edge sharing octahedral lead bromide chains [PbBr4 2−]∞ are surrounded by the organic cations C4N2H14 2+ to form the bulk assembly of core-shell quantum wires. This unique one-dimensional structure enables strong quantum confinement with the formation of self-trapped excited states that give efficient bluish white-light emissions with photoluminescence quantum efficiencies of approximately 20% for the bulk single crystals and 12% for the microscale crystals. This work verifies once again that one-dimensional systems are favourable for exciton self-trapping to produce highly efficient below-gap broadband luminescence, and opens up a new route towards superior light emitters based on bulk quantum materials. PMID:28051092

One-dimensional organic lead halide perovskites with efficient bluish white-light emission.

PubMed

Yuan, Zhao; Zhou, Chenkun; Tian, Yu; Shu, Yu; Messier, Joshua; Wang, Jamie C; van de Burgt, Lambertus J; Kountouriotis, Konstantinos; Xin, Yan; Holt, Ethan; Schanze, Kirk; Clark, Ronald; Siegrist, Theo; Ma, Biwu

2017-01-04

Organic-inorganic hybrid metal halide perovskites, an emerging class of solution processable photoactive materials, welcome a new member with a one-dimensional structure. Herein we report the synthesis, crystal structure and photophysical properties of one-dimensional organic lead bromide perovskites, C 4 N 2 H 14 PbBr 4 , in which the edge sharing octahedral lead bromide chains [PbBr 4   2- ] ∞ are surrounded by the organic cations C 4 N 2 H 14   2+ to form the bulk assembly of core-shell quantum wires. This unique one-dimensional structure enables strong quantum confinement with the formation of self-trapped excited states that give efficient bluish white-light emissions with photoluminescence quantum efficiencies of approximately 20% for the bulk single crystals and 12% for the microscale crystals. This work verifies once again that one-dimensional systems are favourable for exciton self-trapping to produce highly efficient below-gap broadband luminescence, and opens up a new route towards superior light emitters based on bulk quantum materials.

Effect of Cryorolling and Aging on Fatigue Behavior of Ultrafine-grained Al6061

NASA Astrophysics Data System (ADS)

Yadollahpour, M.; Hosseini-Toudeshky, H.; Karimzadeh, F.

2016-05-01

The effects of cryorolling (rolling at liquid nitrogen temperature) and heat treatment on tensile and high-cycle fatigue properties and fatigue crack growth rate of Al6061 alloy have been investigated in the present work. First, the solid solution-treated bulk Al6061 alloy was subjected to cryorolling with 90% total thickness reduction and subsequent short annealing at 205°C for 5 min and peak aging at 148°C for 39 h to achieve grain refinement and simultaneous improvement of the strength and ductility. Then, hardness measurements, tensile tests, fatigue life, and fatigue crack growth rate tests including fractography analyses using scanning electron microscopy were performed on bulk Al6061 alloy, cryorolled (CR), and cryorolled material followed by peak aging (PA). The PA specimen showed improved yield strength by 24%, ultimate tensile strength by 20%, and ductility by 12% as compared with the bulk Al6061 alloy. It is shown that the fatigue strength of both CR and PA specimens under a high-cycle fatigue regime are larger than that of the bulk Al6061 alloy. Also, fatigue crack growth rates of the CR and PA specimens show significant enhancement in fatigue crack growth resistances as compared with the bulk Al6061 alloy, as a result of grain refinement.

Theoretical study of turbulent channel flow - Bulk properties, pressure fluctuations, and propagation of electromagnetic waves

NASA Technical Reports Server (NTRS)

Canuto, V. M.; Hartke, G. J.; Battaglia, A.; Chasnov, J.; Albrecht, G. F.

1990-01-01

In this paper, we apply two theoretical turbulence models, DIA and the recent GISS model, to study properties of a turbulent channel flow. Both models provide a turbulent kinetic energy spectral function E(k) as the solution of a non-linear equation; the two models employ the same source function but different closures. The source function is characterized by a rate n sub s (k) which is derived from the complex eigenvalues of the Orr-Sommerfeld (OS) equation in which the basic flow is taken to be of a Poiseuille type. The O-S equation is solved for a variety of Reynolds numbers corresponding to available experimental data. A physical argument is presented whereby the central line velocity characterizing the basic flow, U0 sup L, is not to be identified with the U0 appearing in the experimental Reynolds number. The theoretical results are compared with two types of experimental data: (1) turbulence bulk properties, and (2) properties that depend strongly on the structure of the turbulence spectrum at low wave numbers. The only existing analytical expression for Pi (k) cannot be used in the present case because it applies to the case of a flat plate, not a finite channel.

Adsorption of mixtures of poly(amidoamine) dendrimers and sodium dodecyl sulfate at the air-water interface.

PubMed

Arteta, Marianna Yanez; Campbell, Richard A; Nylander, Tommy

2014-05-27

We relate the adsorption from mixtures of well-defined poly(amidoamine) (PAMAM) dendrimers of generations 4 and 8 with sodium dodecyl sulfate (SDS) at the air-water interface to the bulk solution properties. The anionic surfactant shows strong attractive interactions with the cationic dendrimers at pH 7, and electrophoretic mobility measurements indicate that the association is primarily driven by electrostatic interactions. Optical density measurements highlight the lack of colloidal stability of the formed bulk aggregates at compositions close to charge neutrality, the time scale of which is dependent on the dendrimer generation. Adsorption at the air-water interface was followed from samples immediately after mixing using a combination of surface tension, neutron reflectometry, and ellipsometry measurements. In the phase separation region for dendrimers of generation 4, we observed high surface tension corresponding to a depleted surfactant solution but only when the aggregates carried an excess of surfactant. Interestingly, these depleted adsorption layers contained spontaneously adsorbed macroscopic aggregates, and these embedded particles do not rearrange to spread monomeric material at the interface. These findings are discussed in relation to the interfacial properties of mixtures involving dendrimers of generation 8 as well as polydisperse linear and hyperbranched polyelectrolytes where there is polyelectrolyte bound to a surfactant monolayer. The results presented here demonstrate the capability of dendrimers to sequester anionic surfactants in a controllable manner, with potential applications as demulsification and antifoaming agents.

Solvent Effects on the Photothermal Regeneration of CO 2 in Monoethanolamine Nanofluids

DOE PAGES

Nguyen, Du; Stolaroff, Joshuah; Esser-Kahn, Aaron

2015-11-02

We present that a potential approach to reduce energy costs associated with carbon capture is to use external and renewable energy sources. The photothermal release of CO 2 from monoethanolamine mediated by nanoparticles is a unique solution to this problem. When combined with light-absorbing nanoparticles, vapor bubbles form inside the capture solution and release the CO 2 without heating the bulk solvent. The mechanism by which CO 2 is released remained unclear, and understanding this process would improve the efficiency of photothermal CO 2 release. Here we report the use of different cosolvents to improve or reduce the photothermal regenerationmore » of CO 2 captured by monoethanolamine. We found that properties that reduce the residence time of the gas bubbles (viscosity, boiling point, and convection direction) can enhance the regeneration efficiencies. The reduction of bubble residence times minimizes the reabsorption of CO 2 back into the capture solvent where bulk temperatures remain lower than the localized area surrounding the nanoparticle. These properties shed light on the mechanism of release and indicated methods for improving the efficiency of the process. We used this knowledge to develop an improved photothermal CO 2 regeneration system in a continuously flowing setup. Finally, using techniques to reduce residence time in the continuously flowing setup, such as alternative cosolvents and smaller fluid volumes, resulted in regeneration efficiency enhancements of over 200%.« less

Solvent Effects on the Photothermal Regeneration of CO 2 in Monoethanolamine Nanofluids

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

Nguyen, Du; Stolaroff, Joshuah; Esser-Kahn, Aaron

We present that a potential approach to reduce energy costs associated with carbon capture is to use external and renewable energy sources. The photothermal release of CO 2 from monoethanolamine mediated by nanoparticles is a unique solution to this problem. When combined with light-absorbing nanoparticles, vapor bubbles form inside the capture solution and release the CO 2 without heating the bulk solvent. The mechanism by which CO 2 is released remained unclear, and understanding this process would improve the efficiency of photothermal CO 2 release. Here we report the use of different cosolvents to improve or reduce the photothermal regenerationmore » of CO 2 captured by monoethanolamine. We found that properties that reduce the residence time of the gas bubbles (viscosity, boiling point, and convection direction) can enhance the regeneration efficiencies. The reduction of bubble residence times minimizes the reabsorption of CO 2 back into the capture solvent where bulk temperatures remain lower than the localized area surrounding the nanoparticle. These properties shed light on the mechanism of release and indicated methods for improving the efficiency of the process. We used this knowledge to develop an improved photothermal CO 2 regeneration system in a continuously flowing setup. Finally, using techniques to reduce residence time in the continuously flowing setup, such as alternative cosolvents and smaller fluid volumes, resulted in regeneration efficiency enhancements of over 200%.« less

Tuning of the Morphology and Optoelectronic Properties of ZnO/P3HT/P3HT- b-PEO Hybrid Films via Spray Deposition Method.

PubMed

Wang, Kun; Bießmann, Lorenz; Schwartzkopf, Matthias; Roth, Stephan V; Müller-Buschbaum, Peter

2018-06-20

The self-assembly of amphiphilic diblock copolymers yields the possibility of using them as a template for tailoring the film morphologies of sol-gel chemistry-derived inorganic electron transport materials, such as mesoporous ZnO and TiO 2 . However, additional steps including etching and backfilling are required for the common bulk heterojunction fabrication process when using insulating diblock copolymers. Here, we use the conducting diblock copolymer poly(3-hexylthiophene)- block-poly(ethylene oxide) (P3HT- b-PEO) in which P3HT acts as charge carrier transport material and light absorber, whereas PEO serves as a template for ZnO synthesis. The initial solution is subsequently spray-coated to obtain the hybrid film. Scanning electron microscopy and grazing-incidence small-angle X-ray scattering measurements reveal a significant change in the morphology of the hybrid films during deposition. Optoelectronic properties illustrate the improved charge separation and charge transfer process. Both the amount of the diblock copolymer and the annealing temperature play an important role in tuning the morphology and the optoelectronic properties. Hybrid films being sprayed from a solution with the ratio of ω ZnO , ω P3HT , and ω P3HT- b-PEO of 2:1:1 and subsequent annealing at 80 °C show the most promising morphology combined with an optimal photoluminescence quenching. Thus, the presented simple, reagent- and energy-saving fabrication method provides a promising approach for a large-scale preparation of bulk heterojunction P3HT/ZnO films on flexible substrates.

Effect of surfactant on microstructure, surface hydrophilicity, mechanical and thermal properties of different multi-walled carbon nanotube/polystyrene composites

NASA Astrophysics Data System (ADS)

Li, Zhipeng; Zhang, Yanxia; Liang, Shaolei; Li, Guangfen

2018-05-01

We prepared nanocomposites of multi-walled carbon nanotube (MWCNT)/polystyrene via a solution casting method, where deionized water was used as coagulation bath. The influences of the type of MWCNTs and existence of surfactant on surface morphology, thermal properties and mechanical properties of MWCNT/polystyrene composites were extensively investigated. The pristine and two functionalized MWCNTs with the loading of 5 wt% were chosen for comparison. Both scanning electron microscopy and mercury intrusion porosimetry show that the composites without surfactant contain fewer pores and thus have higher bulk density, tensile strength, as well as low surface hydrophobicity. However, the porous structures within micro-range appear in all surfactant-treated composites, which decrease the bulk density and the tensile strength of their composites. This especially pronounced for the MWCNT-OH composite as the smallest pore size/highest porosity is found in the composites with loading of 5 wt% MWCNT-OH due to the higher content of hydroxyl groups. Despite the glass transition temperatures (Tg) of all the surfactant-treated composites lower compared with Tg for pure polystyrene, they increase for MWCNTs and MWCNT-OH composite without surfactant.

Highly Enhanced Thermoelectric Properties of Bi/Bi2S3 Nanocomposites.

PubMed

Ge, Zhen-Hua; Qin, Peng; He, DongSheng; Chong, Xiaoyu; Feng, Dan; Ji, Yi-Hong; Feng, Jing; He, Jiaqing

2017-02-08

Bismuth sulfide (Bi 2 S 3 ) has been of high interest for thermoelectric applications due to the high abundance of sulfur on Earth. However, the low electrical conductivity of pristine Bi 2 S 3 results in a low figure of merit (ZT). In this work, Bi 2 S 3 @Bi core-shell nanowires with different Bi shell thicknesses were prepared by a hydrothermal method. The core-shell nanowires were densified to Bi/Bi 2 S 3 nanocomposite by spark plasma sintering (SPS), and the structure of the nanowire was maintained as the nanocomposite due to rapid SPS processing and low sintering temperature. The thermoelectric properties of bulk samples were investigated. The electrical conductivity of a bulk sample after sintering at 673 K for 5 min using Bi 2 S 3 @Bi nanowire powders prepared by treating Bi 2 S 3 nanowires in a hydrazine solution for 3 h is 3 orders of magnitude greater than that of a pristine Bi 2 S 3 sample. The nanocomposite possessed the highest ZT value of 0.36 at 623 K. This represents a new strategy for densifying core-shell powders to enhance their thermoelectric properties.

Phonon scattering mechanisms dictating the thermal conductivity of lead zirconate titanate (PbZr 1- xTi xO 3) thin films across the compositional phase diagram

DOE PAGES

Foley, Brian M.; Paisley, Elizabeth A.; DiAntonio, Christopher; ...

2017-05-23

This paper represents a thorough investigation of the thermal conductivity (κ) in both thin film and bulk PbZr 1–xTi xO 3 (PZT) across the compositional phase diagram. Given the technological importance of PZT as a superb piezoelectric and ferroelectric material in devices and systems impacting a wide array of industries, this research serves to fill the gap in knowledge regarding the thermal properties. The thermal conductivities of both thin film and bulk PZT are found to vary by a considerable margin as a function of composition x. Additionally, we observe a discontinuity in κ in the vicinity of the morphotropicmore » phase boundary (MPB, x = 0.48) where there is a 20%–25% decrease in κ in our thin film data, similar to that found in literature data for bulk PZT. The comparison between bulk and thin film materials highlights the sensitivity of κ to size effects such as film thickness and grain size even in disordered alloy/solid-solution materials. A model for the thermal conductivity of PZT as a function of composition (κ(x)) is presented, which enables the application of the virtual crystal approximation for alloy-type material systems with very different crystals structures, resulting in differing temperature trends for κ. We show that in the case of crystalline solid-solutions where the thermal conductivity of one of the parent materials exhibits glass-like temperature trends the compositional dependence of thermal conductivity is relatively constant for most values of x. Finally, this is in stark contrast with the typical trends of thermal conductivity with x in alloys, where the thermal conductivity increases dramatically as the composition of the alloy or solid-solution approaches that of a pure parent materials (i.e., as x = 0 or 1).« less

Phonon scattering mechanisms dictating the thermal conductivity of lead zirconate titanate (PbZr 1- xTi xO 3) thin films across the compositional phase diagram

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

Foley, Brian M.; Paisley, Elizabeth A.; DiAntonio, Christopher

This paper represents a thorough investigation of the thermal conductivity (κ) in both thin film and bulk PbZr 1–xTi xO 3 (PZT) across the compositional phase diagram. Given the technological importance of PZT as a superb piezoelectric and ferroelectric material in devices and systems impacting a wide array of industries, this research serves to fill the gap in knowledge regarding the thermal properties. The thermal conductivities of both thin film and bulk PZT are found to vary by a considerable margin as a function of composition x. Additionally, we observe a discontinuity in κ in the vicinity of the morphotropicmore » phase boundary (MPB, x = 0.48) where there is a 20%–25% decrease in κ in our thin film data, similar to that found in literature data for bulk PZT. The comparison between bulk and thin film materials highlights the sensitivity of κ to size effects such as film thickness and grain size even in disordered alloy/solid-solution materials. A model for the thermal conductivity of PZT as a function of composition (κ(x)) is presented, which enables the application of the virtual crystal approximation for alloy-type material systems with very different crystals structures, resulting in differing temperature trends for κ. We show that in the case of crystalline solid-solutions where the thermal conductivity of one of the parent materials exhibits glass-like temperature trends the compositional dependence of thermal conductivity is relatively constant for most values of x. Finally, this is in stark contrast with the typical trends of thermal conductivity with x in alloys, where the thermal conductivity increases dramatically as the composition of the alloy or solid-solution approaches that of a pure parent materials (i.e., as x = 0 or 1).« less

Physicochemical Properties of Defatted Rambutan (Nephelium lappaceum) Seed Flour after Alkaline Treatment.

PubMed

Eiamwat, Jirawat; Wanlapa, Sorada; Kampruengdet, Sukit

2016-03-31

Rambutan seeds were subjected to SC-CO₂ extraction at 35 MPa, 45 °C to obtain defatted rambutan seed flour. Its physicochemical properties before and after treatment with alkali solution using 0.075 N NaOH were investigated. Alkali-treated flour had a significant increment in bulk density, swelling power, water adsorption capacity, emulsion capacity and stability but a reduction in turbidity, solubility and oil absorption capacity. Pasting measurements showed peak viscosity, breakdown, setback and final viscosity increased significantly for the alkali-treated flour, while pasting temperature decreased. The alkaline treatment decreased the least gelation concentration, but increased the apparent viscosity.

Quantum mechanical/molecular mechanical modeling finds Diels-Alder reactions are accelerated less on the surface of water than in water.

PubMed

Thomas, Laura L; Tirado-Rives, Julian; Jorgensen, William L

2010-03-10

Quantum and molecular mechanics calculations for the Diels-Alder reactions of cyclopentadiene with 1,4-naphthoquinone, methyl vinyl ketone, and acrylonitrile have been carried out at the vacuum-water interface and in the gas phase. In conjunction with previous studies of these cycloadditions in dilute solution, a more complete picture of aqueous environmental effects emerges with implications for the origin of observed rate accelerations using heterogeneous aqueous suspensions, "on water" conditions. The pure TIP4P water slab maintains the bulk density and hydrogen-bonding properties in central water layers. The bulk region merges to vacuum over a ca. 5 A band with progressive diminution of the density and hydrogen bonding. The relative free energies of activation and transition structures for the reactions at the interface are found to be intermediate between those calculated in the gas phase and in bulk water; i.e., for the reaction with 1,4-naphthoquinone, the DeltaDeltaG(++) values relative to the gas phase are -3.6 and -7.3 kcal/mol at the interface and in bulk water, respectively. Thus, the results do not support the notion that a water surface is more effective than bulk water for catalysis of such pericyclic reactions. The trend is in qualitative agreement with expectations based on density considerations and estimates of experimental rate constants for the gas phase, a heterogeneous aqueous suspension, and a dilute aqueous solution for the reaction of cyclopentadiene with methyl vinyl ketone. Computed energy pair distributions reveal a uniform loss of 0.5-1.0 hydrogen bond for the reactants and transition states in progressing from bulk water to the vacuum-water interface. Orientational effects are apparent at the surface; e.g., the carbonyl group in the methyl vinyl ketone transition structure is preferentially oriented into the surface. Also, the transition structure for the 1,4-naphthoquinone case is buried more in the surface, and the free energy of activation for this reaction is most similar to the result in bulk water.

Bulk Heterojunction Solar Cell with Nitrogen-Doped Carbon Nanotubes in the Active Layer: Effect of Nanocomposite Synthesis Technique on Photovoltaic Properties

PubMed Central

Keru, Godfrey; Ndungu, Patrick G.; Mola, Genene T.; Nyamori, Vincent O.

2015-01-01

Nanocomposites of poly(3-hexylthiophene) (P3HT) and nitrogen-doped carbon nanotubes (N-CNTs) have been synthesized by two methods; specifically, direct solution mixing and in situ polymerization. The nanocomposites were characterized by means of transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray dispersive spectroscopy, UV-Vis spectrophotometry, photoluminescence spectrophotometry (PL), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, thermogravimetric analysis, and dispersive surface energy analysis. The nanocomposites were used in the active layer of a bulk heterojunction organic solar cell with the composition ITO/PEDOT:PSS/P3HT:N-CNTS:PCBM/LiF/Al. TEM and SEM analysis showed that the polymer successfully wrapped the N-CNTs. FTIR results indicated good π-π interaction within the nanocomposite synthesized by in situ polymerization as opposed to samples made by direct solution mixing. Dispersive surface energies of the N-CNTs and nanocomposites supported the fact that polymer covered the N-CNTs well. J-V analysis show that good devices were formed from the two nanocomposites, however, the in situ polymerization nanocomposite showed better photovoltaic characteristics.

Unsteady Crystal Growth Due to Step-Bunch Cascading

NASA Technical Reports Server (NTRS)

Vekilov, Peter G.; Lin, Hong; Rosenberger, Franz

1997-01-01

Based on our experimental findings of growth rate fluctuations during the crystallization of the protein lysozym, we have developed a numerical model that combines diffusion in the bulk of a solution with diffusive transport to microscopic growth steps that propagate on a finite crystal facet. Nonlinearities in layer growth kinetics arising from step interaction by bulk and surface diffusion, and from step generation by surface nucleation, are taken into account. On evaluation of the model with properties characteristic for the solute transport, and the generation and propagation of steps in the lysozyme system, growth rate fluctuations of the same magnitude and characteristic time, as in the experiments, are obtained. The fluctuation time scale is large compared to that of step generation. Variations of the governing parameters of the model reveal that both the nonlinearity in step kinetics and mixed transport-kinetics control of the crystallization process are necessary conditions for the fluctuations. On a microscopic scale, the fluctuations are associated with a morphological instability of the vicinal face, in which a step bunch triggers a cascade of new step bunches through the microscopic interfacial supersaturation distribution.

Photodetachment and UV-Vis spectral properties of Cl2rad -·nHO clusters: Extrapolation to bulk

NASA Astrophysics Data System (ADS)

Pathak, A. K.; Mukherjee, T.; Maity, D. K.

2008-03-01

Vertical detachment energy (VDE) and UV-Vis spectra of Cl2rad -·nHO clusters ( n = 1-11) are reported based on first principle electronic structure calculations. VDE of the hydrated clusters are calculated following second order Moller-Plesset perturbation (MP2) as well as coupled cluster theory with 6-311++G(d,p) set of basis function. The excess electron in these hydrated clusters is mainly localized over the solute Cl atoms. A linear relationship is obtained for VDE vs. ( n + 2.6) -1/3 and bulk VDE of Cl2rad - aqueous solution is calculated as 10.61 eV at CCSD(T) level of theory. UV-Vis spectra of these hydrated clusters are calculated applying CI with single electron (CIS) excitation procedure. Simulated UV-Vis spectra of Cl2rad -·10HO cluster is noted to be in excellent agreement with the reported spectra of Cl2rad - (aq) system, λmax for Cl2rad -·11HO system is calculated to be red shifted though.

The applications of small-angle X-ray scattering in studying nano-scaled polyoxometalate clusters in solutions

NASA Astrophysics Data System (ADS)

Li, Mu; Zhang, Mingxin; Wang, Weiyu; Cheng, Stephen Z. D.; Yin, Panchao

2018-05-01

Nano-scaled polyoxometalates (POMs) clusters with sizes ranging from 1 to 10 nm attract tremendous attention and have been extensively studied due to POMs' fascinating structural characteristics and prospects for wide-ranging applications. As a unique class of nanoparticles with well-defined structural topologies and monodispersed masses, the structures and properties of POMs in both bulk state and solutions have been explored with several well-developed protocols. Small-angle X-ray scattering (SAXS) technique, as a powerful tool for studying polymers and nanoparticles, has been recently extended to the investigating of solution behaviors of POMs. In this mini-review, the general principle and typical experimental procedures of SAXS are illustrated first. The applications of SAXS in characterizing POMs' morphology, counterion distribution around POMs, and short-range interactions among POMs in solutions are highlighted. [Figure not available: see fulltext.

Hyperbranched exopolysaccharide-enhanced foam properties of sodium fatty alcohol polyoxyethylene ether sulfate.

PubMed

Deng, Quanhua; Li, Haiping; Sun, Haoyang; Sun, Yange; Li, Ying

2016-05-01

The foam properties, such as the foamability, foam stability, drainage, coalescence and bulk rheology, of aqueous solutions containing an eco-friendly exopolysaccharide (EPS) secreted by a deep-sea mesophilic bacterium, Wangia profunda SM-A87, and an anionic surfactant, sodium fatty alcohol polyoxyethylene ether sulfate (AES), were studied. Both the foamability and foam stability of the EPS/AES solutions are considerably higher than those of single AES solutions, even at very low AES concentrations, although pure EPS solutions cannot foam. The improved foamability and foam stability arise from the formation of the EPS/AES complex via hydrogen bonds at the interfaces. The synergism between the EPS and AES decreases the surface tension, increases the interfacial elasticity and water-carrying capacity, and suppresses the coalescence and collapse of the foams. The EPS/AES foams are more salt-resistant than the AES foams. This work provides not only a new eco-friendly foam with great potential for use in enhanced oil recovery and health-care products but also useful guidance for designing other environmentally friendly foam systems that exhibit high performance. Copyright © 2016 Elsevier B.V. All rights reserved.

46 CFR 153.1065 - Sodium chlorate solutions.

Code of Federal Regulations, 2013 CFR

2013-10-01

... 46 Shipping 5 2013-10-01 2013-10-01 false Sodium chlorate solutions. 153.1065 Section 153.1065 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES SHIPS CARRYING BULK LIQUID, LIQUEFIED GAS, OR COMPRESSED GAS HAZARDOUS MATERIALS Operations Special Cargo...

46 CFR 153.1065 - Sodium chlorate solutions.

Code of Federal Regulations, 2014 CFR

2014-10-01

... 46 Shipping 5 2014-10-01 2014-10-01 false Sodium chlorate solutions. 153.1065 Section 153.1065 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES SHIPS CARRYING BULK LIQUID, LIQUEFIED GAS, OR COMPRESSED GAS HAZARDOUS MATERIALS Operations Special Cargo...

Growth And Characterization Of LPE CdHgTe/CdZnTe/CdZnTe Structure

NASA Astrophysics Data System (ADS)

Pelliciari, B.; Chamonal, J. P.; Destefanis, G. L.; Dicioccio, L.

1988-05-01

The liquid phase epitaxial technique is used to grow Hgl_x Cdx Te (x = .23) from a Te - rich solution onto a Cdl_y ZnyTe (y = .04) buffer layer grown from a Te-rich solution onto a Cdi_yZnyTe bulk substrate in an open tube multibin horizontal slider apparatus.Growth conditions and physical characterizations of both the buffer layer and the CdHgTe layer are given ; electrical properties of the CdHgTe layer are also presen-ted. PV detectors were successfully obtained on such a structure using an ion-implanted technology and their characteristics at 77 K for a 10.1 ,um cut-off wavelength are given.

Effect of confinement in nano-porous materials on the solubility of a supercritical gas

NASA Astrophysics Data System (ADS)

Hu, Yaofeng; Huang, Liangliang; Zhao, Shuangliang; Liu, Honglai; Gubbins, Keith E.

2016-11-01

By combining Gibbs Ensemble Monte Carlo simulations and density functional theory, we investigate the influence of confinement in a slit-shaped carbon pore on the solubility of a supercritical solute gas in a liquid solvent. In the cases studied here, competing adsorption of the solvent and solute determines whether the solubility is enhanced or suppressed for larger pores. We find that the solubility in the confined system is strongly dependent on pore width, and that molecular packing effects are important for small pore widths. In addition, the solubility decreases on increase in the temperature, as for the bulk mixture, but the rate of decrease is greater in the pore due to a decrease in the partial molar enthalpy of the solute in the pore; this effect becomes greater as pore width is decreased. The solubility is increased on increasing the bulk pressure of the gas in equilibrium with the pore, and obeys Henry's law at lower pressures. However, the Henry constant differs significantly from that for the bulk mixture, and the range of pressure over which Henry's law applies is reduced relative to that for the bulk mixture. The latter observation indicates that solute-solute interactions become more important in the pore than for the bulk at a given bulk pressure. Finally, we note that different authors use different definitions of the solubility in pores, leading to some confusion over the reported phenomenon of 'oversolubility'. We recommend that solubility be defined as the overall mole fraction of solute in the pores, since it takes into account the increase in density of the solvent in the pores, and avoids ambiguity in the definition of the pore volume.

A survey of biofilms on wastewater aeration diffusers suggests bacterial community composition and function vary by substrate type and time.

PubMed

Noble, Peter A; Park, Hee-Deung; Olson, Betty H; Asvapathanagul, Pitiporn; Hunter, M Colby; Garrido-Baserba, Manel; Lee, Sang-Hoon; Rosso, Diego

2016-07-01

Aeration diffusers in wastewater treatment plants generate air bubbles that promote mixing, distribution of dissolved oxygen, and microbial processing of dissolved and suspended matter in bulk solution. Biofouling of diffusers represents a significant problem to wastewater treatment plants because biofilms decrease oxygen transfer efficiency and increase backpressure on the blower. To better understand biofouling, we conducted a pilot study to survey the bacterial community composition and function of biofilms on different diffuser substrates and compare them to those in the bulk solution. DNA was extracted from the surface of ethylene-propylene-diene monomer (EPDM), polyurethane, and silicone diffusers operated for 15 months in a municipal treatment plant and sampled at 3 and 9 months. The bacterial community composition and function of the biofilms and bulk solution were determined by amplifying the 16S rRNA genes and pyrosequencing the amplicons and raw metagenomic DNA. The ordination plots and dendrograms of the 16S rRNA and functional genes showed that while the bacterial community composition and function of the bulk solution was independent of sampling time, the composition and function of the biofilms differed by diffuser type and testing time. For the EPDM and silicone diffusers, the biofilm communities were more similar in composition to the bulk solution at 3 months than 9 months. In contrast, the bacteria on the polyurethane diffusers were more dissimilar to the bulk solution at 3 months than 9 months. Taken together, the survey showed that the community composition and function of bacterial biofilms depend on the diffuser substrate and testing time, which warrants further elucidation.

Characterization of the Properties of Photopatterned Hydrogels for Use in Regenerative Medicine

NASA Astrophysics Data System (ADS)

Fiedler, Callie Irene

The goal of this thesis was to locally photopattern cytocompatible hydrogels to exhibit a wide range of mechanical properties and to probe the fundamental parameters governing these materials printed via stereolithography (SLA). Fabricating cell-laden structures with locally defined mechanical properties is non-trivial because the use of multiple precursor materials is wasteful, slow, and can lead to cell-death. To investigate the range of mechanical properties a single precursor solution can produce, I initially formed a single-network hydrogel and cyclically in- swelled fresh precursor solution followed by photo-exposure of the swollen gel ("swelling + exposure" or SE cycle). Because transport (i.e., diffusion and swelling) can occur on the same time scale as photopolymerization reaction kinetics, I first characterized the variable modulus hydrogels in bulk to isolate the reaction kinetics. In these experiments, I demonstrated the ability modify the mechanical and chemical (i.e., compressive modulus, toughness, crosslink density, swelling ratio) properties by up to 10-fold using only 2-4 SE cycles. I then used the understanding gained via these bulk experiments to locally photopattern the elastic modulus of a cytocompatible hydrogel with pixel-limited resolution (˜10s mum) employing a custom SLA system. Here I demonstrated the ability to fabricate hydrogels with a 500% elastic moduli increase with respect to the unpatterned hydrogel using atomic force microscopy. I monitored monomer attachment to the existing matrix as a function of SE cycle using confocal fluorescence microscopy to characterize the shape and size of printed features. I validated that the dependence of these features on material and processing conditions could be explained by a first-order reaction/diffusion model. With this understanding, I fabricated SLA 3D printed, soft, cytocompatible hydrogels (˜10s kPa) with ˜250 mum channels in addition to fabricating 3D printed stiff, cytocompatible hydrogels (39 MPa) both with ˜10 mum resolution.

A new approximate sum rule for bulk alloy properties

NASA Technical Reports Server (NTRS)

Bozzolo, Guillermo; Ferrante, John

1991-01-01

A new, approximate sum rule is introduced for determining bulk properties of multicomponent systems, in terms of the pure components properties. This expression is applied for the study of lattice parameters, cohesive energies, and bulk moduli of binary alloys. The correct experimental trends (i.e., departure from average values) are predicted in all cases.

Pierre Turq, an inspirational scientist in charge and at interfaces

NASA Astrophysics Data System (ADS)

Ancian, Bernard; Bernard, Olivier; Chevalet, Jean; Dahirel, Vincent; Devilliers, Didier; Dubois, Emmanuelle; Dufrêche, Jean-François; Durand-Vidal, Serge; Groult, Henri; Jardat, Marie; Lantelme, Frédéric; Malikova, Natalie; Marry, Virginie; Mériguet, Guillaume; Perzynski, Régine; Rollet, Anne-Laure; Rotenberg, Benjamin; Salanne, Mathieu; Simon, Christian

2014-05-01

Pierre Turq has made decisive contributions to the theory and to the multiscale simulation of charged systems, such as molten salts, electrolyte solutions and colloidal suspensions, in the bulk, at interfaces and under confinement. His research line focussed on dynamical properties and was characterised by constant efforts to connect his theoretical work to both experiments and practical applications. In this article, his colleagues and former students pay a tribute to his past and current research interests by illustrating some recent developments accomplished in his laboratory.

Reverse-Selective Diffusion in Nanocomposite Membranes

NASA Astrophysics Data System (ADS)

Hill, Reghan J.

2006-06-01

The permeability of certain polymer membranes with impenetrable nanoinclusions increases with the particle volume fraction [T. C. Merkel , Science 296, 519 (2002)SCIEAS0036-807510.1126/science.1069580]. The discovery contradicts qualitative expectations based on Maxwell’s classical theory of conduction or diffusion in composites with homogeneous phases. This Letter presents a theory based on an hypothesis that polymer chains are repelled from the inclusions during membrane casting. The accompanying increase in free volume, and hence solute diffusivity, yields bulk transport properties that are in good agreement with experiments.

Technical issues of a high-Tc superconducting bulk magnet

NASA Astrophysics Data System (ADS)

Fujimoto, Hiroyuki

2000-06-01

Superconducting magnets made of high-Tc superconductors are promising for industrial applications. It is well known that REBa2Cu3O7-x superconductors prepared by melt processes have a high critical current density, Jc, at 77 K and high magnetic fields. The materials are very promising for high magnetic field applications as a superconducting permanent/bulk magnet with liquid-nitrogen refrigeration. Light rare-earth (LRE) BaCuO bulks, compared with REBaCuO bulks, exhibit a larger Jc in high magnetic fields and a much improved irreversibility field, Hirr, at 77 K. In this study, we discuss technical issues of a high-Tc superconducting bulk magnet, namely the aspects of the melt processing for bulk superconductors, their characteristic superconducting properties and mechanical properties, and trapped field properties of a superconducting bulk magnet. One of the possible applications is a superconducting bulk magnet for the magnetically levitated (Maglev) train in the future.

In-line bulk supersaturation measurement by electrical conductometry in KDP crystal growth from aqueous solution

NASA Astrophysics Data System (ADS)

Bordui, P. F.; Loiacono, G. M.

1984-07-01

A method is presented for in-line bulk supersaturation measurement in crystal growth from aqueous solution. The method is based on a computer-controlled concentration measurement exploiting an experimentally predetermined cross-correlation between the concentration, electrical conductivity, and temperature of the growth solution. The method was applied to Holden crystallization of potassium dihydrogen phosphate (KDP). An extensive conductivity-temperature-concentration data base was generated for this system over a temperature range of 31 to 41°C. The method yielded continous, automated bulk supersaturation output accurate to within ±0.05 g KDP100 g water (±0.15% relative supersaturation).

Bulk microstructure and local elastic properties of carbon nanocomposites studied by impulse acoustic microscopy technique

NASA Astrophysics Data System (ADS)

Levin, V.; Petronyuk, Yu.; Morokov, E.; Chernozatonskii, L.; Kuzhir, P.; Fierro, V.; Celzard, A.; Bellucci, S.; Bistarelli, S.; Mastrucci, M.; Tabacchioni, I.

2016-05-01

Bulk microstructure and elastic properties of epoxy-nanocarbon nanocomposites for diverse types and different content of carbon nanofiller has been studied by using impulse acoustic microscopy technique. It has been shown occurrence of various types of mesoscopic structure formed by nanoparticles inside the bulk of nanocomposite materials, including nanoparticle conglomerates and nanoparticle aerogel systems. In spite of the bulk microstructure, nanocarbon composites demonstrate elastic uniformity and negligible influence of nanofiller on elastic properties of carbon nanocomposite materials.

Characterization of a backbone cleavage product of BMS-196854 (Oncostatin M), a recombinant anti-inflammatory cytokine.

PubMed

Zhao, F; Stein, D J; Paborji, M; Cash, P W; Root, B J; Wei, Z; Knupp, C J

2001-01-01

BMS-196843 (Oncostatin M) is a therapeutic recombinant protein in development. Scale-up process changes led to unexpected instability of the bulk drug substance solution during storage. A product with an apparent higher MW than the parent protein was observed by the size-exclusion chromatography (SEC). This study was aimed to fully characterize the product and to identify a solution to stabilize the protein. SEC, SDS-PAGE, tryptic mapping, and N-terminal sequencing were performed to characterize the unknown product. The effect of pH, temperature, bulk concentration, and immobilized trypsin inhibitor on the degradation rate was studied to elucidate the mechanism and to identify stabilization strategies. Despite the apparent high MW indicated initially by SEC, the unknown was characterized to be a degradation product resulted from a backbone cleavage between residues Arg145-Gly146. The resulting fragments from the backbone cleavage were, however, still linked through an intramolecular disulfide bond. Thus, the final product had a more open structure with an increased hydrodynamic radius compared to the parent protein, which explains the initial SEC results. The site-specific backbone cleavage was suspected to be catalyzed by trypsin-like protease impurities in the bulk solution. The bulk drug substance solution was subsequently treated with immobilized soybean trypsin inhibitor, and the degradation rate was significantly reduced. Furthermore, increasing the solution pH from 5 to 8 led to an increase in the degradation rate, which was consistent with the expected pH dependency of trypsin activity. In addition, the effect of bulk concentration also supported the involvement of protease impurities rather than a spontaneous peptide bond hydrolysis reaction. Trace trypsin-like protease impurities led to an unusual site-specific backbone cleavage of BMS-196854. The proteolytic degradation can be minimized by treating the bulk solution with immobilized soybean trypsin inhibitor and/or controlling the solution pH and storage temperature.

Intrinsic properties and strengthening mechanism of monocrystalline Ni-containing ternary concentrated solid solutions

DOE PAGES

Jin, K.; Gao, Y. F.; Bei, H.

2017-04-07

Ternary single-phase concentrated solid solution alloys (SP-CSAs), so-called "medium entropy alloys", not only possess notable mechanical and physical properties but also form a model system linking the relatively simple binary alloys to the complex high entropy alloys. Our knowledge of their intrinsic properties is vital to understand the material behavior and to prompt future applications. To this end, three model alloys NiCoFe, NiCoCr, and NiFe-20Cr have been selected and grown as single crystals. We measured their elastic constants using an ultrasonic method, and several key materials properties, such as shear modulus, bulk modulus, elastic anisotropy, and Debye temperatures have beenmore » derived. Furthermore, nanoindentation tests have been performed on these three alloys together with Ni, NiCo and NiFe on their (100) surface, to investigate the strengthening mechanisms. NiCoCr has the highest hardness, NiFe, NiCoFe and NiFe-20Cr share a similar hardness that is apparently lower than NiCoCr; NiCo has the lowest hardness in the alloys, which is similar to elemental Ni. The Labusch-type solid solution model has been applied to interpret the nanoindentation data, with two approaches used to calculate the lattice mismatch. Finally, by adopting an interatomic spacing matrix method, the Labusch model can reasonably predict the hardening effects for the whole set of materials.« less

Comparison of vapor formation of water at the solid/water interface to colloidal solutions using optically excited gold nanostructures.

PubMed

Baral, Susil; Green, Andrew J; Livshits, Maksim Y; Govorov, Alexander O; Richardson, Hugh H

2014-02-25

The phase transformation properties of liquid water to vapor is characterized by optical excitation of the lithographically fabricated single gold nanowrenches and contrasted to the phase transformation properties of gold nanoparticles located and optically excited in a bulk solution system [two and three dimensions]. The 532 nm continuous wave excitation of a single gold nanowrench results in superheating of the water to the spinodal decomposition temperature of 580 ± 20 K with bubble formation below the spinodal decomposition temperature being a rare event. Between the spinodal decomposition temperature and the boiling point liquid water is trapped into a metastable state because a barrier to vapor nucleation exists that must be overcome before the thermodynamically stable state is realized. The phase transformation for an optically heated single gold nanowrench is different from the phase transformation of optically excited colloidal gold nanoparticles solution where collective heating effects dominates and leads to the boiling of the solution exactly at the boiling point. In the solution case, the optically excited ensemble of nanoparticles collectively raises the ambient temperature of water to the boiling point where liquid is converted into vapor. The striking difference in the boiling properties of the single gold nanowrench and the nanoparticle solution system can be explained in terms of the vapor-nucleation mechanism, the volume of the overheated liquid, and the collective heating effect. The interpretation of the observed regimes of heating and vaporization is consistent with our theoretical modeling. In particular, we explain with our theory why the boiling with the collective heating in a solution requires 3 orders of magnitude less intensity compared to the case of optically driven single nanowrench.

Polynuclear Speciation of Trivalent Cations near the Surface of an Electrolyte Solution

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

Bera, Mrinal K.; Antonio, Mark R.

Despite long-standing efforts, there is no agreed upon structural model for electrolyte solutions at air-liquid interfaces. We report the simultaneous detection of the near-surface and bulk coordination environments of a trivalent metal cation (europium) in an aqueous solution by use of X-ray absorption spectroscopy. Within the first few nanometers of the liquid surface, the cations exhibit oxygen coordination typical of inner-sphere hydration of an aquated Eu3+ cation. Beyond that, outer-sphere ion-ion correlations are observed that are otherwise not present in the bulk electrolyte. The combination of near-surface and bulk sensitivities to probe metal ion speciation in electrolyte solutions is achievedmore » by detecting electron-yield and X-ray fluorescence signals from an inverted pendant drop. The results provide new knowledge about the near-surface chemistry of aqueous solutions of relevance to aerosols and ion transport processes in chemical separations and biological systems.« less

Controlling mechanisms of metals release form cement-based waste form in acetic acid solution

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

Cheng, Kuang Ye.

1991-01-01

The purpose of this dissertation is to identify the individual leaching mechanisms of metals by knowing the pH profile within the leached specimen and the physical and chemical properties of the leached material. Leaching of cement-based waste form in acetic acid solutions with different acidic strengths has been investigated in this work. The pH profile along the acid penetration route in the cement-based waste form was identified by various pH color indicators. The pH in the surface altered layer varies from 5.0 to 6.0, which is very close to the pH in the bulk leachate. A reacting zone, where themore » pH abruptly changes from 6 to 12, sharply divides the altered surface layer from the remaining unleached waste form or kernel. Leaching of metals is controlled by the acidity available in the leachant. Dissolution of alkaline materials leaves a silica-rich layer on the surface of the cement-based waste form. This surface layer exhibits different properties than those of the unleached material. The surface layer has a higher water content, is lighter weight, and is soft and friable. Furthermore, the abundant silicate content on the solid surface detains portion of the leached metals, while they are moving through the leached layer into bulk solution. The leaching of metals is a consequence of acid penetration. The distance from the solid/solution interface to the front of the leaching boundary can be regarded as the depth of leaching zone, where the metals dissolve and diffuse out of the waste form. The metal ions diffuse through the leached layer may be retarded on the solid surface by the pH-dependent adsorption reactions. It is found that the leaching process through the leached layer is diffusion-controlled for calcium and cadmium, whereas diffusion and adsorption occur simultaneously in the leached layer for lead and arsenic.« less

Influence of indian mustard (Brassica juncea) on rhizosphere soil solution chemistry in long-term contaminated soils: a rhizobox study.

PubMed

Kim, Kwon-Rae; Owens, Gary; Kwon, Soon-lk

2010-01-01

This study investigated the influence of Indian mustard (Brassica juncea) root exudation on soil solution properties (pH, dissolved organic carbon (DOC), metal solubility) in the rhizosphere using a rhizobox. Measurement was conducted following the cultivation of Indian mustard in the rhizobox filled four different types of heavy metal contaminated soils (two alkaline soils and two acidic soils). The growth of Indian mustard resulted in a significant increase (by 0.6 pH units) in rhizosphere soil solution pH of acidic soils and only a slight increase (< 0.1 pH units) in alkaline soils. Furthermore, the DOC concentration increased by 17-156 mg/L in the rhizosphere regardless of soil type and the extent of contamination, demonstrating the exudation of DOC from root. Ion chromatographic determination showed a marked increase in the total dissolved organic acids (OAs) in rhizosphere. While root exudates were observed in all soils, the amount of DOC and OAs in soil solution varied considerably amongst different soils, resulting in significant changes to soil solution metals in the rhizosphere. For example, the soil solution Cd, Cu, Pb, and Zn concentrations increased in the rhizosphere of alkaline soils compared to bulk soil following plant cultivation. In contrast, the soluble concentrations of Cd, Pb, and Zn in acidic soils decreased in rhizosphere soil when compared to bulk soils. Besides the influence of pH and DOC on metal solubility, the increase of heavy metal concentration having high stability constant such as Cu and Pb resulted in a release of Cd and Zn from solid phase to liquid phase.

The radiation shielding potential of CI and CM chondrites

NASA Astrophysics Data System (ADS)

Pohl, Leos; Britt, Daniel T.

2017-03-01

Galactic Cosmic Rays (GCRs) and Solar Energetic Particles (SEPs) pose a serious limit on the duration of deep space human missions. A shield composed of a bulk mass of material in which the incident particles deposit their energy is the simplest way to attenuate the radiation. The cost of bringing the sufficient mass from the Earth's surface is prohibitive. The shielding properties of asteroidal material, which is readily available in space, are investigated. Solution of Bethe's equation is implemented for incident protons and the application in composite materials and the significance of various correction terms are discussed; the density correction is implemented. The solution is benchmarked and shows good agreement with the results in literature which implement more correction terms within the energy ranges considered. The shielding properties of CI and CM asteroidal taxonomy groups and major asteroidal minerals are presented in terms of stopping force. The results show that CI and CM chondrites have better stopping properties than Aluminium. Beneficiation is discussed and is shown to have a significant effect on the stopping power.

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.

Mechanical characterization of injection-molded macro porous bioceramic bone scaffolds.

PubMed

Vivanco, Juan; Aiyangar, Ameet; Araneda, Aldo; Ploeg, Heidi-Lynn

2012-05-01

Bioactive ceramic materials like tricalcium phosphate (TCP) have been emerging as viable material alternatives to the current therapies of bone scaffolding to target fracture healing and osteoporosis. Both material and architectural characteristics play a critical role in the osteoconductive capacity and strength of bone scaffolds. Thus, the objective of this research was to investigate the sintering temperature effect of a cost-effective manufacturing process on the architecture and mechanical properties of a controlled macro porous bioceramic bone scaffold. In this study the physical and mechanical properties of β-TCP bioceramic scaffolds were investigated as a function of the sintering temperature in the range of 950-1150 °C. Physical properties investigated included bulk dimensions, pore size, and strut thickness; and, compressive mechanical properties were evaluated in air at room temperature and in saline solution at body temperature. Statistically significant increases in apparent elastic modulus were measured for scaffolds sintered at higher temperatures. Structural stiffness for all the specimens was significantly reduced when tested at body temperature in saline solution. These findings support the development of clinically successful bioceramic scaffolds that may stimulate bone regeneration and scaffold integration while providing structural integrity. Copyright © 2012 Elsevier Ltd. All rights reserved.

Predicting the pKa and stability of organic acids and bases at an oil-water interface.

PubMed

Andersson, M P; Olsson, M H M; Stipp, S L S

2014-06-10

We have used density functional theory and the implicit solvent model, COSMO-RS, to investigate how the acidity constant, pKa, of organic acids and bases adsorbed at the organic compound-aqueous solution interface changes, compared to its value in the aqueous phase. The pKa determine the surface charge density of the molecules that accumulate at the fluid-fluid interface. We have estimated the pKa by comparing the stability of the protonated and unprotonated forms of a series of molecules in the bulk aqueous solution and at an interface where parts of each molecule reside in the hydrophobic phase and the rest remains in the hydrophilic phase. We found that the pKa for acids is shifted by ∼1 pH unit to higher values compared to the bulk water pKa, whereas they are shifted to lower values by a similar amount for bases. Because this pKa shift is similar in magnitude for each of the molecules studied, we propose that the pKa for molecules at a water-organic compound interface can easily be predicted by adding a small shift to the aqueous pKa. This shift is general and correlates with the functional group. We also found that the relative composition of molecules at the fluid-fluid interface is not the same as in the bulk. For example, species such as carboxylic acids are enriched at the interface, where they can dominate surface properties, even when they are a modest component in the bulk fluid. For high surface concentrations of carboxylic acid groups at an interface, such as a self-assembled monolayer, we have demonstrated that the pKa depends on the degree of deprotonation through direct hydrogen bonding between protonated and deprotonated acidic headgroups.

Perspective: Aerosol microphysics: From molecules to the chemical physics of aerosols

NASA Astrophysics Data System (ADS)

Bzdek, Bryan R.; Reid, Jonathan P.

2017-12-01

Aerosols are found in a wide diversity of contexts and applications, including the atmosphere, pharmaceutics, and industry. Aerosols are dispersions of particles in a gas, and the coupling of the two phases results in highly dynamic systems where chemical and physical properties like size, composition, phase, and refractive index change rapidly in response to environmental perturbations. Aerosol particles span a wide range of sizes from 1 nm to tens of micrometres or from small molecular clusters that may more closely resemble gas phase molecules to large particles that can have similar qualities to bulk materials. However, even large particles with finite volumes exhibit distinct properties from the bulk condensed phase, due in part to their higher surface-to-volume ratio and their ability to easily access supersaturated solute states inaccessible in the bulk. Aerosols represent a major challenge for study because of the facile coupling between the particle and gas, the small amounts of sample available for analysis, and the sheer breadth of operative processes. Time scales of aerosol processes can be as short as nanoseconds or as long as years. Despite their very different impacts and applications, fundamental chemical physics processes serve as a common theme that underpins our understanding of aerosols. This perspective article discusses challenges in the study of aerosols and highlights recent chemical physics advancements that have enabled improved understanding of these complex systems.

On the kinetics of acid sodium caseinate gelation using particle tracking to probe the microrheology.

PubMed

Moschakis, Thomas; Murray, Brent S; Dickinson, Eric

2010-05-15

The sol-gel transition of a model dairy system (sodium caseinate solution) which undergoes gelation by acidification has been studied by conventional bulk rheology and particle tracking microrheology, via confocal microscopy. The Brownian diffusion of fluorescent microspheres (0.21, 0.32, 0.5, and 0.89 μm in diameter) with different surface coatings (polyethylene glycol, carboxylate groups and polystyrene) was used to probe spatial mechanical properties of the gels at the scale of microns. The microrheological results are compared with the macroscopic viscoelastic properties (storage and loss shear modulus) measured in a concentric cylinder rheometer (double gap, at shear strain of 0.005 and frequency of 1 Hz). At pH values close to pI of the caseins, where formation of a protein network, i.e., gelation, became obvious from the confocal microscopy and bulk rheological measurements, all the particles had a tendency to adhere to the network. In spite of this, the microrheological values of the moduli were only slightly lower than the macroscopically determined values and the gel points calculated via both techniques tended to be in good agreement. However, the particle tracking method has higher sensitivity and can detect changes in the structuring of the system before these are registered by the bulk rheological measurement. Copyright © 2010 Elsevier Inc. All rights reserved.

Large dimensions and small curvatures from supersymmetric brane back-reaction

NASA Astrophysics Data System (ADS)

Burgess, C. P.; van Nierop, L.

2011-04-01

We compute the back-reaction of pairs of codimension-two branes within an explicit flux-stabilized compactification, to trace how its properties depend on the parameters that define the brane-bulk couplings. Both brane tension and magnetic couplings to the stabilizing flux play an important role in the resulting dynamics, with the magnetic coupling allowing some of the flux to be localized on the branes (thus changing the flux-quantization conditions). We find that back-reaction lifts the classical flat directions of the bulk supergravity, and we calculate both the scalar potential and changes to the extra-dimensional and on-brane geometries that result, as functions of the assumed brane couplings. When linearized about simple rugby-ball geometries the resulting solutions allow a systematic exploration of the system's response. Several of the systems we explore have remarkable properties. Among these are a propensity for the extra dimensions to stabilize at exponentially large sizes, providing a mechanism for generating extremely large volumes. In some circumstances the brane-dilaton coupling allows the bulk dilaton to adjust to suppress the on-brane curvature parametrically below the change in brane tension, potentially providing a mechanism for reducing the vacuum energy. We explore the stability of this suppression to quantum effects in the case where their strength is controlled by the value of the field along the classical flat direction, and find it can (but need not) be stable.

Solutions on a brane in a bulk spacetime with Kalb–Ramond field

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

Chakraborty, Sumanta, E-mail: sumanta@iucaa.in; SenGupta, Soumitra, E-mail: tpssg@iacs.res.in

Effective gravitational field equations on a brane have been derived, when the bulk spacetime is endowed with the second rank antisymmetric Kalb–Ramond field. Since both the graviton and the Kalb–Ramond field are closed string excitations, they can propagate in the bulk. After deriving the effective gravitational field equations on the brane, we solve them for a static spherically symmetric solution. It turns out that the solution so obtained represents a black hole or naked singularity depending on the parameter space of the model. The stability of this model is also discussed. Cosmological solutions to the gravitational field equations have beenmore » obtained, where the Kalb–Ramond field is found to behave as normal pressure free matter. For certain specific choices of the parameters in the cosmological solution, the solution exhibits a transition in the behaviour of the scale factor and hence a transition in the expansion history of the universe. The possibility of accelerated expansion of the universe in this scenario is also discussed.« less

Water at surfaces with tunable surface chemistries

NASA Astrophysics Data System (ADS)

Sanders, Stephanie E.; Vanselous, Heather; Petersen, Poul B.

2018-03-01

Aqueous interfaces are ubiquitous in natural environments, spanning atmospheric, geological, oceanographic, and biological systems, as well as in technical applications, such as fuel cells and membrane filtration. Where liquid water terminates at a surface, an interfacial region is formed, which exhibits distinct properties from the bulk aqueous phase. The unique properties of water are governed by the hydrogen-bonded network. The chemical and physical properties of the surface dictate the boundary conditions of the bulk hydrogen-bonded network and thus the interfacial properties of the water and any molecules in that region. Understanding the properties of interfacial water requires systematically characterizing the structure and dynamics of interfacial water as a function of the surface chemistry. In this review, we focus on the use of experimental surface-specific spectroscopic methods to understand the properties of interfacial water as a function of surface chemistry. Investigations of the air-water interface, as well as efforts in tuning the properties of the air-water interface by adding solutes or surfactants, are briefly discussed. Buried aqueous interfaces can be accessed with careful selection of spectroscopic technique and sample configuration, further expanding the range of chemical environments that can be probed, including solid inorganic materials, polymers, and water immiscible liquids. Solid substrates can be finely tuned by functionalization with self-assembled monolayers, polymers, or biomolecules. These variables provide a platform for systematically tuning the chemical nature of the interface and examining the resulting water structure. Finally, time-resolved methods to probe the dynamics of interfacial water are briefly summarized before discussing the current status and future directions in studying the structure and dynamics of interfacial water.

Light transmittance and micro-mechanical properties of bulk fill vs. conventional resin based composites.

PubMed

Bucuta, Stefan; Ilie, Nicoleta

2014-11-01

The aim of this study was to quantify the blue light that passes through different incremental thicknesses of bulk fill in comparison to conventional resin-based composites (RBCs) and to relate it to the induced mechanical properties. Seven bulk fill, five nanohybrid and two flowable RBCs were analysed. Specimens (n = 5) of three incremental thicknesses (2, 4 and 6 mm) were cured from the top for 20 s, while at the bottom, a spectrometer monitored in real time the transmitted irradiance. Micro-mechanical properties (Vickers hardness, HV, and indentation modulus, E) were measured at the top and bottom after 24 h of storage in distilled water at 37 °C. Electron microscope images were taken for assessing the filler distribution and size. Bulk fill RBCs (except SonicFill) were more translucent than conventional RBCs. Low-viscosity bulk fill materials showed the lowest mechanical properties. HV depends highly on the following parameters: material (ηp (2) = 0.952), incremental thickness (0.826), filler volume (0.747), filler weight (0.746) and transmitted irradiance (0.491). The bottom-to-top HV ratio (HVbt) was higher than 80 % in all materials in 2- and 4-mm increments (except for Premise), whereas in 6-mm increments, this is valid only in four bulk fill materials (Venus Bulk Fill, SDR, x-tra fil, Tetric EvoCeram Bulk Fill). The depth of cure is dependent on the RBC's translucency. Low-viscosity bulk fill RBCs have lower mechanical properties than all other types of analysed materials. All bulk fill RBCs (except SonicFill) are more translucent for blue light than conventional RBCs. Although bulk fill RBCs are generally more translucent, the practitioner has to follow the manufacturer's recommendations on curing technique and maximum incremental thickness.

Competition between organics and bromide at the aqueous solution-air interface as seen from ozone uptake kinetics and X-ray photoelectron spectroscopy.

PubMed

Lee, Ming-Tao; Brown, Matthew A; Kato, Shunsuke; Kleibert, Armin; Türler, Andreas; Ammann, Markus

2015-05-14

A more detailed understanding of the heterogeneous chemistry of halogenated species in the marine boundary layer is required. Here, we studied the reaction of ozone (O3) with NaBr solutions in the presence and absence of citric acid (C6H8O7) under ambient conditions. Citric acid is used as a proxy for oxidized organic material present at the ocean surface or in sea spray aerosol. On neat NaBr solutions, the observed kinetics is consistent with bulk reaction-limited uptake, and a second-order rate constant for the reaction of O3 + Br(-) is 57 ± 10 M(-1) s(-1). On mixed NaBr-citric acid aqueous solutions, the uptake kinetics was faster than that predicted by bulk reaction-limited uptake and also faster than expected based on an acid-catalyzed mechanism. X-ray photoelectron spectroscopy (XPS) on a liquid microjet of the same solutions at 1.0 × 10(-3)-1.0 × 10(-4) mbar was used to obtain quantitative insight into the interfacial composition relative to that of the bulk solutions. It revealed that the bromide anion becomes depleted by 30 ± 10% while the sodium cation gets enhanced by 40 ± 20% at the aqueous solution-air interface of a 0.12 M NaBr solution mixed with 2.5 M citric acid in the bulk, attributed to the role of citric acid as a weak surfactant. Therefore, the enhanced reactivity of bromide solutions observed in the presence of citric acid is not necessarily attributable to a surface reaction but could also result from an increased solubility of ozone at higher citric acid concentrations. Whether the acid-catalyzed chemistry may have a larger effect on the surface than in the bulk to offset the effect of bromide depletion also remains open.

Size and surface effects on the magnetism of magnetite and maghemite nanoparticles

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

Nikiforov, V. N., E-mail: pppnvn@yandex.ru; Ignatenko, A. N.; Irkhin, V. Yu.

2017-02-15

The size effects of magnetite and maghemite nanoparticles on their magnetic properties (magnetic moment, Curie temperature, blocking temperature, etc.) have been investigated. Magnetic separation and centrifugation of an aqueous solution of nanoparticles were used for their separation into fractions; their sizes were measured by atomic force microscopy, dynamic light scattering, and electron microscopy. A change in the size leads to a change in the Curie temperature and magnetic moment per formula unit. Both native nanoparticles and those covered with a bioresorbable layer have been considered. The magnetic properties have been calculated by the Monte Carlo method for the classical Heisenbergmore » model with various bulk and surface magnetic moments.« less

Low-Dimensional Palladium Nanostructures for Fast and Reliable Hydrogen Gas Detection

PubMed Central

Noh, Jin-Seo; Lee, Jun Min; Lee, Wooyoung

2011-01-01

Palladium (Pd) has received attention as an ideal hydrogen sensor material due to its properties such as high sensitivity and selectivity to hydrogen gas, fast response, and operability at room temperature. Interestingly, various Pd nanostructures that have been realized by recent developments in nanotechnologies are known to show better performance than bulk Pd. This review highlights the characteristic properties, issues, and their possible solutions of hydrogen sensors based on the low-dimensional Pd nanostructures with more emphasis on Pd thin films and Pd nanowires. The finite size effects, relative strengths and weaknesses of the respective Pd nanostructures are discussed in terms of performance, manufacturability, and practical applicability. PMID:22346605

Aggregation, adsorption, and surface properties of multiply end-functionalized polystyrenes.

PubMed

Ansari, Imtiyaz A; Clarke, Nigel; Hutchings, Lian R; Pillay-Narrainen, Amilcar; Terry, Ann E; Thompson, Richard L; Webster, John R P

2007-04-10

The properties of polystyrene blends containing deuteriopolystyrene, multiply end-functionalized with C8F17 fluorocarbon groups, are strikingly analogous to those of surfactants in solution. These materials, denoted FxdPSy, where x is the number of fluorocarbon groups and y is the molecular weight of the dPS chain in kg/mol, were blended with unfunctionalized polystyrene, hPS. Nuclear reaction analysis experiments show that FxdPSy polymers adsorb spontaneously to solution and blend surfaces, resulting in a reduction in surface energy inferred from contact angle analysis. Aggregation of functionalized polymers in the bulk was found to be sensitive to FxdPSy structure and closely related to surface properties. At low concentrations, the functionalized polymers are freely dispersed in the hPS matrix, and in this range, the surface excess concentration grows sharply with increasing bulk concentration. At higher concentrations, surface excess concentrations and contact angles reach a plateau, small-angle neutron scattering data indicate small micellar aggregates of six to seven F2dPS10 polymer chains and much larger aggregates of F4dPS10. Whereas F2dPS10 aggregates are miscible with the hPS matrix, F4dPS10 forms a separate phase of multilamellar vesicles. Using neutron reflectometry (NR), we found that the extent of the adsorbed layer was approximately half the lamellar spacing of the multilamellar vesicles. NR data were fitted using an error function profile to describe the concentration profile of the adsorbed layer, and reasonable agreement was found with concentration profiles predicted by the SCFT model. The thermodynamic sticking energy of the fluorocarbon-functionalized polymer chains to the blend surface increases from 5.3kBT for x = 2 to 6.6kBT for x = 4 but appears to be somewhat dependent upon the blend concentration.

Alloying Behavior and Properties of FeSiBAlNiCo x High Entropy Alloys Fabricated by Mechanical Alloying and Spark Plasma Sintering

NASA Astrophysics Data System (ADS)

Wang, Wen; Li, Boyu; Zhai, Sicheng; Xu, Juan; Niu, Zuozhe; Xu, Jing; Wang, Yan

2018-02-01

In this paper, FeSiBAlNiCo x (x = 0.2, 0.8) high-entropy alloy (HEA) powders were fabricated by mechanical alloying process, and the powders milled for 140 h were sintered by spark plasma sintering (SPS) technique. The microstructures and properties of as-milled powders and as-sintered samples were investigated. The results reveal that the final milling products (140 h) of both sample powders present the fully amorphous structure. The increased Co contents obviously enhance the glass forming ability and thermal stability of amorphous HEA powders, which are reflected by the shorter formation time of fully amorphous phase and the higher onset crystallization temperature, respectively. According to coercivity, the as-milled FeSiBAlNiCo x (x = 0.2, 0.8) powders (140 h) are the semi-hard magnetic materials. FeSiBAlNiCo0.8 HEA powders possess the highest saturation magnetization and largest remanence ratio. The SPS-ed products of both bulk HEAs are composed of body-centered cubic solid solution, and FeSi and FeB intermetallic phases. They possess the high relative density above 97% and excellent microhardness exceeding 1150 HV. The as-sintered bulks undergo the remarkable increase in saturation magnetization compared with the as-milled state. The SPS-ed FeSiBAlNiCo0.8 HEA exhibits the soft magnetic properties. The electrochemical corrosion test is carried out in 3.5% NaCl solution. The SPS-ed FeSiBAlNiCo0.2 HEA reveals the better passivity with low passive current density, and the higher pitting resistance with wide passive region.

Theoretical study on the electronic and optical properties of bulk and surface (001) InxGa1-xAs

NASA Astrophysics Data System (ADS)

Liu, XueFei; Ding, Zhao; Luo, ZiJiang; Zhou, Xun; Wei, JieMin; Wang, Yi; Guo, Xiang; Lang, QiZhi

2018-05-01

The optical properties of surface and bulk InxGa1-xAs materials are compared systematically first time in this paper. The band structures, density of states and optical properties including dielectric function, reflectivity, absorption coefficient, loss function and refractive index of bulk and surface InxGa1-xAs materials are investigated by first-principles based on plane-wave pseudo-potentials method within the LDA approximation. The results agree well with the available theoretical and experimental studies and indicate that the electronic and optical properties of bulk and surface InxGa1-xAs materials are much different, and the results show that the considered optical properties of the both materials vary with increasing indium composition in an opposite way. The calculations show that the optical properties of surface In0.75Ga0.25As material are unexpected to be far from the other two indium compositions of surface InxGa1-xAs materials while the optical properties of bulk InxGa1-xAs materials vary with increasing indium composition in an expected regular way.

Impact of small-scale saline tracer heterogeneity on electrical resistivity monitoring in fully and partially saturated porous media: Insights from geoelectrical milli-fluidic experiments

NASA Astrophysics Data System (ADS)

Jougnot, Damien; Jiménez-Martínez, Joaquín; Legendre, Raphaël; Le Borgne, Tanguy; Méheust, Yves; Linde, Niklas

2018-03-01

Time-lapse electrical resistivity tomography (ERT) is a geophysical method widely used to remotely monitor the migration of electrically-conductive tracers and contaminant plumes in the subsurface. Interpretations of time-lapse ERT inversion results are generally based on the assumption of a homogeneous solute concentration below the resolution limits of the tomogram depicting inferred electrical conductivity variations. We suggest that ignoring small-scale solute concentration variability (i.e., at the sub-resolution scale) is a major reason for the often-observed apparent loss of solute mass in ERT tracer studies. To demonstrate this, we developed a geoelectrical milli-fluidic setup where the bulk electric conductivity of a 2D analogous porous medium, consisting of cylindrical grains positioned randomly inside a Hele-Shaw cell, is monitored continuously in time while saline tracer tests are performed through the medium under fully and partially saturated conditions. High resolution images of the porous medium are recorded with a camera at regular time intervals, and provide both the spatial distribution of the fluid phases (aqueous solution and air), and the saline solute concentration field (where the solute consists of a mixture of salt and fluorescein, the latter being used as a proxy for the salt concentration). Effective bulk electrical conductivities computed numerically from the measured solute concentration field and the spatial distributions of fluid phases agree well with the measured bulk conductivities. We find that the effective bulk electrical conductivity is highly influenced by the connectivity of high electrical conductivity regions. The spatial distribution of air, saline tracer fingering, and mixing phenomena drive temporal changes in the effective bulk electrical conductivity by creating preferential paths or barriers for electrical current at the pore-scale. The resulting heterogeneities in the solute concentrations lead to strong anisotropy of the effective bulk electrical conductivity, especially for partially saturated conditions. We highlight how these phenomena contribute to the typically large apparent mass loss observed when conducting field-scale time-lapse ERT.

A computational method for the coupled solution of reaction-diffusion equations on evolving domains and manifolds: Application to a model of cell migration and chemotaxis.

PubMed

MacDonald, G; Mackenzie, J A; Nolan, M; Insall, R H

2016-03-15

In this paper, we devise a moving mesh finite element method for the approximate solution of coupled bulk-surface reaction-diffusion equations on an evolving two dimensional domain. Fundamental to the success of the method is the robust generation of bulk and surface meshes. For this purpose, we use a novel moving mesh partial differential equation (MMPDE) approach. The developed method is applied to model problems with known analytical solutions; these experiments indicate second-order spatial and temporal accuracy. Coupled bulk-surface problems occur frequently in many areas; in particular, in the modelling of eukaryotic cell migration and chemotaxis. We apply the method to a model of the two-way interaction of a migrating cell in a chemotactic field, where the bulk region corresponds to the extracellular region and the surface to the cell membrane.

Thermoelastic properties of grossular–andradite solid solution at high pressures and temperatures

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

Fan, Dawei; Kuang, Yunqian; Xu, Jingui

2016-09-21

The pressure–volume–temperature (P–V–T) equation of state (EoS) of synthetic grossular (Grs)–andradite (And) solid-solution garnet sample have been measured at high temperature up to 900 K and high pressures up to 22.75 GPa for Grs50And50, by using in situ angle-dispersive X-ray diffraction and diamond anvil cell. Analysis of room-temperature P–V data to a third-order Birch–Murnaghan (BM) EoS yields: V0 = 1706.8 ± 0.2 Å3, K0 = 164 ± 2 GPa and K'0 = 4.7 ± 0.5. Fitting of our P–V–T data by means of the high-temperature third-order BM EoS gives the thermoelastic parameters: V0 = 1706.9 ± 0.2 Å3, K0 =more » 164 ± 2 GPa, K'0 = 4.7 ± 0.2, (∂K/∂T)P = -0.018 ± 0.002 GPa K-1, and α0 = (2.94 ± 0.07) × 10-5 K-1. The results also confirm that grossular content increases the bulk modulus of the Grs-And join following a nearly ideal mixing model. The relation between bulk modulus and Grs mole fraction (XGrs) in this garnet join is derived to be K0 (GPa) = (163.7 ± 0.7) + (0.14 ± 0.02) XGrs (R2 = 0.985). Present results are also compared to previously studies determined the thermoelastic properties of Grs-And garnets.« less

Phenanthrene sorption with heterogeneous organic matter in a landfill aquifer material

USGS Publications Warehouse

Karapanagioti, H.K.; Sabatini, D.A.; Kleineidam, S.; Grathwohl, P.; Ligouis, B.

1999-01-01

Phenanthrene was used as a model chemical to study the sorption properties of Canadian River Alluvium aquifer material. Both equilibrium and kinetic sorption processes were evaluated through batch studies. The bulk sample was divided into subsamples with varying properties such as particle size, organic content, equilibration time, etc. in order to determine the effect of these properties on resulting sorption parameters. The data have been interpreted and the effect of experimental variables was quantified using the Freundlich isotherm model and a numerical solution of Fick's 2nd law in porous media. Microscopic organic matter characterization proved to be a valuable tool for explaining the results. Different organic matter properties and sorption mechanisms were observed for each soil subsample. Samples containing coal particles presented high Koc values. Samples with organic matter dominated by organic coatings on quartz grains presented low Koc values and contained a high percentage of fast sorption sites. The numerical solution of Fick's 2ndlaw requires the addition of two terms (fast and slow) in order to fit the kinetics of these heterogeneous samples properly. These results thus demonstrate the need for soil organic matter characterization in order to predict and explain the sorption properties of a soil sample containing heterogeneous organic matter and also the difficulty and complexity of modeling sorption in such samples.

Tribological characterisation of Zr-based bulk metallic glass in simulated physiological media

NASA Astrophysics Data System (ADS)

Chen, Q.; Chan, K. C.; Liu, L.

2011-10-01

Due to their excellent wear resistant properties and high strength, as well as a low Young's modulus, Zr-based bulk metallic glasses (BMGs) are potentially suitable biomaterials for low-friction arthroplasty. The wear characteristics of the Zr60.14Cu22.31Fe4.85Al9.7Ag3 bulk amorphous alloy against ultra-high-molecular-weight polyethylene (UHMWPE) compared to a CoCrMo/UHMWPE combination were investigated in two different wear screening test devices, reciprocating and unidirectional. Hank's solution and sterile calf bovine serum were selected as the lubricant fluid media. It was found that different fluid media had insignificant effect on polyethylene wear against BMG counterfaces. The wear behaviour obtained on both test devices demonstrated that Zr-based BMG achieved UHMWPE counterface wear rates superior to conventional cast CoCrMo alloy, where the wear rate of UHMWPE is decreased by over 20 times. The tribological performance of these joints is superior to that of conventional metal-on-polymer designs. Contact angle measurements suggested that the advantage of BMG over a CoCrMo alloy counterface is attributed to its highly hydrophilic surfaces.

Geochemical heterogeneity in a sand and gravel aquifer: Effect of sediment mineralogy and particle size on the sorption of chlorobenzenes

USGS Publications Warehouse

Barber, Larry B.; Thurman, E. Michael; Runnells, Donald D.

1992-01-01

The effect of particle size, mineralogy and sediment organic carbon (SOC) on sorption of tetrachlorobenzene and pentachlorobenzene was evaluated using batch-isotherm experiments on sediment particle-size and mineralogical fractions from a sand and gravel aquifer, Cape Cod, Massachusetts. Concentration of SOC and sorption of chlorobenzenes increase with decreasing particle size. For a given particle size, the magnetic fraction has a higher SOC content and sorption capacity than the bulk or non-magnetic fractions. Sorption appears to be controlled by the magnetic minerals, which comprise only 5–25% of the bulk sediment. Although SOC content of the bulk sediment is <0.1%, the observed sorption of chlorobenzenes is consistent with a partition mechanism and is adequately predicted by models relating sorption to the octanol/water partition coefficient of the solute and SOC content. A conceptual model based on preferential association of dissolved organic matter with positively-charged mineral surfaces is proposed to describe micro-scale, intergranular variability in sorption properties of the aquifer sediments.

Hydration of AMP and ATP molecules in aqueous solution and solid films.

PubMed

Faizullin, Dzhigangir; Zakharchenko, Nataliya; Zuev, Yuriy; Puzenko, Alexander; Levy, Evgeniya; Feldman, Yuri

2013-11-20

Water enables life and plays a critical role in biology. Considered as a versatile and adaptive component of the cell, water engages a wide range of biomolecular interactions. An organism can exist and function only if its self-assembled molecular structures are hydrated. It was shown recently that switching of AMP/ATP binding to the insulin-independent glucose transporter Human Erythrocyte Glucose Transport Protein (GLUT1) may greatly influence the ratio of bulk and bound water during regulation of glucose uptake by red blood cells. In this paper, we present the results on the hydration properties of AMP/ATP obtained by means of dielectric spectroscopy in aqueous solution and for fully ionized forms in solid amorphous films with the help of gravimetric studies.

Nanometrization of Lanthanide-Based Coordination Polymers.

PubMed

Neaime, Chrystelle; Daiguebonne, Carole; Calvez, Guillaume; Freslon, Stéphane; Bernot, Kevin; Grasset, Fabien; Cordier, Stéphane; Guillou, Olivier

2015-11-23

Heteronuclear lanthanide-based coordination polymers are microcrystalline powders, the luminescence properties of which can be precisely tuned by judicious choice of the rare-earth ions. In this study, we demonstrate that such materials can also be obtained as stable solutions of nanoparticles in non-toxic polyols. Bulk powders of the formula [Ln2-2x Ln'2x (bdc)3 ⋅4 H2 O]∞ (where H2 bdc denotes 1,4-benzene-dicarboxylic acid, 0≤x≤1, and Ln and Ln' denote lanthanide ions of the series La to Tm plus Y) afford nanoparticles that have been characterized by dynamic light-scattering (DLS) and transmission electron microscopy (TEM) measurements. Their luminescence properties are similar to those of the bulk materials. Stabilities versus time and versus dilution with another solvent have been studied. This study has revealed that it is possible to tune the size of the nanoparticles. This process offers a reliable means of synthesizing suspensions of nanoparticles with tunable luminescence properties and tunable size distributions in a green solvent (glycerol). The process is also extendable to other coordination polymers and other solvents (ethylene glycol, for example). It constitutes a new route for the facile solubilization of lanthanide-based coordination polymers. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Computational Screening of 2D Materials for Photocatalysis.

PubMed

Singh, Arunima K; Mathew, Kiran; Zhuang, Houlong L; Hennig, Richard G

2015-03-19

Two-dimensional (2D) materials exhibit a range of extraordinary electronic, optical, and mechanical properties different from their bulk counterparts with potential applications for 2D materials emerging in energy storage and conversion technologies. In this Perspective, we summarize the recent developments in the field of solar water splitting using 2D materials and review a computational screening approach to rapidly and efficiently discover more 2D materials that possess properties suitable for solar water splitting. Computational tools based on density-functional theory can predict the intrinsic properties of potential photocatalyst such as their electronic properties, optical absorbance, and solubility in aqueous solutions. Computational tools enable the exploration of possible routes to enhance the photocatalytic activity of 2D materials by use of mechanical strain, bias potential, doping, and pH. We discuss future research directions and needed method developments for the computational design and optimization of 2D materials for photocatalysis.

Optical and Thermo-optical Properties of Polyimide-Single-Walled Carbon Nanotube Films: Experimental Results and Empirical Equations

NASA Technical Reports Server (NTRS)

Smith, Joseph G., Jr.; Connell, John W.; Watson, Kent A.; Danehy, Paul M.

2005-01-01

The incorporation of single-walled carbon nanotubes (SWNTs) into the bulk of space environmentally durable polymers at loading levels greater than or equal to 0.05 wt % has afforded thin films with surface and volume resistivities sufficient for electrostatic charge mitigation. However, the optical transparency at 500 nm decreased and the thermo-optical properties (solar absorptivity and thermal emissivity) increased with increaed SWNT loading. These properties were also dependent on film thickness. The absorbance characteristics of the films as a function of SWNT loading and film thickness were measured and determined to follow the classical Beer-Lambert law. Based on these results, an empirical relationship was derived and molar absorptivities determined for both the SWNTs and polymer matrix to provide a predictive approximation of these properties. The molar absorptivity determined for SWNTs dispersed in the polymer was comparable to reported solution determined values for HiPco SWNTs.

Effect of sample thickness on the extracted near-infrared bulk optical properties of Bacillus subtilis in liquid culture.

PubMed

Dzhongova, Elitsa; Harwood, Colin R; Thennadil, Suresh N

2011-11-01

In order to determine the bulk optical properties of a Bacillus subtilis culture during growth phase we investigated the effect of sample thickness on measurements taken with different measurement configurations, namely total diffuse reflectance and total diffuse transmittance. The bulk optical properties were extracted by inverting the measurements using the radiative transfer theory. While the relationship between reflectance and biomass changes with sample thickness and the intensity (absorbance) levels vary significantly for both reflectance and transmittance measurements, the extracted optical properties show consistent behavior in terms of both the relationship with biomass and magnitude. This observation indicates the potential of bulk optical properties for building models that could be more easily transferable compared to those built using raw measurements.

Smart membranes: Hydroxypropyl cellulose for flavor delivery

NASA Astrophysics Data System (ADS)

Heitfeld, Kevin A.

2007-12-01

This work focuses on the use of temperature responsive gels (TRGs) (polymeric hydrogels with a large temperature-dependent change in volume) for flavor retention at cooking temperatures. Specifically, we have studied a gel with a lower critical solution temperature (LCST) that swells at low temperatures and collapses at high temperatures. In the collapsed state, the polymer acts as a transport barrier, keeping the volatile flavors inside. An encapsulation system was designed to utilize the solution (phase separation) behavior of a temperature responsive gel. The gel morphology was understood and diffusive properties were tailored through morphology manipulation. Heterogeneous and homogeneous gels were processed by understanding the effect of temperature on gel morphology. A morphology model was developed linking bulk diffusive properties to molecular morphology. Flavor was encapsulated within the gel and the emulsifying capability was determined. The capsules responded to temperature similarly to the pure polymer. The release kinetcs were compared to commercial gelatin capsules and the temperature responsive polymer took longer to release.

Effect of phytoplackton-derived organic matter on the behavior of marine aerosols

NASA Astrophysics Data System (ADS)

Fuentes, E.; Coe, H.; McFiggans, G.; Green, D.

2009-04-01

The presence of significant concentrations of organic material in marine aerosols has been appreciated for several decades; however, only recently has significant progress been made towards demonstrating that this organic content is biogenically formed. Biogenic organics of placktonic life origin are incorporated in marine aerosol composition as a result of bubble bursting/breaking waves mechanisms that occur at the ocean surface. The presence of organic surfactants in the marine aerosol composition might have a significant impact on the properties of the generated aerosols by affecting the particles surface tension and solution balance properties. Nevertheless, it remains uncertain the role of such organics on the physical-chemical behavior of marine aerosols. In this work an experimental study was performed in order to determine the influence of biogenic marine organic compounds on the size distribution, hygroscopicity and cloud-nucleating properties of marine aerosols. For the experimental study a laboratory water recirculation system (bubble tank), designed for the simulation of bubble-burst aerosol formation, was used as marine aerosol generator. The bubble spectra produced by such system was characterized by means of an optical bubble measuring device (BMS) and it was found to be consistent with oceanic bubble spectra properties. Seawater proxy solutions were prepared from laboratory biologically-synthesized exudates produced by oceanic representative algal species and introduced in the tank for the generation of marine aerosol by bubble bursting. Two experimental methods were employed for seawater proxies preparation: the formation of surface monolayers from the biogenic surfactants extracted by a solid phase extraction technique (monolayer method) and the mixing of the exudates in the sea salt water bulk (bulk mixing method). Particle size distribution, hygroscopicity and cloud condensation nuclei experiments for different monolayers, and exudate mixtures were performed. This contribution provides an overview of the experimental study conducted and the most relevant results found in this research work.

Extended analytical solutions for effective elastic moduli of cracked porous media

NASA Astrophysics Data System (ADS)

Nguyen, Sy-Tuan; To, Quy Dong; Vu, Minh Ngoc

2017-05-01

Extended solutions are derived, on the basis of the micromechanical methods, for the effective elastic moduli of porous media containing stiff pores and both open and closed cracks. Analytical formulas of the overall bulk and shear moduli are obtained as functions of the elastic moduli of the solid skeleton, porosity and the densities of open and closed cracks families. We show that the obtained results are extensions of the classical widely used Walsh's (JGR, 1965) and Budiansky-O‧Connell's (JGR, 1974) solutions. Parametric sensitivity analysis clarifies the impact of the model parameters on the effective elastic properties. An inverse analysis, using sonic and density data, is considered to quantify the density of both open and closed cracks. It is observed that the density of closed cracks depends strongly on stress condition while the dependence of open cracks on the confining stress is negligible.

Mesoscale modeling of vacancy-mediated Si segregation near an edge dislocation in Ni under irradiation

NASA Astrophysics Data System (ADS)

Li, Zebo; Trinkle, Dallas R.

2017-04-01

We use a continuum method informed by transport coefficients computed using self-consistent mean field theory to model vacancy-mediated diffusion of substitutional Si solutes in FCC Ni near an a/2 [1 1 ¯0 ] (111 ) edge dislocation. We perform two sequential simulations: first under equilibrium boundary conditions and then under irradiation. The strain field around the dislocation induces heterogeneity and anisotropy in the defect transport properties and determines the steady-state vacancy and Si distributions. At equilibrium both vacancies and Si solutes diffuse to form Cottrell atmospheres with vacancies accumulating in the compressive region above the dislocation core while Si segregates to the tensile region below the core. Irradiation raises the bulk vacancy concentration, driving vacancies to flow into the dislocation core. The out-of-equilibrium vacancy fluxes drag Si atoms towards the core, causing segregation to the compressive region, despite Si being an oversized solute in Ni.

Visible and near-infrared bulk optical properties of raw milk.

PubMed

Aernouts, B; Van Beers, R; Watté, R; Huybrechts, T; Lammertyn, J; Saeys, W

2015-10-01

The implementation of optical sensor technology to monitor the milk quality on dairy farms and milk processing plants would support the early detection of altering production processes. Basic visible and near-infrared spectroscopy is already widely used to measure the composition of agricultural and food products. However, to obtain maximal performance, the design of such optical sensors should be optimized with regard to the optical properties of the samples to be measured. Therefore, the aim of this study was to determine the visible and near-infrared bulk absorption coefficient, bulk scattering coefficient, and scattering anisotropy spectra for a diverse set of raw milk samples originating from individual cow milkings, representing the milk variability present on dairy farms. Accordingly, this database of bulk optical properties can be used in future simulation studies to efficiently optimize and validate the design of an optical milk quality sensor. In a next step of the current study, the relation between the obtained bulk optical properties and milk quality properties was analyzed in detail. The bulk absorption coefficient spectra were found to mainly contain information on the water, fat, and casein content, whereas the bulk scattering coefficient spectra were found to be primarily influenced by the quantity and the size of the fat globules. Moreover, a strong positive correlation (r ≥ 0.975) was found between the fat content in raw milk and the measured bulk scattering coefficients in the 1,300 to 1,400 nm wavelength range. Relative to the bulk scattering coefficient, the variability on the scattering anisotropy factor was found to be limited. This is because the milk scattering anisotropy is nearly independent of the fat globule and casein micelle quantity, while it is mainly determined by the size of the fat globules. As this study shows high correlations between the sample's bulk optical properties and the milk composition and fat globule size, a sensor that allows for robust separation between the absorption and scattering properties would enable accurate prediction of the raw milk quality parameters. Copyright © 2015 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Brane f(R) gravity cosmologies

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

Balcerzak, Adam; DaPbrowski, Mariusz P.

2010-06-15

By the application of the generalized Israel junction conditions we derive cosmological equations for the fourth-order f(R) brane gravity and study their cosmological solutions. We show that there exists a nonstatic solution which describes a four-dimensional de Sitter (dS{sub 4}) brane embedded in a five-dimensional anti-de Sitter (AdS{sub 5}) bulk for a vanishing Weyl tensor contribution. On the other hand, for the case of a nonvanishing Weyl tensor contribution, there exists a static brane solution only. We claim that in order to get some more general nonstatic f(R) brane configurations, one needs to admit a dynamical matter energy-momentum tensor inmore » the bulk rather than just a bulk cosmological constant.« less

Performance of journal bearings with semi-compressible fluids

NASA Technical Reports Server (NTRS)

Carpino, M.; Peng, J.-P.

1991-01-01

Cryogenic fluids in isothermal rigid surface and foil type journal bearings can sometimes be treated as semicompressible fluids. In these applications, the fluid density is a function of the pressure. At low pressures, the fluids can change from a liquid to a saturated liquid-vapor phase. The performance of a rigid surface journal bearing with an idealized semicompressible fluid is discussed. Pressure solutions are based upon a Reynolds equation which includes the effects of a compressibility via the bulk modulus of the fluid. Results are contrasted with the performance of isothermal constant property incompressible fluids.

Low-temperature slip along intergrain boundaries

NASA Astrophysics Data System (ADS)

Bakai, A. S.; Lazarev, P. N.

2017-10-01

Equations are derived for slip in a disordered atomic layer which describe diffusive creep as well as high-speed slip at low temperatures. An exact solution for the slip velocity is found in the form of a functional of the distribution function of the threshold shear stresses in the slip layer. The relationship between the microscopic parameters of the theory and the macroscopic properties of metallic glass is established in terms of the Mott intergrain slip model. The calculated rate of deformation of bulk metallic glass is compared with published experimental data.

Random fiber laser.

PubMed

de Matos, Christiano J S; de S Menezes, Leonardo; Brito-Silva, Antônio M; Martinez Gámez, M A; Gomes, Anderson S L; de Araújo, Cid B

2007-10-12

We investigate the effects of two-dimensional confinement on the lasing properties of a classical random laser system operating in the incoherent feedback (diffusive) regime. A suspension of 250 nm rutile (TiO2) particles in a rhodamine 6G solution was inserted into the hollow core of a photonic crystal fiber generating the first random fiber laser and a novel quasi-one-dimensional random laser geometry. A comparison with similar systems in bulk format shows that the random fiber laser presents an efficiency that is at least 2 orders of magnitude higher.

The Constellation-X Focal Plane Microcalorimeter Array: An NTD-Germanium Solution

NASA Technical Reports Server (NTRS)

Beeman, J.; Silver, E.; Bandler, S.; Schnopper, H.; Murray, S.; Madden, N.; Landis, D.; Haller, E. E.; Barbera, M.

2001-01-01

The hallmarks of Neutron Transmutation Doped (NTD) germanium cryogenic thermistors include high reliability, reproducibility, and long term stability of bulk carrier transport properties. Using micro-machined NTD Ge thermistors with integral 'flying' leads, we can now fabricate two-dimensional arrays that are built up from a series of stacked linear arrays. We believe that this modular approach of building, assembling, and perhaps replacing individual modules of detectors is essential to the successful fabrication and testing of large multi-element instruments. Details of construction are presented.

Runoff and Solute Mobilisation in a Semi-arid Headwater Catchment

NASA Astrophysics Data System (ADS)

Hughes, J. D.; Khan, S.; Crosbie, R.; Helliwell, S.; Michalk, D.

2006-12-01

Runoff and solute transport processes contributing to stream flow were determined in a small headwater catchment in the eastern Murray-Darling Basin of Australia using hydrometric and tracer methods. Stream flow and electrical conductivity were monitored from two gauges draining a portion of upper catchment area (UCA), and a saline scalded area respectively. Results show that the bulk of catchment solute export, occurs via a small saline scald (< 2% of catchment area) where solutes are concentrated in the near surface zone (0-40 cm). Non-scalded areas of the catchment are likely to provide the bulk of catchment runoff, although the scalded area is a higher contributor on an areal basis. Runoff from the non-scalded area is about two orders of magnitude lower in electrical conductivity than the scalded area. This study shows that the scalded zone and non-scalded parts of the catchment can be managed separately since they are effectively de-coupled except over long time scales, and produce runoff of contrasting quality. Such differences are "averaged out" by investigations that operate at larger scales, illustrating that observations need to be conducted at a range of scales. EMMA modelling using six solutes shows that "event" or "new" water dominated the stream hydrograph from the scald. This information together with hydrometric data and soil physical properties indicate that saturated overland flow is the main form of runoff generation in both the scalded area and the UCA. Saturated areas make up a small proportion of the catchment, but are responsible for production of all run off in conditions experienced throughout the experimental period. The process of saturation and runoff bears some similarities to the VSA concept (Hewlett and Hibbert 1967).

Glymphatic solute transport does not require bulk flow

PubMed Central

Asgari, Mahdi; de Zélicourt, Diane; Kurtcuoglu, Vartan

2016-01-01

Observations of fast transport of fluorescent tracers in mouse brains have led to the hypothesis of bulk water flow directed from arterial to venous paravascular spaces (PVS) through the cortical interstitium. At the same time, there is evidence for interstitial solute transport by diffusion rather than by directed bulk fluid motion. It has been shown that the two views may be consolidated by intracellular water flow through astrocyte networks combined with mainly diffusive extracellular transport of solutes. This requires the presence of a driving force that has not been determined to date, but for which arterial pulsation has been suggested as the origin. Here we show that arterial pulsation caused by pulse wave propagation is an unlikely origin of this hypothetical driving force. However, we further show that such pulsation may still lead to fast para-arterial solute transport through dispersion, that is, through the combined effect of local mixing and diffusion in the para-arterial space. PMID:27929105

Multi-octave supercontinuum generation from mid-infrared filamentation in a bulk crystal

PubMed Central

Silva, F.; Austin, D.R.; Thai, A.; Baudisch, M.; Hemmer, M.; Faccio, D.; Couairon, A.; Biegert, J.

2012-01-01

In supercontinuum generation, various propagation effects combine to produce a dramatic spectral broadening of intense ultrashort optical pulses. With a host of applications, supercontinuum sources are often required to possess a range of properties such as spectral coverage from the ultraviolet across the visible and into the infrared, shot-to-shot repeatability, high spectral energy density and an absence of complicated pulse splitting. Here we present an all-in-one solution, the first supercontinuum in a bulk homogeneous material extending from 450 nm into the mid-infrared. The spectrum spans 3.3 octaves and carries high spectral energy density (2 pJ nm−1–10 nJ nm−1), and the generation process has high shot-to-shot reproducibility and preserves the carrier-to-envelope phase. Our method, based on filamentation of femtosecond mid-infrared pulses in the anomalous dispersion regime, allows for compact new supercontinuum sources. PMID:22549836

Dielectric and acoustical high frequency characterisation of PZT thin films

NASA Astrophysics Data System (ADS)

Conde, Janine; Muralt, Paul

2010-02-01

Pb(Zr, Ti)O3 (PZT) is an interesting material for bulk acoustic wave resonator applications due to its high electromechanical coupling constant, which would enable fabrication of large bandwidth frequency filters. The major challenge of the PZT solid solution system is to overcome mechanical losses generally observed in PZT ceramics. To increase the understanding of these losses in textured thin films, thin film bulk acoustic resonators (TFBAR's) based on PZT thin films with compositions either in the tetragonal region or at the morphotropic phase boundary and (111) or {100} textures were fabricated and studied up to 2 GHz. The dielectric and elastic materials coefficients were extracted from impedance measurements at the resonance frequency. The dispersion of the dielectric constant was obtained from impedance measurements up to 2 GHz. The films with varying compositions, textures and deposition methods (sol-gel or sputtering) were compared in terms of dielectric and acoustical properties.

Microstructure and mechanical properties of bulk yttria-partially-stabilized zirconia

NASA Technical Reports Server (NTRS)

Valentine, P. G.; Maier, R. D.; Mitchell, T. E.

1981-01-01

A commercially available bulk 4.5 mole percent yttria-(Y2O3) partially stabilized zirconia (PSZ) was studied by light microscopy, X-ray analysis, microhardness measurement, and fracture toughness testing. The growth of the precipitates and the phase transformations were studied as a function of aging in air at 1500 C. Aging curves were constructed for both the as received and the solution annealed and quenched materials; the curves showed hardness peaks at 1397 and 1517 Kg/sq mm respectively. The rectangular plate shaped tetragonal precipitates were found to have a 110 habit plane. A total of twelve different types of tetragonal precipitates were found. Grinding of the Y2O3 PSZ into powder did not cause a significant amount of metastable tetragonal precipitates to transform into the monoclinc phase, thus indicating that transformation toughening is not a significant mechanism for the material.

Fluids of the Lower Crust: Deep Is Different

NASA Astrophysics Data System (ADS)

Manning, Craig E.

2018-05-01

Deep fluids are important for the evolution and properties of the lower continental and arc crust in tectonically active settings. They comprise four components: H2O, nonpolar gases, salts, and rock-derived solutes. Contrasting behavior of H2O-gas and H2O-salt mixtures yields immiscibility and potential separation of phases with different chemical properties. Equilibrium thermodynamic modeling of fluid-rock interaction using simple ionic species known from shallow-crustal systems yields solutions too dilute to be consistent with experiments and resistivity surveys, especially if CO2 is added. Therefore, additional species must be present, and H2O-salt solutions likely explain much of the evidence for fluid action in high-pressure settings. At low salinity, H2O-rich fluids are powerful solvents for aluminosilicate rock components that are dissolved as polymerized clusters. Addition of salts changes solubility patterns, but aluminosilicate contents may remain high. Fluids with Xsalt = 0.05 to 0.4 in equilibrium with model crustal rocks have bulk conductivities of 10‑1.5 to 100 S/m at porosity of 0.001. Such fluids are consistent with observed conductivity anomalies and are capable of the mass transfer seen in metamorphic rocks exhumed from the lower crust.

Investigation of Solution Polymerizations in Microgravity and 1 G

NASA Technical Reports Server (NTRS)

Kennedy, Alvin P.

1998-01-01

The in-situ dielectric spectra for the solution polymerization of polydiacetylene has been successfully measured. The results show a distinct difference between the response for the bulk solution and surface polymerization. It also shows a low frequency peak in the dissipation factor which is present in both the bulk and surface polymerizations. These features may prove to be significant indicators for important polymerization processes. Future studies will investigate the mechanisms responsible for these dielectric responses. This technique will eventually be used to monitor microgravity polymerizations and provide in-situ data on how microgravity affects solution polymerization.

Fluids of the lower crust and upper mantle: deep is different

NASA Astrophysics Data System (ADS)

Manning, C. E.

2017-12-01

Deep fluids are important for the evolution and properties of the lower crust and upper mantle in tectonically active settings. Uncertainty about their chemistry has led past workers to use upper crustal fluids as analogues. However, recent results show that fluids at >15 km differ fundamentally from shallow fluids and help explain high-pressure metasomatism and resistivity patterns. Deep fluids are comprised of four components: H2O, non-polar gases (chiefly CO2), salts (mostly alkali chlorides), and rock-derived solutes (dominated by aluminosilicates and related components). The first three generally define the solvent properties of the fluid, and models must account for observations that H2O activity may be quite low. The contrasting behavior of H2O-gas and H2O-salt mixtures yields immiscibility in the ternary system, which can lead to separation of two phases with fundamentally different chemical and transport properties. Thermodynamic modeling of equilibrium between rocks and H2O using simple ionic species known from shallow-crustal systems yields solutions possessing total dissolved solids and ionic strength that are too low to be consistent with experiments and resistivity surveys. Addition of CO2 further lowers bulk solubility and conductivity. Therefore, additional species must be present in H2O, and H2O-salt solutions likely explain much of the evidence for fluid action in high-P settings. At low salinity, H2O-rich fluids are powerful solvents for aluminosilicate rock components that are dissolved as previously unrecognized polymerized clusters. Experiments show that, near H2O-saturated melting, Al-Si polymers comprise >80% of solutes. The stability of these species facilitates critical critical mixing in rock-H2O systems. Addition of salt (e.g., NaCl) changes solubility patterns, but aluminosilicate contents remain high. Thermodynamic models indicate that the ionic strength of fluids with Xsalt = 0.05 to 0.4 and equilibrated with model crustal rocks have predicted bulk conductivities of 10-1.5 to 100 S/m at porosity of 0.001. Such fluids are thus consistent with conductivity anomalies commonly observed in the lower crust (e.g., the "G" anomaly), and are capable of the mass transfer commonly seen in metamorphic rocks exhumed from the lower crust and subduction zones.

The use of shale ash in dry mix construction materials

NASA Astrophysics Data System (ADS)

Gulbe, L.; Setina, J.; Juhnevica, I.

2017-10-01

The research was made to determine the use of shale ash usage in dry mix construction materials by replacing part of cement amount. Cement mortar ZM produced by SIA Sakret and two types of shale ashes from Narva Power plant (cyclone ash and electrostatic precipitator ash) were used. Fresh mortar properties, hardened mortar bulk density, thermal conductivity (λ10, dry) (table value) were tested in mortar ZM samples and mortar samples in which 20% of the amount of cement was replaced by ash. Compressive strenght, frost resistance and resistance to sulphate salt solutions were checked. It was stated that the use of electrostatic precipitator ash had a little change of the material properties, but the cyclone ash significantly reduced the mechanical strength of the material.

Plasma Jet Interactions with Liquids in Partial Fulfillment of an NRL Karles Fellowship

DTIC Science & Technology

2015-11-30

water (DI H2O) as the reference solution, two concentrations of NaCl mixtures (0.6 Molar, and 1.0 Molar saturated NaCl), and three electroless solutions...by diffusion) to the bulk surface in net excess; that oxygen ions/radicals are being consumed from the bulk by an electrolysis path way; or that the

On the intermolecular vibrational coupling, hydrogen bonding, and librational freedom of water in the hydration shell of mono- and bivalent anions.

PubMed

Ahmed, Mohammed; Namboodiri, V; Singh, Ajay K; Mondal, Jahur A

2014-10-28

The hydration energy of an ion largely resides within the first few layers of water molecules in its hydration shell. Hence, it is important to understand the transformation of water properties, such as hydrogen-bonding, intermolecular vibrational coupling, and librational freedom in the hydration shell of ions. We investigated these properties in the hydration shell of mono- (Cl(-) and I(-)) and bivalent (SO4(2-) and CO3(2-)) anions by using Raman multivariate curve resolution (Raman-MCR) spectroscopy in the OH stretch, HOH bend, and [bend+librational] combination bands of water. Raman-MCR of aqueous Na-salt (NaCl, NaI, Na2SO4, and Na2CO3) solutions provides ion-correlated spectra (IC-spectrum) which predominantly bear the vibrational characteristics of water in the hydration shell of respective anions. Comparison of these IC-spectra with the Raman spectrum of bulk water in different spectral regions reveals that the water is vibrationally decoupled with its neighbors in the hydration shell. Hydrogen-bond strength and librational freedom also vary with the nature of anion: hydrogen-bond strength, for example, decreases as CO3(2-) > SO4(2-) > bulk water ≈ Cl(-) > I(-); and the librational freedom increases as CO3(2-) ≈ SO4(2-) < bulk water < Cl(-) < I(-). It is believed that these structural perturbations influence the dynamics of coherent energy transfer and librational reorientation of water in the hydration shell of anions.

Elucidating the Solvation Structure and Dynamics of Lithium Polysulfides Resulting from Competitive Salt and Solvent Interactions

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

Rajput, Nav Nidhi; Murugesan, Vijayakumar; Shin, Yongwoo

2017-04-10

Fundamental molecular level understanding of functional properties of liquid solutions provides an important basis for designing optimized electrolytes for numerous applica-tions. In particular, exhaustive knowledge of solvation structure, stability and transport properties is critical for developing stable electrolytes for fast charging and high energy density next-generation energy storage systems. Here we report the correlation between solubility, solvation structure and translational dynamics of a lithium salt (Li-TFSI) and polysulfides species using well-benchmarked classical molecular dynamics simulations combined with nuclear magnetic resonance (NMR). It is observed that the polysulfide chain length has a significant effect on the ion-ion and ion-solvent interaction asmore » well as on the diffusion coefficient of the ionic species in solution. In particular, extensive cluster formation is observed in lower order poly-sulfides (Sx2-; x≤4), whereas the longer polysulfides (Sx2-; x>4) show high solubility and slow dynamics in the solu-tion. It is observed that optimal solvent/salt ratio is essen-tial to control the solubility and conductivity as the addi-tion of Li salt increases the solubility but decreases the mo-bility of the ionic species. This work provides a coupled theoretical and experimental study of bulk solvation struc-ture and transport properties of multi-component electro-lyte systems, yielding design metrics for developing optimal electrolytes with improved stability and solubility.« less

The structure of aqueous sodium hydroxide solutions: a combined solution x-ray diffraction and simulation study.

PubMed

Megyes, Tünde; Bálint, Szabolcs; Grósz, Tamás; Radnai, Tamás; Bakó, Imre; Sipos, Pál

2008-01-28

To determine the structure of aqueous sodium hydroxide solutions, results obtained from x-ray diffraction and computer simulation (molecular dynamics and Car-Parrinello) have been compared. The capabilities and limitations of the methods in describing the solution structure are discussed. For the solutions studied, diffraction methods were found to perform very well in describing the hydration spheres of the sodium ion and yield structural information on the anion's hydration structure. Classical molecular dynamics simulations were not able to correctly describe the bulk structure of these solutions. However, Car-Parrinello simulation proved to be a suitable tool in the detailed interpretation of the hydration sphere of ions and bulk structure of solutions. The results of Car-Parrinello simulations were compared with the findings of diffraction experiments.

Physicochemical mechanisms of plasma-liquid interactions within plasma channels in liquid

NASA Astrophysics Data System (ADS)

Franclemont, Joshua; Fan, Xiangru; Mededovic Thagard, Selma

2015-10-01

The goal of this study is to advance the fundamental understanding of the physical and chemical mechanisms by which excited radical species produced by electrical plasmas directly in water, OH radicals especially, induce chemical changes in aqueous organic compounds and to exploit this for the development and optimization of drinking and wastewater plasma-based treatment systems. To achieve this goal, this study measured and correlated the production rate of hydrogen peroxide (H2O2) with physicochemical properties of 11 organic compounds. The observed individual correlations between the investigated physicochemical properties and the resulting H2O2 concentrations were used to develop an equation that would allow predicting the measured H2O2 concentration from physicochemical properties of a compound. Results reveal that the production rate of H2O2 directly depends on the surface tension of the solution and compounds’ bulk liquid concentration, hydrophobicity (K ow value), and molecular volume. Other properties such as vapor pressure, Henry’s constant, enthalpy of vaporization, ionization energy, electron affinity, and molecular dipole moment do not affect the H2O2 chemistry. K ow value and surface tension of the solution determine the compound’s concentration at the plasma interface. Once at the interface, the molecular volume determines the rate at which the molecule will react with OH radicals.

Protein hydration in solution: Experimental observation by x-ray and neutron scattering

PubMed Central

Svergun, D. I.; Richard, S.; Koch, M. H. J.; Sayers, Z.; Kuprin, S.; Zaccai, G.

1998-01-01

The structure of the protein–solvent interface is the subject of controversy in theoretical studies and requires direct experimental characterization. Three proteins with known atomic resolution crystal structure (lysozyme, Escherichia coli thioredoxin reductase, and protein R1 of E. coli ribonucleotide reductase) were investigated in parallel by x-ray and neutron scattering in H2O and D2O solutions. The analysis of the protein–solvent interface is based on the significantly different contrasts for the protein and for the hydration shell. The results point to the existence of a first hydration shell with an average density ≈10% larger than that of the bulk solvent in the conditions studied. Comparisons with the results of other studies suggest that this may be a general property of aqueous interfaces. PMID:9482874

How do glycerol and dimethyl sulphoxide affect local tetrahedral structure of water around a nonpolar solute at low temperature? Importance of preferential interaction.

PubMed

Daschakraborty, Snehasis

2018-04-07

Glycerol and dimethyl sulphoxide (DMSO) have vital roles in cryoprotection of living cells, tissues, etc. The above action has been directly linked with disruption of hydrogen (H-) bond structure and dynamics of water by these cosolvents at bulk region and around various complex units, such as peptide, amino acid, protein, and lipid membrane. However, the disruption of the local structure of the water solvent around a purely hydrophobic solute is still not studied extensively. The latter is also important in the context of stabilization of protein from cold denaturation. Through all-atom molecular dynamics simulation, we have investigated the comparative effect of glycerol and DMSO on the orientational order of water around a nonpolar solute at -5 °C. A steady reduction of the tetrahedral order of water is observed at bulk (>10 Å distance from the solute) and solute interface (<5.5 Å distance from the solute) with increasing the cosolvent concentration. Contrasting roles of glycerol and DMSO have been evidenced. While DMSO affects the H-bond structure of the interfacial water more than that of the bulk water, glycerol affects the water structure almost uniformly at all regions around the solute. Furthermore, while glycerol helps to retain water molecules at the interface, DMSO significantly reduces the water content in that region. We have put forward a plausible mechanism for these contrasting roles of these cosolvents. The solute-cosolvent hydrophobic-interaction-induced orientational alignment of an interfacial cosolvent molecule determines whether the involvement of the cosolvent molecules in H-bonding with solvent water in the interface is akin to the bulk region or not.

How do glycerol and dimethyl sulphoxide affect local tetrahedral structure of water around a nonpolar solute at low temperature? Importance of preferential interaction

NASA Astrophysics Data System (ADS)

Daschakraborty, Snehasis

2018-04-01

Glycerol and dimethyl sulphoxide (DMSO) have vital roles in cryoprotection of living cells, tissues, etc. The above action has been directly linked with disruption of hydrogen (H-) bond structure and dynamics of water by these cosolvents at bulk region and around various complex units, such as peptide, amino acid, protein, and lipid membrane. However, the disruption of the local structure of the water solvent around a purely hydrophobic solute is still not studied extensively. The latter is also important in the context of stabilization of protein from cold denaturation. Through all-atom molecular dynamics simulation, we have investigated the comparative effect of glycerol and DMSO on the orientational order of water around a nonpolar solute at -5 °C. A steady reduction of the tetrahedral order of water is observed at bulk (>10 Å distance from the solute) and solute interface (<5.5 Å distance from the solute) with increasing the cosolvent concentration. Contrasting roles of glycerol and DMSO have been evidenced. While DMSO affects the H-bond structure of the interfacial water more than that of the bulk water, glycerol affects the water structure almost uniformly at all regions around the solute. Furthermore, while glycerol helps to retain water molecules at the interface, DMSO significantly reduces the water content in that region. We have put forward a plausible mechanism for these contrasting roles of these cosolvents. The solute-cosolvent hydrophobic-interaction-induced orientational alignment of an interfacial cosolvent molecule determines whether the involvement of the cosolvent molecules in H-bonding with solvent water in the interface is akin to the bulk region or not.

Enhanced simulation software for rocket turbopump, turbulent, annular liquid seals

NASA Technical Reports Server (NTRS)

Padavala, Satya; Palazzolo, Alan

1994-01-01

One of the main objectives of this work is to develop a new dynamic analysis for liquid annular seals with arbitrary profile and to analyze a general distorted interstage seal of the space shuttle main engine high pressure oxygen turbopump (SSME-ATD-HPOTP). The dynamic analysis developed is based on a method originally proposed by Nelson and Nguyen. A simpler scheme based on cubic splines is found to be computationally more efficient and has better convergence properties at higher eccentricities. The first order solution of the original analysis is modified by including a more exact solution that takes into account the variation of perturbed variables along the circumference. A new set of equations for dynamic analysis are derived based on this more general model. A unified solution procedure that is valid for both Moody's and Hirs' friction models is presented. Dynamic analysis is developed for three different models: constant properties, variable properties, and thermal effects with variable properties. Arbitrarily varying seal profiles in both axial and circumferential directions are considered. An example case of an elliptical seal with varying degrees of axial curvature is analyzed in detail. A case study based on predicted clearances of an interstage seal of the SSME-ATD-HPOTP is presented. Dynamic coefficients based on external specified load are introduced to analyze seals that support a preload. The other objective of this work is to study the effect of large rotor displacements of SSME-ATD-HPOTP on the dynamics of the annular seal and the resulting transient motion. One task is to identify the magnitude of motion of the rotor about the centered position and establish limits of effectiveness of using current linear models. This task is accomplished by solving the bulk flow model seal governing equations directly for transient seal forces for any given type of motion, including motion with large eccentricities. Based on the above study, an equivalence is established between linearized coefficients based transient motion and the same motion as predicted by the original governing equations. An innovative method is developed to model nonlinearities in an annular seal based on dynamic coefficients computed at various static eccentricities. This method is thoroughly tested for various types of transient motion using bulk flow model results as a benchmark.

Facilitated fabrication of high strength silica aerogels using cellulose nanofibrils as scaffold.

PubMed

Fu, Jingjing; Wang, Siqun; He, Chunxia; Lu, Zexiang; Huang, Jingda; Chen, Zhilin

2016-08-20

Monolithic cellulose nanofibrils (CNF)-silica composite aerogels were successfully prepared by immersing CNF aerogels into a silica solution in a two-step sol-gel process (initial hydrolysis of tetraethyl orthosilicate (TEOS) followed by condensation of silica particles). Aerogels were characterized by SEM, BET surface area test, bulk density and silica content analysis, FTIR spectroscopy, and compression test. The form of SiO2 existing in the composite aerogel was the spherical individual particles coated on CNF fibrils. The pH value of condensation solution was found to have great influence on the properties of the composite aerogels. By varying the pH value of condensation atmosphere from 8 to 12, the bulk densities of composite aerogels were able to be linearly increased from 0.059gcm(-3) to 0.29gcm(-3)，and the silica content in the matrix sharply jumped from 3wt% to 79wt%. The porosities of the aerogels remained very high, between 85 and 96%, and the surface area of the composite aerogel reached up to 700.1m(2)g(-1). The compression properties of the composite aerogel improved greatly compared with those of the silica aerogel, about 8-30 times higher. Moreover, the compressive strength of the composite aerogel prepared in this work greatly exceeded the conventional insulation materials found in the recent commercial market, and without substantial increases in thermal conductivity. Hence, the findings of this research offer a promising application for composite aerogels and give a theoretical basis for developing new advanced materials. Copyright © 2016 Elsevier Ltd. All rights reserved.

Kaluza-Klein Bulk Viscous Fluid Cosmological Models and the Validity of the Second Law of Thermodynamics in f(R, T) Gravity

NASA Astrophysics Data System (ADS)

Samanta, Gauranga Charan; Myrzakulov, Ratbay; Shah, Parth

2017-04-01

The authors considered the bulk viscous fluid in f(R, T) gravity within the framework of Kaluza-Klein space time. The bulk viscous coefficient (ξ) expressed as ξ = {ξ_0} + {ξ_1}{{\\dot a} \\over a} + {ξ_2}{{\\ddot a} \\over {\\dot a}}, where ξ0, ξ1, and ξ2 are positive constants. We take p=(γ-1)ρ, where 0≤γ≤2 as an equation of state for perfect fluid. The exact solutions to the corresponding field equations are given by assuming a particular model of the form of f(R, T)=R+2f(T), where f(T)=λT, λ is constant. We studied the cosmological model in two stages, in first stage: we studied the model with no viscosity, and in second stage: we studied the model involve with viscosity. The cosmological model involve with viscosity is studied by five possible scenarios for bulk viscous fluid coefficient (ξ). The total bulk viscous coefficient seems to be negative, when the bulk viscous coefficient is proportional to {ξ _2}{{\\ddot a} \\over {\\dot a}}, hence, the second law of thermodynamics is not valid; however, it is valid with the generalised second law of thermodynamics. The total bulk viscous coefficient seems to be positive, when the bulk viscous coefficient is proportional to ξ = {ξ _1}{{\\dot a} \\over a} + {ξ _2}{{\\ddot a} \\over {\\dot a}} and ξ = {ξ _0} + {ξ _1}{{\\dot a} \\over a} + {ξ _2}{{\\ddot a} \\over {\\dot a}}, so the second law of thermodynamics and the generalised second law of thermodynamics is satisfied throughout the evolution. We calculate statefinder parameters of the model and observed that it is different from the ∧CDM model. Finally, some physical and geometrical properties of the models are discussed.

On the localisation of four-dimensional brane-world black holes: II. The general case

NASA Astrophysics Data System (ADS)

Kanti, P.; Pappas, N.; Pappas, T.

2016-01-01

We perform a comprehensive analysis of a number of scalar field theories in an attempt to find analytically five-dimensional, localised-on-the-brane, black-hole solutions. Extending a previous analysis, we assume a generalised Vaidya ansatz for the five-dimensional metric tensor that allows for a time-dependent, non-trivial profile of the mass function in terms of the bulk coordinate and a deviation from the over-restricting Schwarzschild-type solution on the brane. In order to support such a solution, we study a variety of theories including single or multiple scalar fields, with canonical or non-canonical kinetic terms, minimally or non-minimally coupled to gravity. We demonstrate that for such a metric ansatz and for a carefully chosen energy-momentum tensor which is non-isotropic in five dimensions, solutions that have the form of a Schwarzschild-(anti)de Sitter or Reissner-Nordstrom type of solution do emerge. However, the resulting profile of the mass function along the bulk coordinate, when allowed, is not the correct one for eliminating bulk singularities.

Relationship between Solvation Thermodynamics from IST and DFT Perspectives.

PubMed

Levy, Ronald M; Cui, Di; Zhang, Bin W; Matubayasi, Nobuyuki

2017-04-20

Inhomogeneous solvation theory (IST) and classical density functional theory (DFT) each provide a framework for relating distribution functions of solutions to their thermodynamic properties. As reviewed in this work, both IST and DFT can be formulated in a way that use two "end point" simulations, one of the pure solvent and the other of the solution, to determine the solute chemical potential and other thermodynamic properties of the solution and of subvolumes in regions local to the solute containing hydrating waters. In contrast to IST, where expressions for the excess energy and entropy of solution are the object of analysis, in the DFT end point formulation of the problem, the solute-solvent potential of mean force (PMF) plays a central role. The indirect part of the PMF corresponds to the lowest order (1-body) truncation of the IST expression. Because the PMF is a free energy function, powerful numerical methods can be used to estimate it. We show that the DFT expressions for the solute excess chemical potential can be written in a form which is local, involving integrals only over regions proximate to the solute. The DFT end point route to estimating solvation free energies provides an alternative path to that of IST for analyzing solvation effects on molecular recognition and conformational changes in solution, which can lead to new insights. In order to illustrate the kind of information that is contained in the solute-solvent PMF, we have carried out simulations of β-cyclodextrin in water. This solute is a well studied "host" molecule to which "guest" molecules bind; host-guest systems serve as models for molecular recognition. We illustrate the range of values the direct and indirect parts of the solute-solvent PMF can have as a water molecule is brought to the interface of β-cyclodextrin from the bulk; we discuss the "competition" between these two terms, and the role it plays in molecular recognition.

Depth of cure, flexural properties and volumetric shrinkage of low and high viscosity bulk-fill giomers and resin composites.

PubMed

Tsujimoto, Akimasa; Barkmeier, Wayne W; Takamizawa, Toshiki; Latta, Mark A; Miyazaki, Masashi

2017-03-31

The purpose of this study was to investigate the depth of cure, flexural properties and volumetric shrinkage of low and high viscosity bulk-fill giomers and resin composites. Depth of cure and flexural properties were determined according to ISO 4049, and volumetric shrinkage was measured using a dilatometer. The depths of cure of giomers were significantly lower than those of resin composites, regardless of photo polymerization times. No difference in flexural strength and modulus was found among either high or low viscosity bulk fill materials. Volumetric shrinkage of low and high viscosity bulk-fill resin composites was significantly less than low and high viscosity giomers. Depth of cure of both low and high viscosity bulk-fill materials is time dependent. Flexural strength and modulus of high viscosity or low viscosity bulk-fill giomer or resin composite materials are not different for their respective category. Resin composites exhibited less polymerization shrinkage than giomers.

Interfacial ion solvation: Obtaining the thermodynamic limit from molecular simulations

NASA Astrophysics Data System (ADS)

Cox, Stephen J.; Geissler, Phillip L.

2018-06-01

Inferring properties of macroscopic solutions from molecular simulations is complicated by the limited size of systems that can be feasibly examined with a computer. When long-ranged electrostatic interactions are involved, the resulting finite size effects can be substantial and may attenuate very slowly with increasing system size, as shown by previous work on dilute ions in bulk aqueous solution. Here we examine corrections for such effects, with an emphasis on solvation near interfaces. Our central assumption follows the perspective of Hünenberger and McCammon [J. Chem. Phys. 110, 1856 (1999)]: Long-wavelength solvent response underlying finite size effects should be well described by reduced models like dielectric continuum theory, whose size dependence can be calculated straightforwardly. Applied to an ion in a periodic slab of liquid coexisting with vapor, this approach yields a finite size correction for solvation free energies that differs in important ways from results previously derived for bulk solution. For a model polar solvent, we show that this new correction quantitatively accounts for the variation of solvation free energy with volume and aspect ratio of the simulation cell. Correcting periodic slab results for an aqueous system requires an additional accounting for the solvent's intrinsic charge asymmetry, which shifts electric potentials in a size-dependent manner. The accuracy of these finite size corrections establishes a simple method for a posteriori extrapolation to the thermodynamic limit and also underscores the realism of dielectric continuum theory down to the nanometer scale.

Thermal treatment induced modification of structural, surface and bulk magnetic properties of Fe61.5Co5Ni8Si13.5B9Nb3 metallic glass

NASA Astrophysics Data System (ADS)

Shah, M.; Satalkar, M.; Kane, S. N.; Ghodke, N. L.; Sinha, A. K.; Varga, L. K.; Teixeira, J. M.; Araujo, J. P.

2018-05-01

Effect of thermal annealing induced modification of structural, surface and bulk magnetic properties of Fe61.5Co5Ni8Si13.5B9Nb3 alloy is presented. The changes in properties were observed using synchrotron x-ray diffraction technique (SXRD), atomic force microscopy (AFM), magneto-optical kerr effect (MOKE) and bulk magnetic measurements. Significant variations on the both side of surface occur for the annealing temperature upto 500 °C promotes the surface crystallization. Surface roughness appears due to presence of nanocrystallization plays an important role in determining magnetic properties. Observed lower value of bulk coercivity Hc of 6.2 A/m annealed temperature at 450 °C/1 h ascribed to reduction of disorder as compared to the surface (both shiny and wheel side observed by MOKE measurement) whereas improvement of bulk saturation magnetization with annealing temperature indicates first near neighbor shell of Fe atoms are surrounded by Fe atoms. Evolution of coercivity of surface and bulk with annealing temperature has been presented in conjunction with the structural observations.

Investigation of thermodynamic properties of metal-oxide catalysts

NASA Astrophysics Data System (ADS)

Shah, Parag Rasiklal

An apparatus for Coulometric Titration was developed and used to measure the redox isotherms (i.e. oxygen fugacity P(O2) vs oxygen stoichiometry) of ceria-zirconia solid solutions, mixed oxides of vanadia, and vanadia supported on ZrO2. This data was used to correlate the redox thermodynamics of these oxides to their structure and catalytic properties. From the redox isotherms measured between 873 K and 973 K, the differential enthalpies of oxidation (DeltaH) for Ce0.81Zr0.19O 2.0 and Ce0.25Zr0.75O2.0 were determined, and they were found to be independent of extent of reduction or composition of the solid solution. They were also lower than DeltaH for ceria, which explains the better redox properties of ceria-zirconia solid solutions. The oxidation was driven by entropy in the low reduction region, and a structural model was proposed to explain the observed entropy effects. Redox isotherms were also measured for a number of bulk vanadates between 823 K and 973 K. DeltaG, DeltaH and DeltaS were reported for V 2O5, Mg3(VO4)2, CeVO 4 and ZrV2O7 along with DeltaG values for AlVO 4, LaVO4, CrVO4. V2O5 and ZrV2O7, which were the only oxides having V-O-V bonds, showed a two-step transition of vanadium for V+3↔V +4 and V+4↔V+5 equilibrium in the redox isotherms. The other oxides, all of which have only M-O-V (M=cation other than V), showed a direct one-step transition, V+3↔V +5. The nature of the M-atom also influenced the P(O2) at which the V+3↔V+5 transition occurs. Redox isotherms at 748 K were measured for vanadia supported on ZrO 2; with two different vanadia loadings corresponding to isolated vanadyls and polymeric vanadyls. The isotherm for the sample with isolated vanadyls showed a single-step transition, similar to the one seen in bulk vanadates with M-O-V linkages, while no such one-step transition was observed in the isotherm of the other sample. To study the affect of the varying redox properties of the vanadium-based catalysts on oxidation rates, kinetic studies were performed for methanol and propane oxidation reactions on some of these catalysts. The results suggested that there was no effect of thermodynamic properties of these catalysts on the rates of these oxidation reactions.

Growth and Characteristics of Bulk Single Crystals Grown from Solution on Earth and in Microgravity

NASA Technical Reports Server (NTRS)

Aggarwal, M. D.; Batra, A. K.; Lal, R. B.; Penn, Benjamin G.; Frazier, Donald O.

2011-01-01

The growth of crystals has been of interest to physicists and engineers for a long time because of their unique properties. Single crystals are utilized in such diverse applications as pharmaceuticals, computers, infrared detectors, frequency measurements, piezoelectric devices, a variety of high technology devices and sensors. Solution crystal growth is one of the important techniques to grow a variety of crystals when the material decomposes at the melting point and a suitable solvent is available to make a saturated solution at a desired temperature. In this chapter an attempt is made to give some fundamentals of growing crystals from solution including improved designs of various crystallizers. Since the same solution crystal growth technique could not be used in microgravity, authors had proposed a new cooled sting technique to grow crystals in space. Authors? experiences of conducting two space shuttle experiments relating to solution crystal growth are also detailed in this work. The complexity of these solution growth experiments to grow crystals in space are discussed. These happen to be some of the early experiments performed in space, and various lessons learned are described. A brief discussion of protein crystal growth that also shares basic principles of solution growth technique is given along with some flight hardware information for its growth in microgravity.

Alternative Measurement Configurations for Extracting Bulk Optical Properties Using an Integrating Sphere Setup.

PubMed

Thennadil, Suresh N; Chen, Yi-Chieh

2017-02-01

The usual approach for estimating bulk optical properties using an integrating sphere measurement setup is by acquiring spectra from three measurement modes namely collimated transmittance (T c ), total transmittance (T d ), and total diffuse reflectance (R d ), followed by the inversion of these measurements using the adding-doubling method. At high scattering levels, accurate acquisition of T c becomes problematic due to the presence of significant amounts of forward-scattered light in this measurement which is supposed to contain only unscattered light. In this paper, we propose and investigate the effectiveness of using alternative sets of integrating sphere measurements that avoid the use of T c and could potentially increase the upper limit of concentrations of suspensions at which bulk optical property measurements can be obtained in the visible-near-infrared (Vis-NIR) region of the spectrum. We examine the possibility of replacing T c with one or more reflectance measurements at different sample thicknesses. We also examine the possibility of replacing both the collimated (T c ) and total transmittance (T d ) measurements with reflectance measurements taken from different sample thicknesses. The analysis presented here indicates that replacing T c with a reflectance measurement can reduce the errors in the bulk scattering properties when scattering levels are high. When only multiple reflectance measurements are used, good estimates of the bulk optical properties can be obtained when the absorption levels are low. In addition, we examine whether there is any advantage in using three measurements instead of two to obtain the reduced bulk scattering coefficient and the bulk absorption coefficient. This investigation is made in the context of chemical and biological suspensions which have a much larger range of optical properties compared to those encountered with tissue.

Complex Behavior of Aqueous α-Cyclodextrin Solutions. Interfacial Morphologies Resulting from Bulk Aggregation.

PubMed

Hernandez-Pascacio, Jorge; Piñeiro, Ángel; Ruso, Juan M; Hassan, Natalia; Campbell, Richard A; Campos-Terán, José; Costas, Miguel

2016-07-05

The spontaneous aggregation of α-cyclodextrin (α-CD) molecules in the bulk aqueous solution and the interactions of the resulting aggregates at the liquid/air interface have been studied at 283 K using a battery of techniques: transmission electron microscopy, dynamic light scattering, dynamic surface tensiometry, Brewster angle microscopy, neutron reflectometry, and ellipsometry. We show that α-CD molecules spontaneously form aggregates in the bulk that grow in size with time. These aggregates adsorb to the liquid/air interface with their size in the bulk determining the adsorption rate. The material that reaches the interface coalesces laterally to form two-dimensional domains on the micrometer scale with a layer thickness on the nanometer scale. These processes are affected by the ages of both the bulk and the interface. The interfacial layer formed is not in fast dynamic equilibrium with the subphase as the resulting morphology is locked in a kinetically trapped state. These results reveal a surprising complexity of the parallel physical processes taking place in the bulk and at the interface of what might have seemed initially like a simple system.

Negative refraction and planar focusing based on parity-time symmetric metasurfaces.

PubMed

Fleury, Romain; Sounas, Dimitrios L; Alù, Andrea

2014-07-11

We introduce a new mechanism to realize negative refraction and planar focusing using a pair of parity-time symmetric metasurfaces. In contrast to existing solutions that achieve these effects with negative-index metamaterials or phase conjugating surfaces, the proposed parity-time symmetric lens enables loss-free, all-angle negative refraction and planar focusing in free space, without relying on bulk metamaterials or nonlinear effects. This concept may represent a pivotal step towards loss-free negative refraction and highly efficient planar focusing by exploiting the largely uncharted scattering properties of parity-time symmetric systems.

Aspects of the zero Λ limit in the AdS/CFT correspondence

NASA Astrophysics Data System (ADS)

Caldeira Costa, R. N.

2014-11-01

We examine the correspondence between QFT observables and bulk solutions in the context of AdS/CFT in the limit as the cosmological constant Λ →0 . We focus specifically on the spacetime metric and a nonbackreacting scalar in the bulk, compute the one-point functions of the dual operators, and determine the necessary conditions for the correspondence to admit a well-behaved zero-Λ limit. We discuss holographic renormalization in this limit and find that it requires schemes that partially break diffeomorphism invariance of the bulk theory. In the specific case of three bulk dimensions, we compute the zero-Λ limit of the holographic Weyl anomaly and reproduce the central charge that arises in the central extension of bms3 . We compute holographically the energy and momentum of those QFT states dual to flat cosmological solutions and to the Kerr solution and find an agreement with the bulk theory. We also compute holographically the renormalized two-point function of a scalar operator in the zero-Λ limit and find it to be consistent with that of a conformal operator in two dimensions fewer. Finally, our results can be used in a new definition of asymptotic Ricci flatness at null infinity based on the zero-Λ limit of asymptotically Einstein manifolds.

Fabrication of Bi2223 bulks with high critical current properties sintered in Ag tubes

NASA Astrophysics Data System (ADS)

Takeda, Yasuaki; Shimoyama, Jun-ichi; Motoki, Takanori; Kishio, Kohji; Nakashima, Takayoshi; Kagiyama, Tomohiro; Kobayashi, Shin-ichi; Hayashi, Kazuhiko

2017-03-01

Randomly grain oriented Bi2223 sintered bulks are one of the representative superconducting materials having weak-link problem due to very short coherence length particularly along the c-axis, resulting in poor intergrain Jc properties. In our previous studies, sintering and/or post-annealing under moderately reducing atmospheres were found to be effective for improving grain coupling in Bi2223 sintered bulks. Further optimizations of the synthesis process for Bi2223 sintered bulks were attempted in the present study to enhance their intergrain Jc. Effects of applied pressure of uniaxial pressing and sintering conditions on microstructure and superconducting properties have been systematically investigated. The best sample showed intergrain Jc of 2.0 kA cm-2 at 77 K and 8.2 kA cm-2 at 20 K, while its relative density was low ∼65%. These values are quite high as for a randomly oriented sintered bulk of cuprate superconductors.

Electrochemical quartz crystal microbalance analysis of the oxygen reduction reaction on Pt-based electrodes. Part 2: adsorption of oxygen species and ClO4(-) anions on Pt and Pt-Co alloy in HClO4 solutions.

PubMed

Omura, J; Yano, H; Tryk, D A; Watanabe, M; Uchida, H

2014-01-14

To gain deeper insight into the role of adsorbed oxygenated species in the O2 reduction reaction (ORR) kinetics on platinum and platinum-cobalt alloys for fuel cells, we carried out a series of measurements with the electrochemical quartz crystal microbalance (EQCM) and the rotating disk electrode (RDE) in acid solution. The effects of anion adsorption on the activities for the ORR were first assessed in HClO4 and HF electrolyte solutions at various concentrations. In our previous work (Part 1), we reported that the perchlorate anion adsorbs specifically on bulk-Pt, with a Frumkin-Temkin isotherm, that is, a linear relationship between Δm and log[HClO4]. Here, we find that the specific adsorption on the Pt-skin/Pt3Co alloy was significantly stronger than that on bulk-Pt, in line with its modified electronic properties. The kinetically controlled current density j(k) for the O2 reduction at the Pt-skin/Pt3Co-RDE was about 9 times larger than that of the bulk-Pt-RDE in 0.01 M HClO4 saturated with air, but the j(k) values on Pt-skin/Pt3Co decreased with increasing [HClO4] more steeply than in the case of Pt, due to the blocking of the active sites by the specifically adsorbed ClO4(-). We have detected reversible mass changes for one or more adsorbed oxygen-containing species (Ox = O2, O, OH, H2O) on the Pt-skin/Pt3Co-EQCM and Pt-EQCM in O2-saturated and He-purged 0.01 M HClO4 solutions, in which the specific adsorption of ClO4(-) anions was negligible. The coverages of oxygen species θ(Ox) on the Pt-skin/Pt3Co in the potential range from 0.86 to 0.96 V in the O2-saturated solution were found to be larger than those on pure Pt, providing strong evidence that the higher O2 reduction activity on the Pt3Co is correlated with higher θ(Ox), contrary to the conventional view.

Nanotechnology: From Science Fiction to Reality

NASA Technical Reports Server (NTRS)

Siochi, Mia

2016-01-01

Nanotechnology promises unconventional solutions to challenging problems because of expectations that matter can be manipulated at the atomic scale to yield properties that exceed those predicted for bulk materials. The excitement at this possibility has been fueled by significant investments in this technology area. This talk will focus on three examples of where advances are being made to exploit unique properties made possible by nanoscale features for aerospace applications. The first two topics will involve the development of carbon nanotubes for (a) lightweight structural applications and (b) net shape fabricated multifunctional components. The third topic will highlight lessons learned from the demonstration of the effect of nanoengineered surfaces on insect residue adhesion. In all three cases, the approaches used to mature these emerging technologies are based on the acceleration of technology development through multidisciplinary collaborations.

Thermal Conductivity of a Nanoscale Yttrium Iron Garnet Thin-Film Prepared by the Sol-Gel Process

PubMed Central

2017-01-01

The thermal conductivity of a nanoscale yttrium iron garnet (Y3Fe5O12, YIG) thin-film prepared by a sol-gel method was evaluated using the ultrafast pump-probe technique in the present study. The thermoreflectance change on the surface of a 250 nm thick YIG film, induced by the irradiation of femtosecond laser pulses, was measured, and curve fitting of a numerical solution for the transient heat conduction equation to the experimental data was performed using the finite difference method in order to extract the thermal property. Results show that the film’s thermal conductivity is 22–83% higher than the properties of bulk YIG materials prepared by different fabrication techniques, reflecting the microstructural characteristics and quality of the film. PMID:28858249

Low temperature synthesis of Ru-Cu alloy nanoparticles with the compositions in the miscibility gap

NASA Astrophysics Data System (ADS)

Martynova, S. A.; Filatov, E. Yu.; Korenev, S. V.; Kuratieva, N. V.; Sheludyakova, L. A.; Plusnin, P. E.; Shubin, Yu. V.; Slavinskaya, E. M.; Boronin, A. I.

2014-04-01

A complex salt [Ru(NH3)5Cl][Cu(C2O4)2H2O]-the precursor of nanoalloys combining ruthenium and copper was prepared. It crystallizes in the monoclinic space group P21/n. Thermal properties of the prepared salt were examined in different atmospheres (helium, hydrogen, oxygen). Thermal decomposition of the precursor in inert atmosphere was thoroughly examined and the intermediate products were characterized. Experimental conditions for preparation of copper-rich (up to 12 at% of copper) metastable solid solution CuxRu1-x (based on Ru structure) were optimized, what is in sharp contrast to the bimetallic miscibility gap known for the bulk counterparts in a wide composition range. Catalytic properties of copper-ruthenium oxide composite were tested in catalytic oxidation of CO.

Zinc complexes as fluorescent chemosensors for nucleic acids: new perspectives for a "boring" element.

PubMed

Terenzi, Alessio; Lauria, Antonino; Almerico, Anna Maria; Barone, Giampaolo

2015-02-28

Zinc(II) complexes are effective and selective nucleic acid-binders and strongly fluorescent molecules in the low energy range, from the visible to the near infrared. These two properties have often been exploited to quantitatively detect nucleic acids in biological samples, in both in vitro and in vivo models. In particular, the fluorescent emission of several zinc(II) complexes is drastically enhanced or quenched by the binding to nucleic acids and/or upon visible light exposure, in a different fashion in bulk solution and when bound to DNA. The twofold objective of this perspective is (1) to review recent utilisations of zinc(II) complexes as selective fluorescent probes for nucleic acids and (2) to highlight their novel potential applications as diagnostic tools based on their photophysical properties.

Tailoring properties of reticulated vitreous carbon foams with tunable density

NASA Astrophysics Data System (ADS)

Smorygo, Oleg; Marukovich, Alexander; Mikutski, Vitali; Stathopoulos, Vassilis; Hryhoryeu, Siarhei; Sadykov, Vladislav

2016-06-01

Reticulated vitreous carbon (RVC) foams were manufactured by multiple replications of a polyurethane foam template structure using ethanolic solutions of phenolic resin. The aims were to create an algorithm of fine tuning the precursor foam density and ensure an open-cell reticulated porous structure in a wide density range. The precursor foams were pyrolyzed in inert atmospheres at 700°C, 1100°C and 2000°C, and RVC foams with fully open cells and tunable bulk densities within 0.09-0.42 g/cm3 were synthesized. The foams were characterized in terms of porous structure, carbon lattice parameters, mechanical properties, thermal conductivity, electric conductivity, and corrosive resistance. The reported manufacturing approach is suitable for designing the foam microstructure, including the strut design with a graded microstructure.

Tribological Properties of Aluminium Alloy Composites Reinforced with Multi-Layer Graphene—The Influence of Spark Plasma Texturing Process

PubMed Central

Kostecki, Marek; Woźniak, Jarosław; Cygan, Tomasz; Petrus, Mateusz; Olszyna, Andrzej

2017-01-01

Self-lubricating composites are designed to obtain materials that reduce energy consumption, improve heat dissipation between moving bodies, and eliminate the need for external lubricants. The use of a solid lubricant in bulk composite material always involves a significant reduction in its mechanical properties, which is usually not an optimal solution. The growing interest in multilayer graphene (MLG), characterised by interesting properties as a component of composites, encouraged the authors to use it as an alternative solid lubricant in aluminium matrix composites instead of graphite. Aluminium alloy 6061 matrix composite reinforced with 2–15 vol % of MLG were synthesised by the spark plasma sintering process (SPS) and its modification, spark plasma texturing (SPT), involving deformation of the pre-sintered body in a larger diameter matrix. It was found that the application of the SPT method improves the density and hardness of the composites, resulting in improved tribological properties, particularly in the higher load regime. PMID:28796172

Nanomaterials for Functional Textiles and Fibers

NASA Astrophysics Data System (ADS)

Rivero, Pedro J.; Urrutia, Aitor; Goicoechea, Javier; Arregui, Francisco J.

2015-12-01

Nanoparticles are very interesting because of their surface properties, different from bulk materials. Such properties make possible to endow ordinary products with new functionalities. Their relatively low cost with respect to other nano-additives make them a promising choice for industrial mass-production systems. Nanoparticles of different kind of materials such as silver, titania, and zinc oxide have been used in the functionalization of fibers and fabrics achieving significantly improved products with new macroscopic properties. This article reviews the most relevant approaches for incorporating such nanoparticles into synthetic fibers used traditionally in the textile industry allowing to give a solution to traditional problems for textiles such as the microorganism growth onto fibers, flammability, robustness against ultraviolet radiation, and many others. In addition, the incorporation of such nanoparticles into special ultrathin fibers is also analyzed. In this field, electrospinning is a very promising technique that allows the fabrication of ultrathin fiber mats with an extraordinary control of their structure and properties, being an ideal alternative for applications such as wound healing or even functional membranes.

Nanomaterials for Functional Textiles and Fibers.

PubMed

Rivero, Pedro J; Urrutia, Aitor; Goicoechea, Javier; Arregui, Francisco J

2015-12-01

Nanoparticles are very interesting because of their surface properties, different from bulk materials. Such properties make possible to endow ordinary products with new functionalities. Their relatively low cost with respect to other nano-additives make them a promising choice for industrial mass-production systems. Nanoparticles of different kind of materials such as silver, titania, and zinc oxide have been used in the functionalization of fibers and fabrics achieving significantly improved products with new macroscopic properties. This article reviews the most relevant approaches for incorporating such nanoparticles into synthetic fibers used traditionally in the textile industry allowing to give a solution to traditional problems for textiles such as the microorganism growth onto fibers, flammability, robustness against ultraviolet radiation, and many others. In addition, the incorporation of such nanoparticles into special ultrathin fibers is also analyzed. In this field, electrospinning is a very promising technique that allows the fabrication of ultrathin fiber mats with an extraordinary control of their structure and properties, being an ideal alternative for applications such as wound healing or even functional membranes.

Tensile strengths of polyamide based 3D printed polymers in liquid nitrogen

NASA Astrophysics Data System (ADS)

Cruz, P.; Shoemake, E. D.; Adam, P.; Leachman, J.

2015-12-01

Advances in additive manufacturing technology have made 3D printing a viable solution for many industries, allowing for the manufacture of designs that could not be made through traditional subtractive methods. Applicability of additive manufacturing in cryogenic applications is hindered, however, by a lack of accurate material properties information. Nylon is available for printing using fused deposition modeling (FDM) and selective laser sintering (SLS). We selected 5 SLS (DuraForm® EX, DuraForm® HST, DuraForm® PA, PA 640-GSL, and PA 840-GSL) and 2 FDM (Nylon 12, ULTEM) nylon variants based on the bulk material properties and printed properties at room temperature. Tensile tests were performed on five samples of each material while immersed in liquid nitrogen at approximately 77 Kelvin. Samples were tested in XY and, where available, Z printing directions to determine influence on material properties. Results show typical SLS and FDM nylon ultimate strength retention at 77 K, when compared to (extruded or molded) nylon ultimate strength.

Properties of medium-density fiberboard related to hardwood specific gravity

Treesearch

George E. Woodson

1976-01-01

Boards of acceptable quality were made from barky material, pressure-refined from 14 species of southern hardwoods. Static bending and tensile properties (parallel to surface) of specimens were negatively correlated to stem specific gravity (wood plus bark), chip bulk density, and fiber bulk density. Bending and tensile properties increased with increasing...

Bulk Crystal Growth of Piezoelectric PMN-PT Crystals Using Gradient Freeze Technique for Improved SHM Sensors

NASA Technical Reports Server (NTRS)

Aggarwal, Mohan D.; Kochary, F.; Penn, Benjamin G.; Miller, Jim

2007-01-01

There has been a growing interest in recent years in lead based perovskite ferroelectric and relaxor ferroelectric solid solutions because of their excellent dielectric, piezoelectric and electrostrictive properties that make them very attractive for various sensing, actuating and structural health monitoring (SHM) applications. We are interested in the development of highly sensitive and efficient PMN-PT sensors based on large single crystals for the structural health monitoring of composite materials that may be used in future spacecrafts. Highly sensitive sensors are needed for detection of defects in these materials because they often tend to fail by distributed and interacting damage modes and much of the damage occurs beneath the top surface of the laminate and not detectable by visual inspection. Research is being carried out for various combinations of solid solutions for PMN-PT piezoelectric materials and bigger size crystals are being sought for improved sensor applications. Single crystals of this material are of interest for sensor applications because of their high piezoelectric coefficient (d33 greater than 1700 pC/N) and electromechanical coefficients (k33 greater than 0.90). For comparison, the commonly used piezoelectric ceramic lead zirconate titanate (PZT) has a d33 of about 600 pC/N and electromechanical coefficients k33 of about 0.75. At the present time, these piezoelectric relaxor crystals are grown by high temperature flux growth method and the size of these crystals are rather small (3x4x5 mm(exp 3). In the present paper, we have attempted to grow bulk single crystals of PMN-PT in a 2 inch diameter platinum crucible and successfully grown a large size crystal of 67%PMN-33%PT using the vertical gradient freeze technique with no flux. Piezoelectric properties of the grown crystals are investigated. PMN-PT plates show excellent piezoelectric properties. Samples were poled under an applied electric field of 5 kV/cm. Dielectric properties at a frequency of 1 kHz are examined. The grown PMN-PT crystals show typical relaxor dielectric properties. Additionally, the thermal properties of the sample are tested. The results are in good agreement with those found in the literature and some are reported for the first time.

David Adler Lectureship Award: n-point Correlation Functions in Heterogeneous Materials.

NASA Astrophysics Data System (ADS)

Torquato, Salvatore

2009-03-01

The determination of the bulk transport, electromagnetic, mechanical, and optical properties of heterogeneous materials has a long and venerable history, attracting the attention of some of the luminaries of science, including Maxwell, Lord Rayleigh, and Einstein. The bulk properties can be shown to depend rigorously upon infinite sets of various n-point correlation functions. Many different types of correlation functions arise, depending on the physics of the problem. A unified approach to characterize the microstructure and bulk properties of a large class of disordered materials is developed [S. Torquato, Random Heterogeneous Materials: Microstructure and Macroscopic Properties (Springer-Verlag, New York, 2002)]. This is accomplished via a canonical n-point function Hn from which one can derive exact analytical expressions for any microstructural function of interest. This microstructural information can then be used to estimate accurately the bulk properties of the material. Unlike homogeneous materials, seemingly different bulk properties (e.g., transport and mechanical properties) of a heterogeneous material can be linked to one another because of the common microstructure that they share. Such cross-property relations can be used to estimate one property given a measurement of another. A recently identified decorrelation principle, roughly speaking, refers to the phenomenon that unconstrained correlations that exist in low-dimensional disordered materials vanish as the space dimension becomes large. Among other results, this implies that in sufficiently high dimensions the densest spheres packings may be disordered (rather than ordered) [S. Torquato and F. H. Stillinger, ``New Conjectural Lower Bounds on the Optimal Density of Sphere Packings," Experimental Mathematics, 15, 307 (2006)].

Influence of Osmotic Drying with an Aqueous Poly(ethylene Glycol) Liquid Desiccant on Alumina Objects Gelcast with Gelatin

DOE PAGES

Hammel, E. C.; Campa, J. A.; Armbrister, C. E.; ...

2017-09-06

Gelcasting and liquid desiccant drying are novel forming and drying methods used to mitigate common issues associated with the fabrication of complex advanced ceramic objects. Here, the molecular weight and osmotic pressure of aqueous poly(ethylene glycol) (PEG) desiccant solutions were simultaneously varied to understand their influence on the net mass loss rates of gelcast alumina samples prepared using gelatin as a gelling agent. Additionally, the amount of PEG diffusion and water diffusion to and from the ceramic samples after 150 min of immersion in the liquid desiccant was correlated to the solution properties as was the final bulk density ofmore » the sintered samples. Furthermore, solutions with high molecular weight and low osmotic pressure resulted in low PEG gain and low water loss, while solutions with low molecular weight and high osmotic pressure resulted in high PEG gain and high water loss. In some cases, more than 40 wt% of the total water per sample was removed through the liquid desiccant drying process.« less

Influence of Osmotic Drying with an Aqueous Poly(ethylene Glycol) Liquid Desiccant on Alumina Objects Gelcast with Gelatin

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

Hammel, E. C.; Campa, J. A.; Armbrister, C. E.

Gelcasting and liquid desiccant drying are novel forming and drying methods used to mitigate common issues associated with the fabrication of complex advanced ceramic objects. Here, the molecular weight and osmotic pressure of aqueous poly(ethylene glycol) (PEG) desiccant solutions were simultaneously varied to understand their influence on the net mass loss rates of gelcast alumina samples prepared using gelatin as a gelling agent. Additionally, the amount of PEG diffusion and water diffusion to and from the ceramic samples after 150 min of immersion in the liquid desiccant was correlated to the solution properties as was the final bulk density ofmore » the sintered samples. Furthermore, solutions with high molecular weight and low osmotic pressure resulted in low PEG gain and low water loss, while solutions with low molecular weight and high osmotic pressure resulted in high PEG gain and high water loss. In some cases, more than 40 wt% of the total water per sample was removed through the liquid desiccant drying process.« less

Effect of the Crystal Structure on the Electrical Properties of Thin-Film PZT Structures

NASA Astrophysics Data System (ADS)

Delimova, L. A.; Gushchina, E. V.; Zaitseva, N. V.; Seregin, D. S.; Vorotilov, K. A.; Sigov, A. S.

2018-03-01

A new method of two-stage crystallization of lead zirconate-titanate (PZT) films using a seed sublayer with a low excess lead content has been proposed and realized. A seed layer with a strong texture of perovskite Pe(111) grains is formed from a solution with a lead excess of 0-5 wt %; the fast growth of the grains is provided by the deposition of the main film from a solution with high lead content. As a result, a strong Pe(111) texture with complete suppression of the Pe(100) orientation forms. An analysis of current-voltage dependences of the transient currents and the distributions of the local conductivity measured by the contact AFM method reveals two various mechanisms of current percolation that are determined by traps in the bulk and at the perovskite grain interfaces.

Compressive buckling of a rectangular nanoplate

NASA Astrophysics Data System (ADS)

Bochkarev, A. O.

2018-05-01

This paper considers the constitutive relations of the nanoplate theory with surface stresses taken into account according to the original or complete Gurtin-Murdoch (GM) model and according to the simplified strain-consistent GM model (which does not include any non-strain terms in the surface stress-strain relation). It is shown that the potential energy of a deformed nanoplate according to both GM models preserves the classical structure using the redefined elastic moduli (effective tangential and flexural elastic properties, which contain the characteristics of bulk phase and a surface). This allows to apply the known solutions and methods from macroplates to nanoplates. As example, it is shown that the critical load of the compressive buckling of a nanoplate according to the complete and strain-consistent GM models has the difference between two solutions no more than 1.5%.

A soft-wall dilaton

DOE PAGES

Cox, Peter; Gherghetta, Tony

2015-02-02

Here, we study the properties of the dilaton in a soft-wall background using two solutions of the Einstein equations. These solutions contain an asymptotically AdS metric with a nontrivial scalar profile that causes both the spontaneous breaking of conformal invariance and the generation of a mass gap in the particle spectrum. We first present an analytic solution, using the superpotential method, that describes a CFT spontaneously broken by a finite dimensional operator in which a light dilaton mode appears in the spectrum. This represents a tuning in the vanishing of the quartic coupling in the effective potential that could bemore » naturally realised from an underlying supersymmetry. Instead, by considering a generalised analytic scalar bulk potential that quickly transitions at the condensate scale from a walking coupling in the UV to an order-one β-function in the IR, we obtain a naturally light dilaton. This provides a simple example for obtaining a naturally light dilaton from nearly-marginal CFT deformations in the more realistic case of a soft-wall background.« less

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

PubMed

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

2018-02-01

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

Structure and corrosion behaviour of electrodeposited Co-Mo/TiO2 nano-composite coatings

NASA Astrophysics Data System (ADS)

Krawiec, H.; Vignal, V.; Latkiewicz, M.; Herbst, F.

2018-01-01

The structure and the corrosion behaviour in the Ringer's solution of Co-Mo/TiO2 nano-composite coatings have been investigated. They consist of aggregates of TiO2 nanoparticles uniformly distributed in a Co-Mo alloy matrix (crystallite size of about 2 nm). Both nodular (thickness less than 20 μm) and globular structures (thickness greater than 20 μm) have been observed using field-emission scanning electron microscopy. Under potentiostatic control (in Ringer's solution), oxidation of the coating first occurs followed by (with increasing applied potential) both oxidation and selective dissolution of Co. At the OCP value, Co is oxidized in the form of Co2+-based compounds (CoO, Co(OH)2 or α-CoMoO4) in the coating. This process only occurs in the outermost part of the coating. Therefore, the bulk properties of the coating are not affected after long-term ageing in the Ringer's solution at OCP.

Effects of substituents in silyl groups on the absorption, fluorescence and structural properties of 1,3,6,8-tetrasilylpyrenes.

PubMed

Maeda, Hajime; Suzuki, Tsubasa; Segi, Masahito

2018-05-09

1,3,6,8-Tetrasilylpyrenes and related germyl and stannyl derivatives were synthesized, and their absorption and fluorescence spectroscopic and structural properties were elucidated. The results show that the UV-vis absorption maxima of these substances in CH2Cl2 solutions shift to longer wavelengths as the size of the alkyl groups and numbers of phenyl groups on silicon increase. Fluorescence quantum yields of tetrasilylpyrenes in cyclohexane are larger than that of pyrene, and a pentamethyldisilyl derivative has an emission efficiency of 0.79. Except in the case of the SiMe2H derivative, excimer emission was not observed in concentrated solutions of these substances. The SiMe2H and SiMe3 derivatives were shown to form CT complexes with tetracyanoethylene in CH2Cl2 solutions. The calculated energy barriers for rotation of the silyl groups about the Si-C bond increase as the steric bulk of the silyl group increases. 29Si NMR chemical shifts were found to depend on the sizes of the alkyl groups and numbers of phenyl groups. Data arising from theoretical calculations suggest that the silyl groups act as electron-donating groups, and the donating ability of the groups decreases in the order SiR3 > GeR3 > SnR3.

Ultraviolet-ozone surface modification for non-wetting hole transport materials based inverted planar perovskite solar cells with efficiency exceeding 18%

NASA Astrophysics Data System (ADS)

Xu, Xiuwen; Ma, Chunqing; Cheng, Yuanhang; Xie, Yue-Min; Yi, Xueping; Gautam, Bhoj; Chen, Shengmei; Li, Ho-Wa; Lee, Chun-Sing; So, Franky; Tsang, Sai-Wing

2017-08-01

Non-wetting hole transport materials (HTMs) have great potential in facilitating large-sized perovskite crystal growth and enhancing device stability by opposing moisture ingress, However, the severe non-wetting issue limits the wide application of these materials in low-temperature solution-processed inverted planar perovskite solar cells (PVSCs), and corresponding devices are rarely reported. Here, a facile ultraviolet-ozone (UVO) modification method is demonstrated to overcome this issue. By carefully controlling the UVO modification time, the surface wettability of poly-TPD can be tuned without affecting the bulk properties of the film, hence perovskite films with desired grain size and excellent coverage can be deposited via a one-step spin-coating method. Benefiting from the high-quality perovskite, well-matched energy level alignment and hydrophobic property of poly-TPD, the resulting PVSCs show a champion power conversion efficiency of 18.19% with significantly enhanced stability as compared to the PEDOT:PSS counterparts. Moreover, the UVO modification approach also demonstrates its validity when being extended to other hydrophobic HTMs. This work not only provides a general strategy to broaden the selection pool of HTMs for solution-processed inverted planar PVSCs, but also may triggers the exploration of more advanced strategies to make non-wetting HTMs applicable in solution-processed inverted planar PVSCs.

Ions, metabolites, and cells: Water as a reporter of surface conditions during bacterial growth.

PubMed

Jarisz, Tasha A; Lane, Sarah; Gozdzialski, Lea; Hore, Dennis K

2018-06-14

Surface-specific nonlinear vibrational spectroscopy, combined with bulk solution measurements and imaging, is used to study the surface conditions during the growth of E. coli. As a result of the silica high surface charge density, the water structure at the silica-aqueous interface is known to be especially sensitive to pH and ionic strength, and surface concentration profiles develop that can be appreciably different from the bulk solution conditions. We illustrate that, in the presence of growing cells, a unique surface micro-environment is established as a result of metabolites accumulating on the silica surface. Even in the subsequent absence of the cells, this surface layer works to reduce the interfacial ionic strength as revealed by the enhanced signal from surface water molecules. In the presence of growing cells, an additional boost in surface water signal is attributed to a local pH that is higher than that of the bulk solution.

Ions, metabolites, and cells: Water as a reporter of surface conditions during bacterial growth

NASA Astrophysics Data System (ADS)

Jarisz, Tasha A.; Lane, Sarah; Gozdzialski, Lea; Hore, Dennis K.

2018-06-01

Surface-specific nonlinear vibrational spectroscopy, combined with bulk solution measurements and imaging, is used to study the surface conditions during the growth of E. coli. As a result of the silica high surface charge density, the water structure at the silica-aqueous interface is known to be especially sensitive to pH and ionic strength, and surface concentration profiles develop that can be appreciably different from the bulk solution conditions. We illustrate that, in the presence of growing cells, a unique surface micro-environment is established as a result of metabolites accumulating on the silica surface. Even in the subsequent absence of the cells, this surface layer works to reduce the interfacial ionic strength as revealed by the enhanced signal from surface water molecules. In the presence of growing cells, an additional boost in surface water signal is attributed to a local pH that is higher than that of the bulk solution.

Thermal transport properties of bulk and monolayer MoS2: an ab-initio approach

NASA Astrophysics Data System (ADS)

Bano, Amreen; Khare, Preeti; Gaur, N. K.

2017-05-01

The transport properties of semiconductors are key to the performance of many solid-state devices (transistors, data storage, thermoelectric cooling and power generation devices, etc). In recent years simulation tools based on first-principles calculations have been greatly improved, being able to obtain the fundamental ground-state properties of materials accurately. The quasi harmonic thermal properties of bulk and monolayer of MoS2 has been computed with ab initio periodic simulations based of density functional theory (DFT). The temperature dependence of bulk modulus, specific heat, thermal expansion and gruneisen parameter have been calculated in our work within the temperature range of 0K to 900K with projected augmented wave (PAW) method using generalized gradient approximation (GGA). Our results show that the optimized lattice parameters are in good agreement with the earlier reported works and also for thermoelastic parameter, i.e. isothermal bulk modulus (B) at 0K indicates that monolayer MoS2 (48.5 GPa)is more compressible than the bulk structure (159.23 GPa). The thermal expansion of monolayer structure is slightly less than the bulk. Similarly, other parameters like heat capacity and gruneisen parameter shows different nature which is due to the confinement of 3 dimensional structure to 2 dimension (2D) for improving its transport characteristics.

In vitro analysis of the physical properties of contact lens blister pack solutions.

PubMed

Menzies, Kara L; Jones, Lyndon

2011-04-01

Since the initial development of silicone hydrogels, many modifications to the bulk and surface properties of the lenses have been undertaken to improve the wettability and comfort of the lenses. Recently, manufacturers have incorporated various "wetting agents" or surface-active agents into the blister packaging solutions (BPSs) of the lenses to improve initial comfort of the lens on eye. The purpose of this study was to measure and compare the pH, surface tension (ST), viscosity, and osmolality of BPSs for a variety of silicone hydrogel and polyHEMA-based hydrogel lenses. In addition, two saline solutions were tested for comparison purposes. The pH, osmolality, ST, and viscosity were measured for the BPSs for lotrafilcon B and lotrafilcon A and lotrafilcon B with a "modified BPS" (m-lotrafilcon A, m-lotrafilcon B) (CIBA Vision, Duluth, GA); balafilcon A (Bausch & Lomb, Rochester, NY); galyfilcon A, senofilcon A, and narafilcon A (Johnson & Johnson, Jacksonville, FL); and comfilcon A and enfilcon A (CooperVision, Pleasanton, CA) and BPSs from two conventional polyHEMA-based materials-etafilcon A (Johnson & Johnson) and omafilcon A (CooperVision). The two saline solutions tested were Unisol (Alcon, Fort Worth, TX) and Softwear Saline (CIBA Vision). The pH results for the two saline solutions and all BPSs remained in the pH range of tears (6.6-7.8). The ST of the modified BPS was significantly lower (p < 0.01) than the original non-modified BPS. Viscosity measurements ranged between 0.90 and 1.00 cP for all BPSs and saline solutions, except for the modified BPS, which had significantly higher viscosities (p < 0.001). Osmolality measurements were not significantly different (p > 0.05) between BPSs made by the same manufacturer but were significantly different compared with BPSs made by different manufacturers (p < 0.05). The incorporation of wetting agents and surfactants into BPSs does alter the physical properties of the BPSs, which may have clinical implications regarding initial in-eye comfort.

Molecular modeling the microstructure and phase behavior of bulk and inhomogeneous complex fluids

NASA Astrophysics Data System (ADS)

Bymaster, Adam

Accurate prediction of the thermodynamics and microstructure of complex fluids is contingent upon a model's ability to capture the molecular architecture and the specific intermolecular and intramolecular interactions that govern fluid behavior. This dissertation makes key contributions to improving the understanding and molecular modeling of complex bulk and inhomogeneous fluids, with an emphasis on associating and macromolecular molecules (water, hydrocarbons, polymers, surfactants, and colloids). Such developments apply broadly to fields ranging from biology and medicine, to high performance soft materials and energy. In the bulk, the perturbed-chain statistical associating fluid theory (PC-SAFT), an equation of state based on Wertheim's thermodynamic perturbation theory (TPT1), is extended to include a crossover correction that significantly improves the predicted phase behavior in the critical region. In addition, PC-SAFT is used to investigate the vapor-liquid equilibrium of sour gas mixtures, to improve the understanding of mercaptan/sulfide removal via gas treating. For inhomogeneous fluids, a density functional theory (DFT) based on TPT1 is extended to problems that exhibit radially symmetric inhomogeneities. First, the influence of model solutes on the structure and interfacial properties of water are investigated. The DFT successfully describes the hydrophobic phenomena on microscopic and macroscopic length scales, capturing structural changes as a function of solute size and temperature. The DFT is used to investigate the structure and effective forces in nonadsorbing polymer-colloid mixtures. A comprehensive study is conducted characterizing the role of polymer concentration and particle/polymer size ratio on the structure, polymer induced depletion forces, and tendency towards colloidal aggregation. The inhomogeneous form of the association functional is used, for the first time, to extend the DFT to associating polymer systems, applicable to any association scheme. Theoretical results elucidate how reversible bonding governs the structure of a fluid near a surface and in confined environments, the molecular connectivity (formation of supramolecules, star polymers, etc.) and the phase behavior of the system. Finally, the DFT is extended to predict the inter- and intramolecular correlation functions of polymeric fluids. A theory capable of providing such local structure is important to understanding how local chemistry, branching, and bond flexibility affect the thermodynamic properties of polymers.

Rheological Properties of Commercially Available Hyaluronic Acid Products in the United States for the Treatment of Osteoarthritis Knee Pain

PubMed Central

Nicholls, Mathew; Manjoo, Ajay; Shaw, Peter; Niazi, Faizan; Rosen, Jeffrey

2018-01-01

Objective: The inconsistent results within the current literature regarding the efficacy of intra-articular-hyaluronic acid (IA-HA) for the treatment of knee osteoarthritis (OA) have been suggested to be due to intrinsic differences between individual HA products. The purpose of this investigation is to define the rheological differences between currently available HA products in the United States at the time of this study for the treatment of knee OA, which will help elaborate on the appropriateness of classifying HA products as a class opposed to as individual agents. Methods: The rheological parameters for Euflexxa, Orthovisc, Supartz, Monovisc, Synvisc, Synvisc-One, Gel-One, and Hyalgan were obtained with a TA AR 2000 EX Rheometer with a cone-plate geometry (40-mm plate diameter and a 2° cone angle) at room temperature. Results: The bulk rheological parameters of the different products suggest molecular structures traversing the range of dilute solution (Hyalgan, Supartz), semidilute solution (Euflexxa, Orthovisc), entangled solutions (Monovisc, Synvisc, Synvisc-One), and even gel-like (Gel-One) behavior. Conclusions: Due to the differences in rheological properties between IA-HA products, the universal assessment of these products as a class may not be appropriate. Instead, it may be more appropriate to assess each product individually. Future research should aim to link these differences in rheological properties to the differences in clinical efficacy seen across these IA-HA products. PMID:29326532

Spherically symmetric solutions and gravitational collapse in brane-worlds

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

Heydari-Fard, Malihe; Sepangi, Hamid R., E-mail: heydarifard@qom.ac.ir, E-mail: hr-sepangi@sbu.ac.ir

2009-02-15

We consider spherically symmetric solutions within the context of brane-world theory without mirror symmetry or any form of junction conditions. For a constant curvature bulk, we obtain the modified Tolman-Oppenheimer-Volkoff (TOV) interior solutions in two cases where one is matched to a schwarzschild-de Sitter exterior while the other is consistent with an exterior solution whose structure can be used to explain the galaxy rotation curves without postulating dark matter. We also find the upper bound to the mass of a static brane-world star and show that the influence of the bulk effects on the interior solutions is small. Finally, wemore » investigate the gravitational collapse on the brane and show that the exterior of a collapsing star can be static in this scenario.« less

Effect of accelerated aging on the viscoelastic properties of a medical grade silicone.

PubMed

Mahomed, Aziza; Hukins, David W L; Kukureka, Stephen N

2015-01-01

The viscoelastic properties of cylinders (diameter 5 mm, height 2.2 ± 0.2 mm) of Nagor silicone elastomer of medium hardness, were investigated before and after the specimens had undergone accelerated aging in saline solution at 70°C for 38, 76 and 114 days (to simulate aging at 37°C, for 1, 2 and 3 years, respectively). All sets of specimens were immersed in physiological saline solution at 37°C during testing and the properties were measured using dynamic mechanical analysis (DMA). A sinusoidal cyclic compression of 40 N ± 5 N was applied over a frequency range, f, of 0.02-25 Hz. Values of the storage, E', and loss, E″, moduli were found to depend on f; the dependence of E' or E″ on the logarithm (base 10) of f was represented by a second-order polynomial. After accelerated aging, the E' and E″ values did not increase significantly (p<0.05). Furthermore, scanning electron microscopy (SEM) showed that accelerated aging did not affect the surface morphology of silicone. Attenuated total reflectance Fourier transform infra-red spectroscopy (ATR-FTIR) showed that accelerated aging had a negligible effect on the surface chemical structures of the material. Differential scanning calorimetry (DSC) showed no changes to the bulk properties of silicone, following accelerated aging.

Separating Bulk and Surface Contributions to Electronic Excited-State Processes in Hybrid Mixed Perovskite Thin Films via Multimodal All-Optical Imaging.

PubMed

Simpson, Mary Jane; Doughty, Benjamin; Das, Sanjib; Xiao, Kai; Ma, Ying-Zhong

2017-07-20

A comprehensive understanding of electronic excited-state phenomena underlying the impressive performance of solution-processed hybrid halide perovskite solar cells requires access to both spatially resolved electronic processes and corresponding sample morphological characteristics. Here, we demonstrate an all-optical multimodal imaging approach that enables us to obtain both electronic excited-state and morphological information on a single optical microscope platform with simultaneous high temporal and spatial resolution. Specifically, images were acquired for the same region of interest in thin films of chloride containing mixed lead halide perovskites (CH 3 NH 3 PbI 3-x Cl x ) using femtosecond transient absorption, time-integrated photoluminescence, confocal reflectance, and transmission microscopies. Comprehensive image analysis revealed the presence of surface- and bulk-dominated contributions to the various images, which describe either spatially dependent electronic excited-state properties or morphological variations across the probed region of the thin films. These results show that PL probes effectively the species near or at the film surface.

Effect of solvents on the bulk growth of 4-aminobenzophenone single crystals: A potential material for blue and green lasers

NASA Astrophysics Data System (ADS)

Natarajan, V.; Usharani, S.; Arivanandhan, M.; Anandan, P.; Hayakawa, Y.

2015-06-01

Although 4-aminobenzophenone (4-ABP) is the best derivative of benzophenone with 260 times higher second harmonic generation (SHG) efficiency than potassium dihydrogen phosphate (KDP), growth of high quality bulk crystal still remains a difficult task. In the present work, the effect of solvents on solubility and growth aspects of 4-ABP was investigated to grow inclusion free 4-ABP crystals. The growth processes were discussed based on solute-solvent interaction in two different growth media of ethyl acetate and ethanol. The growth rate and thereby solvent inclusions are relatively higher in ethyl acetate grown crystal than the crystal grown from ethanol. The structural, thermal and optical properties of 4-ABP crystals were studied. The enthalpy of 4-ABP melting process was estimated from differential thermal analysis. The optical transmission study shows that 4-ABP crystals grown from ethanol has high transparency compared to ethyl acetate grown sample due to solvent inclusion in the later crystal.

Development of a Water Soluble Foam Packaging Material

DTIC Science & Technology

1975-01-01

Material, Expanded Polystyrene , Looae-Fill Bulk and standard properties were established. Additional investigations conducted on the loose-fill samples...mechanical properties when tested as described in Federal Specification PPP-O-1683; Cushioning Material, Expanded Polystyrene , Loose-Fill Bulk. The following

Dynamics of bulk versus nanoscale W S2 : Local strain and charging effects

NASA Astrophysics Data System (ADS)

Luttrell, R. D.; Brown, S.; Cao, J.; Musfeldt, J. L.; Rosentsveig, R.; Tenne, R.

2006-01-01

We measured the infrared vibrational properties of bulk and nanoparticle WS2 in order to investigate the structure-property relations in these materials. In addition to the symmetry-breaking effects of local strain, nanoparticle curvature modifies the local charging environment of the bulk material. Performing a charge analysis on the xy -polarized E1u vibrational mode, we find an approximate 1.5:1 intralayer charge difference between the layered 2H material and inorganic fullerene-like (IF) nanoparticles. This effective charge difference may impact the solid-state lubrication properties of nanoscale metal dichalcogenides.

Dynamics of Bulk vs. Nanoscale WS2: Local Strain and Charging Effects

NASA Astrophysics Data System (ADS)

Musfeldt, J. L.; Brown, S.; Luttrell, R. D.; Cao, J.; Rosentsveig, R.; Tenne, R.

2006-03-01

We measured the infrared vibrational properties of bulk and nanoparticle WS2 in order to investigate the structure- property relations in these novel materials. In addition to the symmetry-breaking effects of local strain, nanoparticle curvature modifies the local charging environment of the bulk material. Performing a charge analysis on the xy-polarized E1u vibrational mode, we find an approximate 1.5:1 intralayer charge difference between the layered 2H material and inorganic fullerene-like (IF) nanoparticles. This effective charge difference may impact the solid-state lubrication properties of nanoscale metal dichalcogenides.

Chemical, electronic, and magnetic structure of LaFeCoSi alloy: Surface and bulk properties

NASA Astrophysics Data System (ADS)

Lollobrigida, V.; Basso, V.; Borgatti, F.; Torelli, P.; Kuepferling, M.; Coïsson, M.; Olivetti, E. S.; Celegato, F.; Tortora, L.; Stefani, G.; Panaccione, G.; Offi, F.

2014-05-01

We investigate the chemical, electronic, and magnetic structure of the magnetocaloric LaFeCoSi compound with bulk and surface sensitive techniques. We put in evidence that the surface retains a soft ferromagnetic behavior at temperatures higher than the Curie temperature of the bulk due to the presence of Fe clusters at the surface only. This peculiar magnetic surface effect is attributed to the exchange interaction between the ferromagnetic Fe clusters located at the surface and the bulk magnetocaloric alloy, and it is used here to monitor the magnetic properties of the alloy itself.

Effects of densification of precursor pellets on microstructures and critical current properties of YBCO melt-textured bulks

NASA Astrophysics Data System (ADS)

Setoyama, Yui; Shimoyama, Jun-ichi; Motoki, Takanori; Kishio, Kohji; Awaji, Satoshi; Kon, Koichi; Ichikawa, Naoki; Inamori, Satoshi; Naito, Kyogo

2016-12-01

Effects of densification of precursor disks on the density of residual voids and critical current properties for YBCO melt-textured bulk superconductors were systematically investigated. Six YBCO bulks were prepared from precursor pellets with different initial particle sizes of YBa2Cu3Oy (Y123) powder and applied pressures for pelletization. It was revealed that use of finer Y123 powder and consolidation using cold-isostatic-pressing (CIP) with higher pressures result in reduction of residual voids at inner regions of bulks and enhance Jc especially under low fields below the second peak.

Ionization state of L-phenylalanine at the air-water interface.

PubMed

Griffith, Elizabeth C; Vaida, Veronica

2013-01-16

The ionization state of organic molecules at the air-water interface and the related problem of the surface pH of water have significant consequences on the catalytic role of the surface in chemical reactions and are currently areas of intense research and controversy. In this work, infrared reflection-absorption spectroscopy (IRRAS) is used to identify changes in the ionization state of L-phenylalanine in the surface region versus the bulk aqueous solution. L-phenylalanine has the unique advantage of possessing two different hydrophilic groups, a carboxylic acid and an amine base, which can deprotonate and protonate respectively depending on the ionic environment they experience at the water surface. In this work, the polar group vibrations in the surface region are identified spectroscopically in varying bulk pH solutions, and are subsequently compared with the ionization state of the polar groups of molecules residing in the bulk environment. The polar groups of L-phenylalanine at the surface transition to their deprotonated state at bulk pH values lower than the molecules residing in the bulk, indicating a decrease in their pK(a) at the surface, and implying an enhanced hydroxide ion concentration in the surface region relative to the bulk.

Over-hydration detection in brain by magnetic induction spectroscopy

NASA Astrophysics Data System (ADS)

González, César A.; Pérez, María; Hevia, Nidiyare; Arámbula, Fernándo; Flores, Omar; Aguilar, Eliot; Hinojosa, Ivonne; Joskowicz, Leo; Rubinsky, Boris

2010-04-01

Detection and continuous monitoring of edema in the brain in early stages is useful for assessment of medical condition and treatment. We have proposed a solution in which the bulk measurements of the tissue electrical properties to detect edema or in general accumulation of fluids are made through measurement of the magnetic induction phase shift between applied and measured currents at different frequencies (Magnetic Induction Spectroscopy; MIS). Magnetic Resonant Imaging (MRI) has been characterized because its capability to detect different levels of brain tissue hydration by differences in diffusion-weighted (DW) sequences and it's involve apparent diffusion coefficient (ADC). The objective of this study was to explore the viability to use measurements of the bulk tissue electrical properties to detect edema or in general accumulation of fluids by MIS. We have induced a transitory and generalized tissue over-hydration condition in ten volunteers ingesting 1.5 to 2 liters of water in ten minutes. Basal and over-hydration conditions were monitored by MIS and MRI. Changes in the inductive phase shift at certain frequencies were consistent with changes in the brain tissue hydration level observed by DW-ADC. The results suggest that MIS has the potential to detect pathologies associated to changes in the content of fluids in brain tissue such as edema and hematomas.

Interplay between interface structure and magnetism in NiFe/Cu/Ni-based pseudo-spin valves

NASA Astrophysics Data System (ADS)

Loving, Melissa G.; Ambrose, Thomas F.; Ermer, Henry; Miller, Don; Naaman, Ofer

2018-05-01

Magnetic pseudo spin valves (PSVs) with superconducting Nb electrodes, have been leading candidates for an energy-efficient memory solution compatible with cryogenic operation of ultra-low power superconducting logic. Integration of these PSV Josephson junctions in a standard multi-layer Nb process requires growing high-quality thin magnetic films on a thick Nb bottom electrode (i.e. ≥1.5kÅ, to achieve bulk superconducting properties). However, as deposited, 1.5kÅ Nb exhibits a rough surface with a characteristic rice grain morphology, which severely degrades the switching properties of subsequently deposited PSVs. Therefore, in order to achieve coherent switching throughout a PSV, the Nb interface must be modified. Here, we demonstrate that the Nb surface morphology and PSV crystallinity can be altered with the incorporation of separate 50Å Cu or 100Å Al/50Å Cu non-magnetic seed layers, and demonstrate their impact on the magnetic switching of a 15Å Ni80Fe20/50Å Cu/20Å Ni PSV, at both room temperature and at 10 K. Most notably, these results show that the incorporation of an Al seed layer leads to an improved face centered cubic templating through the bulk of the PSV, and ultimately to superior magnetic switching.

Deducing multiple interfacial dynamics during polymeric foaming.

PubMed

Chandan, Mohammed Rehaan; Naskar, Nilanjon; Das, Anuja; Mukherjee, Rabibrata; Harikrishnan, Gopalakrishna Pillai

2018-06-15

Several interfacial phenomena are active during polymeric foaming, the dynamics of which significantly influence terminal stability, cell structure and in turn the thermo-mechanical properties of temporally evolved foam. Understanding these dynamics is important in achieving desired foam properties. Here, we introduce a method to simultaneously portray the time evolution of bubble growth, lamella thinning and Plateau border drainage, occurring during reactive polymeric foaming. In this method, we initially conduct bulk and surface shear rheology under polymerizing and non-foaming conditions. In a subsequent step, foaming experiments were conducted in a rheometer. The microscopic structural dimensions pertaining to the terminal values of the dynamics of each interfacial phenomena are then measured using a combination of scanning electron microscopy, optical microscopy and imaging ellipsometry, after the foaming is over. The measured surface and bulk rheological parameters are incorporated in time evolution equations that are derived from mass and momentum transport occurring when a model viscoelastic fluid is foamed by gas dispersion. Analytical and numerical solutions to these equations portray the dynamics. We demonstrate this method for a series of reactive polyurethane foams generated from different chemical sources. The effectiveness of our method is in simultaneously obtaining these dynamics that are difficult to directly monitor due to short active durations over multiple length scales.

Tribological properties of silicon carbide in metal removal process

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1980-01-01

Material properties are considered as they relate to adhesion, friction, and wear of single crystal silicon carbide in contact with metals and alloys that are likely to be involved in a metal removal process such as grinding. Metal removal from adhesion between sliding surfaces in contact and metal removal as a result of the silicon carbide sliding against a metal, indenting into it, and plowing a series of grooves or furrows are discussed. Fracture and deformation characteristics of the silicon carbide surface are also covered. The adhesion, friction, and metal transfer to silicon carbide is related to the relative chemical activity of the metals. The more active the metal, the higher the adhesion and friction, and the greater the metal transfer to silicon carbide. Atomic size and content of alloying elements play a dominant role in controlling adhesion, friction, and abrasive wear properties of alloys. The friction and abrasive wear (metal removal) decrease linearly as the shear strength of the bulk metal increases. They decrease as the solute to solvent atomic radius ratio increases or decreases linearly from unity, and with an increase of solute content. The surface fracture of silicon carbide is due to cleavages of 0001, 10(-1)0, and/or 11(-2)0 planes.

A thermodynamic study of the amphiphilic phenothiazine drug thioridazine hydrochloride in water/ethanol solvent

NASA Astrophysics Data System (ADS)

Cheema, Mohammad Arif; Barbosa, Silvia; Taboada, Pablo; Castro, Emilio; Siddiq, Mohammad; Mosquera, Víctor

2006-09-01

The thermodynamic properties of aqueous solutions of the tricyclic antidepressant amphiphilic phenothiazine drug thioridazine hydrochloride in the temperature range 20-50 °C and in the presence of ethanol have been measured. The phenothiazine tranquillizing drugs have interesting association characteristics that derive from their rigid, tricyclic hydrophobic groups. Thioridazine hydrochloride is a drug used in treatment of mental illness that shows side effects. Therefore, it is interesting to study the change of its physico-chemical properties with temperature and with the surrounding environment to understand the action mechanism of the drug. Densities, conductivities, and surface tension were measured to obtain surface and bulk solution properties. Critical concentrations, cc, at different temperatures and in the presence of ethanol, and partition coefficients, K, have been calculated, the latter using an indirect method based in the pseudophase model with the help of apparent molar volume data. This method has the advantage that allows calculating the distribution coefficients at solubilizate concentrations below the saturation. Conductivity data show two critical concentrations. The second critical concentration is not clear by density data. The effect of the alcohol is to decrease the first critical concentration due to a decrease in headgroup repulsion. The molar apparent volumes at infinite dilution and in the aggregate in water and in presence of ethanol have been also obtained.

Influence of organic solvent on optical and structural properties of ultra-small silicon dots synthesized by UV laser ablation in liquid.

PubMed

Intartaglia, Romuald; Bagga, Komal; Genovese, Alessandro; Athanassiou, Athanassia; Cingolani, Roberto; Diaspro, Alberto; Brandi, Fernando

2012-11-28

Ultra small silicon nanoparticles (Si-NPs) with narrow size distribution are prepared in a one step process by UV picosecond laser ablation of silicon bulk in liquid. Characterization by electron microscopy and absorption spectroscopy proves Si-NPs generation with an average size of 2 nm resulting from an in situ photofragmentation effect. In this context, the current work aims to explore the liquid medium (water and toluene) effect on the Si-NPs structure and on the optical properties of the colloidal solution. Si-NPs with high pressure structure (s.g. Fm3m) and diamond-like structure (s.g. Fd3m), in water, and SiC moissanite 3C phase (s.g. F4[combining macron]3m) in toluene are revealed by the means of High-Resolution TEM and HAADF-STEM measurements. Optical investigations show that water-synthesized Si-NPs have blue-green photoluminescence emission characterized by signal modulation at a frequency of 673 cm(-1) related to electron-phonon coupling. The synthesis in toluene leads to generation of Si-NPs embedded in the graphitic carbon-polymer composite which has intrinsic optical properties at the origin of the optical absorption and luminescence of the obtained colloidal solution.

Spherical nitroguanidine process

DOEpatents

Sanchez, John A.; Roemer, Edward L.; Stretz, Lawrence A.

1990-01-01

A process of preparing spherical high bulk density nitroguanidine by dissing low bulk density nitroguanidine in N-methyl pyrrolidone at elevated temperatures and then cooling the solution to lower temperatures as a liquid characterized as a nonsolvent for the nitroguanidine is provided. The process is enhanced by inclusion in the solution of from about 1 ppm up to about 250 ppm of a metal salt such as nickel nitrate, zinc nitrate or chromium nitrate, preferably from about 20 to about 50 ppm.

Investigation into nanoscratching mechanical response of AlCrCuFeNi high-entropy alloys using atomic simulations

NASA Astrophysics Data System (ADS)

Wang, Zining; Li, Jia; Fang, QiHong; Liu, Bin; Zhang, Liangchi

2017-09-01

The mechanical behaviors and deformation mechanisms of scratched AlCrCuFeNi high entropy alloys (HEAs) have been studied by molecular dynamics (MD) simulations, in terms of the scratching forces, atomic strain, atomic displacement, microstructural evolution and dislocation density. The results show that the larger tangential and normal forces and higher friction coefficient take place in AlCrCuFeNi HEA due to its outstanding strength and hardness, and high adhesion and fracture toughness over the pure metal materials. Moreover, the stacking fault energy (SFE) in HEA increases the probability to initiate dislocation and twinning, which is conducive to the formation of complex deformation modes. Compared to the single element metal workpieces, the segregation potency of solutes into twinning boundary (TB) is raised due to the decreasing segregation energy of TB, resulting in the stronger solute effects on improving twinning properties for HEA workpiece. The higher dislocation density and the more activated slipping planes lead to the outstanding plasticity of AlCrCuFeNi HEA. The solute atoms as barriers to hinder the motion of dislocation and the severe lattice distortion to suppress the free slipping of dislocation are significantly stronger obstacles to strengthen HEA. The excellent comprehensive scratching properties of the bulk AlCrCuFeNi HEAs are associated with the combined effects of multiple strengthening mechanisms, such as dislocation strengthening, deformation twinning strengthening as well as solute strengthening. This work provides a basis for further understanding and tailoring SFE in mechanical properties and deformation mechanism of HEAs, which maybe facilitate the design and preparation of new HEAs with high performance.

Pore Scale Dynamics of Microemulsion Formation.

PubMed

Unsal, Evren; Broens, Marc; Armstrong, Ryan T

2016-07-19

Experiments in various porous media have shown that multiple parameters come into play when an oleic phase is displaced by an aqueous solution of surfactant. In general, the displacement efficiency is improved when the fluids become quasi-miscible. Understanding the phase behavior oil/water/surfactant systems is important because microemulsion has the ability to generate ultralow interfacial tension (<10(-2) mN m(-1)) that is required for miscibility to occur. Many studies focus on microemulsion formation and the resulting properties under equilibrium conditions. However, the majority of applications where microemulsion is present also involve flow, which has received relatively less attention. It is commonly assumed that the characteristics of an oil/water/surfactant system under flowing conditions are identical to the one under equilibrium conditions. Here, we show that this is not necessarily the case. We studied the equilibrium phase behavior of a model system consisting of n-decane and an aqueous solution of olefin sulfonate surfactant, which has practical applications for enhanced oil recovery. The salt content of the aqueous solution was varied to provide a range of different microemulsion compositions and oil-water interfacial tensions. We then performed microfluidic flow experiments to study the dynamic in situ formation of microemulsion by coinjecting bulk fluids of n-decane and surfactant solution into a T-junction capillary geometry. A solvatochromatic fluorescent dye was used to obtain spatially resolved compositional information. In this way, we visualized the microemulsion formation and the flow of it along with the excess phases. A complex interaction between the flow patterns and the microemulsion properties was observed. The formation of microemulsion influenced the flow regimes, and the flow regimes affected the characteristics of the microemulsion formation. In particular, at low flow rates, slug flow was observed, which had profound consequences on the pore scale mixing behavior and resulting microemulsion properties.

How water manifests the structural regimes in ionic liquids.

PubMed

Singh, Akhil Pratap; Gardas, Ramesh L; Senapati, Sanjib

2017-03-22

Ionic liquids (ILs) are being considered as greener alternatives to the conventional organic solvents. However, highly viscous nature of ILs often limits their applications. Hence studies on IL/water binary mixtures have received tremendous attention. These mixtures exhibit much lower viscosity, but almost similar density, compressibility and other properties as that of the neat ILs, up to certain water content. Hence, determining the IL-water ratio till which the solution behaves like IL and subsequently changes to a state of solute IL dissolved in continuous water phase is of paramount importance. Noting the very different and characteristic behaviours of neat ILs and pure water over a temperature range, herein, we measured the various thermophysical properties of the binary mixtures of tetramethylguanidinium benzoate/water and tetramethylguanidinium salicylate/water with water content varying from 20 wt% to 95 wt% for a temperature range of 298 K to 343 K. The results show that similar to neat ILs, the measured densities and compressibility of these mixtures display a linear change, and viscosity decreases rapidly as temperature is increased for water content up to 50 wt%. At higher water concentrations, the measured density and compressibility exhibit nonlinear behaviour and the decrease in viscosity with increased temperature is minute, mimicking the behaviour of bulk water. MD simulations were carried out to explain the experimental observations. Simulation results show a greater temperature-induced disintegration of IL ion-water interactions in dense systems, explaining the rapid decay of the properties with temperature. The results also exhibit the presence of a neat, IL-like, H-bond mediated expanded structure in concentrated solution versus a collapsed IL structure in dilute solution.

Membrane fouling in a submerged membrane bioreactor with focus on surface properties and interactions of cake sludge and bulk sludge.

PubMed

Yu, Haiying; Lin, Hongjun; Zhang, Meijia; Hong, Huachang; He, Yiming; Wang, Fangyuan; Zhao, Leihong

2014-10-01

In this study, the fouling behaviors and surface properties of cake sludge and bulk sludge in a submerged membrane bioreactor (MBR) were investigated and compared. It was found that the specific filtration resistance (SFR) of cake sludge was about 5 times higher than that of bulk sludge. Two types of sludge possessed similar extracellular polymeric substances (EPS) content, particle size distribution (PSD) and zeta potential. However, their surface properties in terms of surface tensions were significantly different. Further analysis showed that cake sludge was more hydrophilic and had worse aggregation ability. Moreover, cake sludge surface possessed more hydrocarbon, less oxygen and nitrogen moieties than bulk sludge surface. It was suggested that, rather than EPS and PSD differences, the differences in the surface composition were the main cause of the great differences in SFR and adhesion ability between cake sludge and bulk sludge. Copyright © 2014 Elsevier Ltd. All rights reserved.

Silver-modified mobile phase for normal-phase liquid chromatographic determination of prostaglandins and their 5,6-trans isomers in prostaglandin bulk drugs and triacetin solutions.

PubMed

Kissinger, L D; Robins, R H

1985-03-15

A silver-modified, normal-phase, high-performance liquid chromatographic system has been developed for prostaglanding bulk drugs and triacetin solutions. Silver nitrate present in the mobile phase results in high selectivity for cis/trans isomers with conventional silica columns. Prostaglandins were esterified with alpha-bromo-2'-acetonaphthone prior to chromatography to provide high detectability at 254 nm. For dilute triacetin solutions, a sample preparation scheme based on gravity-flow chromatography with silica columns was developed to isolate the prostaglandin from triacetin prior to derivatization. The analytical technique was applied to triacetin solutions containing as little as 10 micrograms/ml arbaprostil [15-(R)-methyl-PGE2].

A new approach to the problem of bulk-mediated surface diffusion.

PubMed

Berezhkovskii, Alexander M; Dagdug, Leonardo; Bezrukov, Sergey M

2015-08-28

This paper is devoted to bulk-mediated surface diffusion of a particle which can diffuse both on a flat surface and in the bulk layer above the surface. It is assumed that the particle is on the surface initially (at t = 0) and at time t, while in between it may escape from the surface and come back any number of times. We propose a new approach to the problem, which reduces its solution to that of a two-state problem of the particle transitions between the surface and the bulk layer, focusing on the cumulative residence times spent by the particle in the two states. These times are random variables, the sum of which is equal to the total observation time t. The advantage of the proposed approach is that it allows for a simple exact analytical solution for the double Laplace transform of the conditional probability density of the cumulative residence time spent on the surface by the particle observed for time t. This solution is used to find the Laplace transform of the particle mean square displacement and to analyze the peculiarities of its time behavior over the entire range of time. We also establish a relation between the double Laplace transform of the conditional probability density and the Fourier-Laplace transform of the particle propagator over the surface. The proposed approach treats the cases of both finite and infinite bulk layer thicknesses (where bulk-mediated surface diffusion is normal and anomalous at asymptotically long times, respectively) on equal footing.

Enhancing Aluminum Reactivity by Exploiting Surface Chemistry and Mechanical Properties

DTIC Science & Technology

2015-06-01

alter its mechanical properties . In bulk material processing , annealing and quenching metals such as Al can relieve residual stress and improve...increasing  Al  reactivity is to alter its mechanical  properties .  In bulk material  processing , annealing and quenching metals such as  Al  can relieve...mechanical properties . On a single particle level, affecting mechanical properties may also affect Al particle reactivity. Aluminum particles underwent

46 CFR Table 2 to Part 153 - Cargoes Not Regulated Under Subchapters D or O of This Chapter When Carried in Bulk on Non...

Code of Federal Regulations, 2012 CFR

2012-10-01

... Category 2-Amino-2-hydroxymethyl-1,3-propanediol solution III Ammonium hydrogen phosphate solution D...) D Ammonium phosphate, Urea solution, see also Urea, Ammonium phosphate solution D Ammonium..., Magnesium nitrate, Potassium chloride solution III Caramel solutions III Chlorinated paraffins (C14-C17...

Evidence for spin injection and transport in solution-processed TIPS-pentacene at room temperature

NASA Astrophysics Data System (ADS)

Mooser, S.; Cooper, J. F. K.; Banger, K. K.; Wunderlich, J.; Sirringhaus, H.

2012-10-01

Recently, there has been growing interest in the field of organic spintronics, where the research on organic semiconductors (OSCs) has extended from the complex aspects of charge carrier transport to the study of the spin transport properties of those anisotropic and partly localized systems.1 Furthermore, solution-processed OSCs are not only interesting due to their technological applications, but it has recently been shown in 6,13-bis(triisopropylsilylethynyl)-pentacene (TIPS-pentacene) thin film transistors that they can exhibit a negative temperature coefficient of the mobility due to localized transport limited by thermal lattice fluctuations.2 Here, spin injection and transport in solution-processed TIPS-pentacene are investigated exploiting vertical CoPt/TIPSpentacene/AlOx/Co spin valve architectures.3 The antiparallel magnetization state of the relative orientation of CoPt and Co is achieved due to their different coercive fields. A spin valve effect is detected from T = 175 K up to room temperature, where the resistance of the device is lower for the antiparallel magnetization state. The first observation of the scaling of the magnetoresistance (MR) with the bulk mobility of the OSC as a function of temperature, together with the dependence of the MR on the interlayer thickness, clearly indicates spin injection and transport in TIPS-pentacene. From OSC-spacer thickness-dependent MR measurements, a spin relaxation length of TIPS-pentacene of (24+/-6) nm and a spin relaxation time of approximately 3.5 μs at room temperature are estimated, taking the measured bulk mobility of holes into account.

A Two-Step Absorber Deposition Approach To Overcome Shunt Losses in Thin-Film Solar Cells: Using Tin Sulfide as a Proof-of-Concept Material System

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

Steinmann, Vera; Chakraborty, Rupak; Rekemeyer, Paul H.

2016-08-31

As novel absorber materials are developed and screened for their photovoltaic (PV) properties, the challenge remains to reproducibly test promising candidates for high-performing PV devices. Many early-stage devices are prone to device shunting due to pinholes in the absorber layer, producing 'false-negative' results. Here, we demonstrate a device engineering solution toward a robust device architecture, using a two-step absorber deposition approach. We use tin sulfide (SnS) as a test absorber material. The SnS bulk is processed at high temperature (400 degrees C) to stimulate grain growth, followed by a much thinner, low-temperature (200 degrees C) absorber deposition. At a lowermore » process temperature, the thin absorber overlayer contains significantly smaller, densely packed grains, which are likely to provide a continuous coating and fill pinholes in the underlying absorber bulk. We compare this two-step approach to the more standard approach of using a semi-insulating buffer layer directly on top of the annealed absorber bulk, and we demonstrate a more than 3.5x superior shunt resistance Rsh with smaller standard error ..sigma..Rsh. Electron-beam-induced current (EBIC) measurements indicate a lower density of pinholes in the SnS absorber bulk when using the two-step absorber deposition approach. We correlate those findings to improvements in the device performance and device performance reproducibility.« less

46 CFR Table 2 to Part 153 - Cargoes Not Regulated Under Subchapters D or O of This Chapter When Carried in Bulk on Non...

Code of Federal Regulations, 2013 CFR

2013-10-01

...-ethylamino-6-isopropylamino-5-triazine solution # Choline chloride solution D Clay slurry III Coal slurry III... acid, dimethylamine salt solution * Y Choline chloride solutions Z Clay slurry OS Coal slurry OS...

Liquid bridges at the root-soil interface

NASA Astrophysics Data System (ADS)

Carminati, Andrea; Benard, Pascal; Ahmed, Mutez; Zarebanadkouki, Mohsen

2017-04-01

The role of the root-soil interface on soil-plant water relations is unclear. Despite many experimental studies proved that the soil close to the root surface, the rhizosphere, has different properties compared to the adjacent bulk soil, the mechanisms underlying such differences are poorly understood and the implications for plant-water relations remain largely speculative. The objective of this contribution is to discuss the key elements affecting water dynamics in the rhizosphere. Special attention is dedicated to the role of mucilage exuded by roots in shaping the hydraulic properties of the rhizosphere. We identified three key properties: 1) mucilage adsorbs water decreasing its water potential; 2) mucilage decreases the surface tension of the soil solution; 3) mucilage increases the viscosity of the soil solution. These three properties determine the retention and spatial configuration of the liquid phase in porous media. The increase in viscosity and the decrease in surface tension (quantified by the Ohnesorge number) allow the persistence of long liquid filaments even at very negative water potentials. At high mucilage concentrations these filaments form a network that creates an additional matric potential and maintains the continuity of the liquid phase during drying. The biophysical interactions between mucilage and the pore space determine the physical properties of the rhizosphere. Mucilage forms a network that provides mechanical stability to soils upon drying and that maintains the continuity of the liquid phase across the soil-root interface. Such biophysical properties are functional to create an interconnected matrix that maintains the roots in contact with the soil, which is of particular importance when the soil is drying and the transpiration rate is high.

Modification of electrical properties of topological insulators

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

Sharma, Peter Anand

Ion implantation or deposition can be used to modify the bulk electrical properties of topological insulators. More particularly, ion implantation or deposition can be used to compensate for the non-zero bulk conductivity due to extrinsic charge carriers. The direct implantation of deposition/annealing of dopants allows better control over carrier concentrations for the purposes of achieving low bulk conductivity. Ion implantation or deposition enables the fabrication of inhomogeneously doped structures, enabling new types of device designs.

Bulk Properties of Ni3Al(gamma') With Cu and Au Additions

NASA Technical Reports Server (NTRS)

Bozzolo, Guillermo; Ferrante, John

1995-01-01

The BFS method for alloys is applied to the study of 200 alloys obtained from adding Cu and Au impurities to a Ni3Al matrix. We analyze the trends in the bulk properties of these alloys (heat of formation, lattice parameter, and bulk modulus) and detect specific alloy compositions for which these quantities have particular values. A detailed analysis of the atomic interactions that lead to the preferred ordering patterns is presented.

Internal and external atomic steps in graphite exhibit dramatically different physical and chemical properties.

PubMed

Lee, Hyunsoo; Lee, Han-Bo-Ram; Kwon, Sangku; Salmeron, Miquel; Park, Jeong Young

2015-04-28

We report on the physical and chemical properties of atomic steps on the surface of highly oriented pyrolytic graphite (HOPG) investigated using atomic force microscopy. Two types of step edges are identified: internal (formed during crystal growth) and external (formed by mechanical cleavage of bulk HOPG). The external steps exhibit higher friction than the internal steps due to the broken bonds of the exposed edge C atoms, while carbon atoms in the internal steps are not exposed. The reactivity of the atomic steps is manifested in a variety of ways, including the preferential attachment of Pt nanoparticles deposited on HOPG when using atomic layer deposition and KOH clusters formed during drop casting from aqueous solutions. These phenomena imply that only external atomic steps can be used for selective electrodeposition for nanoscale electronic devices.

Investigation of phase segregation using Rietveld refinement in Mg doped BaTiO3 solid solutions and their ferroelectric properties

NASA Astrophysics Data System (ADS)

Aanchal, Kaur, Kiranpreet; Singh, Anupinder; Singh, Mandeep

2018-05-01

Ba(1-x) Mgx Ti O3 (BMT) samples were synthesised using solid state reaction route with `x' varying from 0.025 to 0.10. The structural and ferroelectric properties of the bulk samples were investigated. The XRD analysis shows the presence of two phases, the first phase being magnesium doped BT (space group P4mm) and the second phase being Ba2TiO4 (space group Pna21). The tetragonal phase was found to be the major phase in the samples. The double phase Rietveld refinement was done and the weight percentage of orthorhombic phase was found to vary from 3.43% to 6.96% for x varying from 0.025≤x≤0.10. The P - E measurements reveal that all the samples exhibit lossy behaviour.

Spatial Decomposition of Translational Water–Water Correlation Entropy in Binding Pockets

PubMed Central

2015-01-01

A number of computational tools available today compute the thermodynamic properties of water at surfaces and in binding pockets by using inhomogeneous solvation theory (IST) to analyze explicit-solvent simulations. Such methods enable qualitative spatial mappings of both energy and entropy around a solute of interest and can also be applied quantitatively. However, the entropy estimates of existing methods have, to date, been almost entirely limited to the first-order terms in the IST’s entropy expansion. These first-order terms account for localization and orientation of water molecules in the field of the solute but not for the modification of water–water correlations by the solute. Here, we present an extension of the Grid Inhomogeneous Solvation Theory (GIST) approach which accounts for water–water translational correlations. The method involves rewriting the two-point density of water in terms of a conditional density and utilizes the efficient nearest-neighbor entropy estimation approach. Spatial maps of this second order term, for water in and around the synthetic host cucurbit[7]uril and in the binding pocket of the enzyme Factor Xa, reveal mainly negative contributions, indicating solute-induced water–water correlations relative to bulk water; particularly strong signals are obtained for sites at the entrances of cavities or pockets. This second-order term thus enters with the same, negative, sign as the first order translational and orientational terms. Numerical and convergence properties of the methodology are examined. PMID:26636620

Investigation of Thermal Interface Materials Using Phase-Sensitive Transient Thermoreflectance Technique: Preprint

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

Feng, X.; King, C.; DeVoto, D.

2014-08-01

With increasing power density in electronics packages/modules, thermal resistances at multiple interfaces are a bottleneck to efficient heat removal from the package. In this work, the performance of thermal interface materials such as grease, thermoplastic adhesives and diffusion-bonded interfaces are characterized using the phase-sensitive transient thermoreflectance technique. A multi-layer heat conduction model was constructed and theoretical solutions were derived to obtain the relation between phase lag and the thermal/physical properties. This technique enables simultaneous extraction of the contact resistance and bulk thermal conductivity of the TIMs. With the measurements, the bulk thermal conductivity of Dow TC-5022 thermal grease (70 tomore » 75 um bondline thickness) was 3 to 5 W/(m-K) and the contact resistance was 5 to 10 mm2-K/W. For the Btech thermoplastic material (45 to 80 μm bondline thickness), the bulk thermal conductivity was 20 to 50 W/(m-K) and the contact resistance was 2 to 5 mm2-K/W. Measurements were also conducted to quantify the thermal performance of diffusion-bonded interface for power electronics applications. Results with the diffusion-bonded sample showed that the interfacial thermal resistance is more than one order of magnitude lower than those of traditional TIMs, suggesting potential pathways to efficient thermal management.« 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.

Molecular and Nanoscale Engineering of High Efficiency Excitonic Solar Cells

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

Jenekhe, Samson A.; Ginger, David S.; Cao, Guozhong

We combined the synthesis of new polymers and organic-inorganic hybrid materials with new experimental characterization tools to investigate bulk heterojunction (BHJ) polymer solar cells and hybrid organic-inorganic solar cells during the 2007-2010 period (phase I) of this project. We showed that the bulk morphology of polymer/fullerene blend solar cells could be controlled by using either self-assembled polymer semiconductor nanowires or diblock poly(3-alkylthiophenes) as the light-absorbing and hole transport component. We developed new characterization tools in-house, including photoinduced absorption (PIA) spectroscopy, time-resolved electrostatic force microscopy (TR-EFM) and conductive and photoconductive atomic force microscopy (c-AFM and pc-AFM), and used them to investigatemore » charge transfer and recombination dynamics in polymer/fullerene BHJ solar cells, hybrid polymer-nanocrystal (PbSe) devices, and dye-sensitized solar cells (DSSCs); we thus showed in detail how the bulk photovoltaic properties are connected to the nanoscale structure of the BHJ polymer solar cells. We created various oxide semiconductor (ZnO, TiO 2) nanostructures by solution processing routes, including hierarchical aggregates and nanorods/nanotubes, and showed that the nanostructured photoanodes resulted in substantially enhanced light-harvesting and charge transport, leading to enhanced power conversion efficiency of dye-sensitized solar cells.« less

Trapped magnetic-field properties of prototype for Gd-Ba-Cu-O/MgB2 hybrid-type superconducting bulk magnet

NASA Astrophysics Data System (ADS)

Naito, Tomoyuki; Mochizuki, Hidehiko; Fujishiro, Hiroyuki; Teshima, Hidekazu

2016-03-01

We have studied experimentally and numerically the trapped magnetic-field properties of a hybrid-type superconducting bulk magnet, which comprised an inner Gd-Ba-Cu-O (GdBCO) disk-bulk and an outer MgB2 ring-bulk, under field-cooled magnetization (FCM) and pulsed-field magnetization (PFM). The trapped field by FCM at the center of the hybrid bulk was 4.5 T at 20 K, which was 0.2 T higher than that of the inner GdBCO disk-bulk without MgB2 ring-bulk. The experimental results by FCM were quantitatively reproduced by the numerical estimations for a model, which makes it possible to understand the trapped field properties of the hybrid bulk. The total magnetic flux by FCM, which was estimated numerically, was enhanced by about 1.7 times from 0.91 mWb of the single GdBCO bulk to 1.53 mWb of the hybrid bulk. We also succeeded in magnetizing the whole hybrid bulk by applying multi-pulsed-fields. The central trapped field of 1.88 T was not enhanced, but the total magnetic flux, which was obtained experimentally, was evidently increased by 2.5 times (0.25 \\to 0.62 mWb) for the hybrid bulk. The obtained results suggest that the hybridization is effective to enhance the total magnetic flux. To confirm the reinforcing effect of the MgB2 ring to the GdBCO disk during the cooling and magnetization processes, we have measured the thermal dilatation, {\\text{}}{dL}({\\text{}}T)/{\\text{}}L(300 K), of the GdBCO, MgB2 and stainless steel. As a result, the thermal dilatation of MgB2 was smaller than that of GdBCO. MgB2 ring-bulk shows no compression effect to resist the hoop stress of the GdBCO disk-bulk during the FCM process. The reinforcing material such as the stainless steel ring must be set outside the GdBCO disk-bulk.

First Principles Studies of Electronic and Optical Excitations in Noble Metal and Titania Clusters

NASA Astrophysics Data System (ADS)

Baishya, Kopinjol

Clusters are metastable structures that form a bridge between the atomic and the bulk phase. Due to their small size, quantum confinement effects are very important in clusters. They also have large surface to volume ratio, and as such, surface effects are also important. Due to these effects the properties of clusters are quite different from those of the bulk. When the size of a cluster is increased, its properties change from atomic to bulk values usually in nontrivial ways, often displaying interesting effects. By studying the evolution of cluster properties as a function of size one can try to understand the evolution and origin of bulk properties. This thesis concentrates on two main topics, noble-metal clusters of Ag and Cu, and TiO2 nanocrystals. I present my study of the optical properties of these systems calculated using first principles methods. Noble metal clusters have intriguing physical and chemical properties due to their electronic structure that contains a fully filled and localized d orbital energetically and spatially very close to the half filled s orbital. In Chapters 3 and 4 of this thesis, I present a detailed study of the role of d electrons on the optical properties of Ag and Cu clusters. I also show that the optical spectra of these clusters can be explained remarkably well by the classical Mie-Gans theory which uses the bulk dielectric constant of the material to predict their optical absorption spectra. The fact that the concept of the bulk dielectric constant survives up to the sub-nanometer size range is one of the main findings of this thesis. TiO2 is arguably the most studied single-crystalline material in the field of surface science of metal oxides. In chapter 5 of this thesis I present results and analyses on the electronic and optical excitations in rutile TiO2 nanocrystals. The motivation for this study stems from the following observation: In modeling optical prooperties of DSSC configurations with various organic molecules, a typical approach has been to use a finite, appropriately passivated TiO2 nanocrystal in order to limit the computational demand. In real systems on the other hand, the size of nanocrystalline TiO2 is of the order of several hundreds of nanometers, and hence, they can be considered to be essentially bulk-like. The question is then, whether finite TiO2 nanoparticles can accurately model the optical properties of bulk TiO2. I show in my thesis that the optical absorption absorption spectra of such TiO2 nanocrystals do not have the particular features seen in the imaginary part of the bulk dielectric function of TiO 2 associated with the van Hove singularities in the electronic density of states. Instead, the absorption spectra of bulk-terminated TiO2 nanocrystals can be reproduced quite well by the Mie-Gans theory.

Controlling the scattering properties of thin, particle-doped coatings

NASA Astrophysics Data System (ADS)

Rogers, William; Corbett, Madeleine; Manoharan, Vinothan

2013-03-01

Coatings and thin films of small particles suspended in a matrix possess optical properties that are important in several industries from cosmetics and paints to polymer composites. Many of the most interesting applications require coatings that produce several bulk effects simultaneously, but it is often difficult to rationally formulate materials with these desired optical properties. Here, we focus on the specific challenge of designing a thin colloidal film that maximizes both diffuse and total hemispherical transmission. We demonstrate that these bulk optical properties follow a simple scaling with two microscopic length scales: the scattering and transport mean free paths. Using these length scales and Mie scattering calculations, we generate basic design rules that relate scattering at the single particle level to the film's bulk optical properties. These ideas will be useful in the rational design of future optically active coatings.

Excellent electrical conductivity of the exfoliated and fluorinated hexagonal boron nitride nanosheets.

PubMed

Xue, Yafang; Liu, Qian; He, Guanjie; Xu, Kaibing; Jiang, Lin; Hu, Xianghua; Hu, Junqing

2013-01-24

The insulator characteristic of hexagonal boron nitride limits its applications in microelectronics. In this paper, the fluorinated hexagonal boron nitride nanosheets were prepared by doping fluorine into the boron nitride nanosheets exfoliated from the bulk boron nitride in isopropanol via a facile chemical solution method with fluoboric acid; interestingly, these boron nitride nanosheets demonstrate a typical semiconductor characteristic which were studied on a new scanning tunneling microscope-transmission electron microscope holder. Since this property changes from an insulator to a semiconductor of the boron nitride, these nanosheets will be able to extend their applications in designing and fabricating electronic nanodevices.

Analytical attractor and the divergence of the slow-roll expansion in relativistic hydrodynamics

NASA Astrophysics Data System (ADS)

Denicol, Gabriel S.; Noronha, Jorge

2018-03-01

We find the general analytical solution of the viscous relativistic hydrodynamic equations (in the absence of bulk viscosity and chemical potential) for a Bjorken expanding fluid with an ideal gas equation of state and a constant shear viscosity relaxation time. We analytically determine the hydrodynamic attractor of this fluid and discuss its properties. We show for the first time that the slow-roll expansion, a commonly used approach to characterize the attractor, diverges. This is shown to hold also in a conformal plasma. The gradient expansion is found to converge in an example where causality and stability are violated.

Superacid Passivation of Crystalline Silicon Surfaces.

PubMed

Bullock, James; Kiriya, Daisuke; Grant, Nicholas; Azcatl, Angelica; Hettick, Mark; Kho, Teng; Phang, Pheng; Sio, Hang C; Yan, Di; Macdonald, Daniel; Quevedo-Lopez, Manuel A; Wallace, Robert M; Cuevas, Andres; Javey, Ali

2016-09-14

The reduction of parasitic recombination processes commonly occurring within the silicon crystal and at its surfaces is of primary importance in crystalline silicon devices, particularly in photovoltaics. Here we explore a simple, room temperature treatment, involving a nonaqueous solution of the superacid bis(trifluoromethane)sulfonimide, to temporarily deactivate recombination centers at the surface. We show that this treatment leads to a significant enhancement in optoelectronic properties of the silicon wafer, attaining a level of surface passivation in line with state-of-the-art dielectric passivation films. Finally, we demonstrate its advantage as a bulk lifetime and process cleanliness monitor, establishing its compatibility with large area photoluminescence imaging in the process.

Finite element analysis and simulation of rheological properties of bulk molding compound (BMC)

NASA Astrophysics Data System (ADS)

Ergin, M. Fatih; Aydin, Ismail

2013-12-01

Bulk molding compound (BMC) is one of the important composite materials with various engineering applications. BMC is a thermoset plastic resin blend of various inert fillers, fiber reinforcements, catalysts, stabilizers and pigments that form a viscous, molding compound. Depending on the end-use application, bulk molding compounds are formulated to achieve close dimensional control, flame and scratch resistance, electrical insulation, corrosion and stain resistance, superior mechanical properties, low shrink and color stability. Its excellent flow characteristics, dielectric properties, and flame resistance make this thermoset material well-suited to a wide variety of applications requiring precision in detail and dimensions as well as high performance. When a BMC is used for these purposes, the rheological behavior and properties of the BMC is the main concern. In this paper, finite element analysis of rheological properties of bulk molding composite material was studied. For this purpose, standard samples of composite material were obtained by means of uniaxial hot pressing. 3 point flexural tests were then carried out by using a universal testing machine. Finite element analyses were then performed with defined material properties within a specific constitutive material behavior. Experimental and numerical results were then compared. Good correlation between the numerical simulation and the experimental results was obtained. It was expected with this study that effects of various process parameters and boundary conditions on the rheological behavior of bulk molding compounds could be determined by means of numerical analysis without detailed experimental work.

Self-assembled pentacenequinone derivative for trace detection of picric acid.

PubMed

Bhalla, Vandana; Gupta, Ankush; Kumar, Manoj; Rao, D S Shankar; Prasad, S Krishna

2013-02-01

Pentacenequinone derivative 3 forms luminescent supramolecular aggregates both in bulk as well as in solution phase. In bulk phase at high temperature, long-range stacking of columns leads to formation of stable and ordered columnar mesophase. Further, derivative 3 works as sensitive chemosensor for picric acid (PA) and gel-coated paper strips detect PA at nanomolar level and provide a simple, portable, and low-cost method for detection of PA in aqueous solution, vapor phase, and in contact mode.

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

Lawrence, G.B.; Fernandez, I.J.; Goltz, S.M.

To provide information needed to assess the current and future status of spruce-fir forests in Maine, the Howland Integrated Forest Study (HIFS) was initiated in 1987 as part of the USDA Forest Service Forest Response Program, in conjunction with the establishment of a Mountain Cloud Chemistry Program (MCCP) monitoring site. Through this project, bulk and wet-only precipitation, dry deposition, throughfall and soil solution chemistry has been determined. This paper will focus on soil solution collected between May, 1988 and bulk precipitation collected from June through November, 1988.

Evaluating the hydraulic and transport properties of peat soil using pore network modeling and X-ray micro computed tomography

NASA Astrophysics Data System (ADS)

Gharedaghloo, Behrad; Price, Jonathan S.; Rezanezhad, Fereidoun; Quinton, William L.

2018-06-01

Micro-scale properties of peat pore space and their influence on hydraulic and transport properties of peat soils have been given little attention so far. Characterizing the variation of these properties in a peat profile can increase our knowledge on the processes controlling contaminant transport through peatlands. As opposed to the common macro-scale (or bulk) representation of groundwater flow and transport processes, a pore network model (PNM) simulates flow and transport processes within individual pores. Here, a pore network modeling code capable of simulating advective and diffusive transport processes through a 3D unstructured pore network was developed; its predictive performance was evaluated by comparing its results to empirical values and to the results of computational fluid dynamics (CFD) simulations. This is the first time that peat pore networks have been extracted from X-ray micro-computed tomography (μCT) images of peat deposits and peat pore characteristics evaluated in a 3D approach. Water flow and solute transport were modeled in the unstructured pore networks mapped directly from μCT images. The modeling results were processed to determine the bulk properties of peat deposits. Results portray the commonly observed decrease in hydraulic conductivity with depth, which was attributed to the reduction of pore radius and increase in pore tortuosity. The increase in pore tortuosity with depth was associated with more decomposed peat soil and decreasing pore coordination number with depth, which extended the flow path of fluid particles. Results also revealed that hydraulic conductivity is isotropic locally, but becomes anisotropic after upscaling to core-scale; this suggests the anisotropy of peat hydraulic conductivity observed in core-scale and field-scale is due to the strong heterogeneity in the vertical dimension that is imposed by the layered structure of peat soils. Transport simulations revealed that for a given solute, the effective diffusion coefficient decreases with depth due to the corresponding increase of diffusional tortuosity. Longitudinal dispersivity of peat also was computed by analyzing advective-dominant transport simulations that showed peat dispersivity is similar to the empirical values reported in the same peat soil; it is not sensitive to soil depth and does not vary much along the soil profile.

Flux pinning properties of GdBCO bulk through the infiltration and growth process

NASA Astrophysics Data System (ADS)

Zhang, Y. F.; Wang, J. J.; Zhang, X. J.; Pan, C. Y.; Zhou, W. L.; Xu, Y.; Liu, Y. S.; Izumi, M.

2017-06-01

REBa2Cu3O7-δ(RE123 or REBCO, RE=rare earth elements, Gd, Y, Nd, etc.) bulk high temperature superconductors (HTS) have been used in lots of aspects, such as in magnetic levitation, et al., owing to the performance of high magnetic flux trapping. GdBCO superconductor bulk with 25 mm diameter has been successfully fabricated by top-seeded infiltration and growth (TSIG) method. We chose YBa2Cu3O7-δ (Y123) particles as the liquid source, which provide enough liquid sources during the growth and encourage the growth along a-b plane of GdBCO bulk. Then the existence of Y123 liquid source partly decreases the effect of the sub-grain boundaries in a-growth sectors and improves the properties of GdBCO bulk. The shape of the trapped field is close to circle. The critical current density of C2 and B2 (JC ) enhances. The superconducting transition temperature (TC ) is around 94.5K in the different position and keeps the superconducting properties. It is the important experimental data for the engineering applications of the superconductor bulk.

Physico-mechanical characteristics of commercially available bulk-fill composites.

PubMed

Leprince, Julian G; Palin, William M; Vanacker, Julie; Sabbagh, Joseph; Devaux, Jacques; Leloup, Gaetane

2014-08-01

Bulk-fill composites have emerged, arguably, as a new "class" of resin-based composites, which are claimed to enable restoration in thick layers, up to 4mm. The objective of this work was to compare, under optimal curing conditions, the physico-mechanical properties of most currently available bulk-fill composites to those of two conventional composite materials chosen as references, one highly filled and one flowable "nano-hybrid" composite. Tetric EvoCeram Bulk Fill (Ivoclar-Vivadent), Venus Bulk Fill (Heraeus-Kulzer), SDR (Dentsply), X-tra Fil (VOCO), X-tra Base (VOCO), Sonic Fill (Kerr), Filtek Bulk Fill (3M-Espe), Xenius (GC) were compared to the two reference materials. The materials were light-cured for 40s in a 2mm×2mm×25mm Teflon mould. Degree of conversion was measured by Raman spectroscopy, Elastic modulus and flexural strength were evaluated by three point bending, surface hardness using Vickers microindentation before and after 24h ethanol storage, and filler weight content by thermogravimetric analysis. The ratio of surface hardness before and after ethanol storage was considered as an evaluation of polymer softening. Data were analyzed by one-way ANOVA and post hoc Tukey's test (p=0.05). The mechanical properties of the bulk-fill composites were mostly lower compared with the conventional high viscosity material, and, at best, comparable to the conventional flowable composite. Linear correlations of the mechanical properties investigated were poor with degree of conversion (0.090.8). Softening in ethanol revealed differences in polymer network density between material types. The reduction of time and improvement of convenience associated with bulk-fill materials is a clear advantage of this particular material class. However, a compromise with mechanical properties compared with more conventional commercially-available nano-hybrid materials was demonstrated by the present work. Given the lower mechanical properties of most bulk-fill materials compared to a highly filled nano-hybrid composite, their use for restorations under high occlusal load is subject to caution. Further, the swelling behaviour of some of the bulk-fill materials may be a reason for concern, which highlights the critical requirement for a veneering material, not only to improve aesthetic quality of the translucent material, but to reduce the impact of degradation. Copyright © 2014 Elsevier Ltd. All rights reserved.

Exact solutions of bulk viscous with string cloud attached to strange quark matter for higher dimensional FRW universe in Lyra geometry

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

Çağlar, Halife, E-mail: hlfcglr@gmail.com; Aygün, Sezgin, E-mail: saygun@comu.edu.tr

In this study, we have investigated bulk viscous with strange quark matter attached to the string cloud for higher dimensional Friedman-Robertson-Walker (FRW) universe in Lyra geometry. By using varying deceleration parameter and conservation equations we have solved Einstein Field Equations (EFE’s) and obtained generalized exact solutions for our model. Also we have found that string is not survived for bulk viscous with strange quark matter attached to the string cloud in framework higher dimensional FRW universe in Lyra geometry. This result agrees with Kiran and Reddy, Krori et al, Sahoo and Mishra and Mohanty et al. in four and fivemore » dimensions.« less

Chondritic models of 4 Vesta: Implications for geochemical and geophysical properties

NASA Astrophysics Data System (ADS)

Toplis, M. J.; Mizzon, H.; Monnereau, M.; Forni, O.; McSween, H. Y.; Mittlefehldt, D. W.; McCoy, T. J.; Prettyman, T. H.; De Sanctis, M. C.; Raymond, C. A.; Russell, C. T.

2013-11-01

Simple mass-balance and thermodynamic constraints are used to illustrate the potential geochemical and geophysical diversity of a fully differentiated Vesta-sized parent body with a eucrite crust (e.g., core size and density, crustal thickness). The results of this analysis are then combined with data from the howardite-eucrite-diogenite (HED) meteorites and the Dawn mission to constrain Vesta's bulk composition. Twelve chondritic compositions are considered, comprising seven carbonaceous, three ordinary, and two enstatite chondrite groups. Our analysis excludes CI and LL compositions as plausible Vesta analogs, as these are predicted to have a negative metal fraction. Second, the MELTS thermodynamic calculator is used to show that the enstatite chondrites, the CV, CK and L-groups cannot produce Juvinas-like liquids, and that even for the other groups, depletion in sodium is necessary to produce liquids of appropriate silica content. This conclusion is consistent with the documented volatile-poor nature of eucrites. Furthermore, carbonaceous chondrites are predicted to have a mantle too rich in olivine to produce typical howardites and to have Fe/Mn ratios generally well in excess of those of the HEDs. On the other hand, an Na-depleted H-chondrite bulk composition is capable of producing Juvinas-like liquids, has a mantle rich enough in pyroxene to produce abundant howardite/diogenite, and has a Fe/Mn ratio compatible with eucrites. In addition, its predicted bulk-silicate density is within 100 kg m-3 of solutions constrained by data of the Dawn mission. However, oxidation state and oxygen isotopes are not perfectly reproduced and it is deduced that bulk Vesta may contain approximately 25% of a CM-like component. Values for the bulk-silicate composition of Vesta and a preliminary phase diagram are proposed.

Rapid and solvent-free solid-state synthesis and characterization of Zn3V2O8 nanostructures and their phenol red aqueous solution photodegradation

NASA Astrophysics Data System (ADS)

Mazloom, Fatemeh; Masjedi-Arani, Maryam; Salavati-Niasari, Masoud

2017-08-01

Zinc vanadate (Zn3V2O8) nanostructures have been successfully synthesized via simple, rapid and solvent-free solid-state method by using different complex precursors of Zn and NH4VO3 as novel starting materials. Effects of various zinc (II) Schiff base complex precursors and calcination temperatures were investigated to reach optimum condition. It was found that particle size and optical property of the as-prepared products could be greatly influenced via these parameters. The products were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectra, energy dispersive X-ray microanalysis (EDX), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Photoluminescence and ultraviolet-visible (UV-Vis) spectroscopy. The photocatalytic activity of zinc vanadate nano and bulk structures were compared by degradation of phenol red aqueous solution.

Review of Thermal Spray Coating Applications in the Steel Industry: Part 2—Zinc Pot Hardware in the Continuous Galvanizing Line

NASA Astrophysics Data System (ADS)

Matthews, S.; James, B.

2010-12-01

This two-part article series reviews the application of thermal spray coating technology in the production of steel and steel sheet products. Part 2 of this article series is dedicated to coating solutions in the continuous galvanizing line. The corrosion mechanisms of Fe- and Co-based bulk materials are briefly reviewed as a basis for the development of thermal spray coating solutions. WC-Co thermal spray coatings are commonly applied to low Al-content galvanizing hardware due to their superior corrosion resistance compared to Fe and Co alloys. The effect of phase degradation, carbon content, and WC grain size are discussed. At high Al concentrations, the properties of WC-Co coatings degrade significantly, leading to the application of oxide-based coatings and corrosion-resistant boride containing coatings. The latest results of testing are summarized, highlighting the critical coating parameters.

Solution-Processed Small-Molecule Bulk Heterojunctions: Leakage Currents and the Dewetting Issue for Inverted Solar Cells.

PubMed

Destouesse, Elodie; Chambon, Sylvain; Courtel, Stéphanie; Hirsch, Lionel; Wantz, Guillaume

2015-11-11

In organic photovoltaic (PV) devices based on solution-processed small molecules, we report here that the physicochemical properties of the substrate are critical for achieving high-performances organic solar cells. Three different substrates were tested: ITO coated with PSS, ZnO sol-gel, and ZnO nanoparticles. PV performances are found to be low when the ZnO nanoparticles layer is used. This performance loss is attributed to the formation of many dewetting points in the active layer, because of a relatively high roughness of the ZnO nanoparticles layer, compared to the other layers. We successfully circumvented this phenomenon by adding a small quantity of polystyrene (PS) in the active layer. The introduction of PS improves the quality of film forming and reduces the dark currents of solar cells. Using this method, high-efficiency devices were achieved, even in the case of substrates with higher roughness.

Thermohydrodynamic Analysis of Cryogenic Liquid Turbulent Flow Fluid Film Bearings

NASA Technical Reports Server (NTRS)

SanAndres, Luis

1996-01-01

Computational programs developed for the thermal analysis of tilting and flexure-pad hybrid bearings, and the unsteady flow and transient response of a point mass rotor supported on fluid film bearings are described. The motion of a cryogenic liquid on the thin film annular region of a fluid film bearing is described by a set of mass and momentum conservation, and energy transport equations for the turbulent bulk-flow velocities and pressure, and accompanied by thermophysical state equations for evaluation of the fluid material properties. Zeroth-order equations describe the fluid flow field for a journal static equilibrium position, while first-order (linear) equations govern the fluid flow for small amplitude-journal center translational motions. Solution to the zeroth-order flow field equations provides the bearing flow rate, load capacity, drag torque and temperature rise. Solution to the first-order equations determines the rotordynamic force coefficients due to journal radial motions.

Molecular Simulations of Graphene-Based Electric Double-Layer Capacitors

NASA Astrophysics Data System (ADS)

Kalluri, Raja K.; Konatham, Deepthi; Striolo, Alberto

2011-03-01

Towards deploying renewable energy sources it is crucial to develop efficient and cost-effective technologies to store electricity. Traditional batteries are plagued by a number of practical problems that at present limit their widespread applicability. One possible solution is represented by electric double-layer capacitors (EDLCs). To deploy EDLCs at the large scale it is necessary to better understand how electrolytes pack and diffuse within narrow charged pores. We present here simulation results for the concentrated aqueous solutions of NaCl, CsCl, and NaI confined within charged graphene-based porous materials. We discuss how the structure of confined water, the salt concentration, the ions size, and the surface charge density determine the accumulation of electrolytes within the porous network. Our results, compared to data available for bulk systems, are critical for relating macroscopic observations to molecular-level properties of the confined working fluids. Research supported by the Department of Energy.

Double-diffusive boundary layers along vertical free surfaces

NASA Astrophysics Data System (ADS)

Napolitano, L. G.; Viviani, A.; Savino, R.

1992-05-01

This paper deals with double-diffusive (or thermosolutal) combined free convection, i.e., free convection due to buoyant forces (natural convection) and surface tension gradients (Marangoni convection), which are generated by volume differences and surface gradients of temperature and solute concentration. Attention is focused on boundary layers that form along a vertical liquid-gas interface, when the appropriately defined nondimensional characteristic transport numbers are large enough, in problems of thermosolutal natural and Marangoni convection, such as buoyancy and surface tension driven flows in differentially heated open cavities and liquid bridges. Classes of similar solutions are derived for each class of convection on the basis of a rigorous order of magnitude analysis. Velocity, temperature and concentration profiles are reported in the similarity plane; flow and transport properties at the liquid-gas interface (interfacial velocity, heat and mass transfer bulk coefficients) are obtained for a wide range of Prandtl and Schmidt numbers and different values of the similarity parameter.

Adsorption Studies of Gadolinium ion on Graphitic Carbon Nitride

NASA Astrophysics Data System (ADS)

Kuila, S. K.; Kundu, T. K.

2018-03-01

Bulk graphitic carbon nitride (g-C3N4) is synthesized by thermal decomposition of urea and used as an adsorbent for gadolinium ion (Gd3+) from aqueous solution. Adsorption capacity of g-C3N4 is found to be influenced by initial Gd3+ concentration, solution pH and contact time. Adsorbed Gd3+is separated from g-C3N4 by ultracentrifuge. Initial and Gd ion accumulated g-C3N4 adsorbent are characterized by X-ray diffraction technique (XRD) for phase identification, UV-visible and Fourier transform infrared (FTIR) spectroscopy for adsorption characteristics and optical property, scanning electron microscopy (SEM) for morphological behaviour along with energy dispersive X-ray spectroscopy (EDS) for elemental study. HNO3(0.1M), NaOH (0.1M) and de-ionized water are used for desorption and around 97% quantitative recovery of Gd ion is observed.

Mechanism of radiative recombination in acceptor-doped bulk GaN crystals

NASA Astrophysics Data System (ADS)

Godlewski, M.; Suski, T.; Grzegory, I.; Porowski, S.; Bergman, J. P.; Chen, W. M.; Monemar, B.

1999-12-01

Optical and electrical properties of acceptor-doped bulk GaN crystals are discussed. Though introducing Zn and Ca to bulk GaN does not significantly change electron concentration, it results in the appearance of a blue photoluminescence band accompanying the relatively strong yellow band usually present. Highly resistive GaN : Mg crystals are obtained when high amount of Mg is introduced to the Ga melt during high-pressure synthesis. Change of electrical properties of Mg-doped bulk crystals is accompanied by the appearance of a strong blue emission of GaN similar to that in Ca- and Zn-doped crystals. Optically detected magnetic resonance investigations indicate a multi-band character of this blue emission and suggest possible mechanism of compensation in acceptor-doped bulk GaN.

Competitive adsorption in model charged protein mixtures: Equilibrium isotherms and kinetics behavior

NASA Astrophysics Data System (ADS)

Fang, F.; Szleifer, I.

2003-07-01

The competitive adsorption of proteins of different sizes and charges is studied using a molecular theory. The theory enables the study of charged systems explicitly including the size, shape, and charge distributions in all the molecular species in the mixture. Thus, this approach goes beyond the commonly used Poisson-Boltzmann approximation. The adsorption isotherms of the protein mixtures are studied for mixtures of two proteins of different size and charge. The amount of proteins adsorbed and the fraction of each protein is calculated as a function of the bulk composition of the solution and the amount of salt in the system. It is found that the total amount of proteins adsorbed is a monotonically decreasing function of the fraction of large proteins on the bulk solution and for fixed protein composition of the salt concentration. However, the composition of the adsorbed layer is a complicated function of the bulk composition and solution ionic strength. The structure of the adsorb layer depends upon the bulk composition and salt concentration. In general, there are multilayers adsorbed due to the long-range character of the electrostatic interactions. When the composition of large proteins in bulk is in very large excess it is found that the structure of the adsorb multilayer is such that the layer in contact with the surface is composed by a mixture of large and small proteins. However, the second and third layers are almost exclusively composed of large proteins. The theory is also generalized to study the time-dependent adsorption. The approach is based on separation of time scales into fast modes for the ions from the salt and the solvent and slow for the proteins. The dynamic equations are written for the slow modes, while the fast ones are obtained from the condition of equilibrium constrained to the distribution of proteins given by the slow modes. Two different processes are presented: the adsorption from a homogeneous solution to a charged surface at low salt concentration, and large excess of the large proteins in bulk. The second process is the kinetics of structural and adsorption change by changing the salt concentration of the bulk solution from low to high. The first process shows a large overshoot of the large proteins on the surface due to their excess in solution, followed by a surface replacement by the smaller molecules. The second process shows a very fast desorption of the large proteins followed by adsorption at latter stages. This process is found to be driven by large electrostatic repulsions induced by the fast ions from the salt approaching the surface. The relevance of the theoretical predictions to experimental system and possible directions for improvements of the theory are discussed.

Low temperature hot air drying of potato cubes subjected to osmotic dehydration and intermittent microwave: drying kinetics, energy consumption and product quality indexes

NASA Astrophysics Data System (ADS)

Dehghannya, Jalal; Bozorghi, Somayyeh; Heshmati, Maryam Khakbaz

2018-04-01

Hot-air drying is a slow energy-extensive process. Use of intermittent microwave (IM) in hot-air (HA) drying of food products is characterized with advantages including reduced process time, energy saving, and improved final quality. In this study, the effect of IM-HA drying following an osmotic dehydration (OD) pretreatment was analyzed on qualitative and quantitative properties of the output (i.e. effective moisture diffusion coefficient (Deff), shrinkage, bulk density, rehydration and energy consumption). Temperature and airflow velocity were fixed at 40°C and 1 m/s, respectively. The process variables included sucrose solution concentration at five levels (0 or control, 10, 30, 50 and 70 w/w%), microwave output power at four levels (0 or control, 360, 600 and 900 W), and pulse ratio at four levels (1, 2, 3 and 4). Use of osmotic dehydration in combination with IM-HA drying reduced the drying time by up to about 54%. Increasing the osmotic solution concentration to 30% and using higher pulse ratios increased the Deff. The lowest shrinkage and bulk density as well as the highest rehydration belonged to the 900 W microwave power and pulse ratio of 4. The lowest energy consumption was observed when using the 900 W power level, showing 63.27% less consumption than the HA drying method.

Microstructure and mechanical properties of bulk and plasma-sprayed y2O3-partially stabilized zirconia

NASA Technical Reports Server (NTRS)

Valentine, P. G.; Maier, R. D.

1980-01-01

Bulk 8.0 weight percent yttria partially stabilied zirconia (PSZ) was studied by light microscopy, transmission electron microscopy, X-ray analysis, microhardness testing, and fracture toughness testing. The as received PSZ contained spheroidal and grain boundary precipitates up to 4 micrometers in size. Spheroids up to 1.26 micrometers were metastable tetragonal; large spheroids were monoclinic. Grinding the PSZ into powder did not cause a significant amount of tetragonal to transform to monoclinic. This indicates that transformation toughness is not a significant mechanism in PSZ. Aging the PSZ at 1500 C caused the fine tetragonal precipitates to grow from 0.06 to 0.12 micrometers, in 250 minutes. A peak hardness of 1400 kg/sq mm was attained after 50 minutes. Solution annealing and quenching the as received PSZ eliminated the large precipitates, but fine tetragonal precipitates reformed on quenching. Aging at 1500 C caused the fine 0.02 micrometers tetragonal precipitates to grow into plates about 0.10 by 0.50 micrometers. A peak hardness of 1517 kg/sq mm was obtained after 250 minutes. On further aging, monoclinic percipitates formed along grain boundaries. The fracture toughness of the aged and unaged solution annealed and quenched PSZ was found to be between 2 and 3 MN /square root of m cubed. This range of fracture toughness is consistent with PSZ's that do not undergo transformation toughening.

Measurements of optical parameters of phantom solution and bulk animal tissues ex vivo at 650 nm

NASA Astrophysics Data System (ADS)

Sun, Ping; Wang, Yu; Liu, Jian

2008-12-01

Optical parameters of biological tissues, including absorption coefficient (μa), reduced scattering coefficient (μs') or scattering coefficient (μs), anisotropy factor (g) and refractive index (n) are investigated extensively and systemically at wavelength of 650 nm. Intralipid solution was selected to be the tissue phantom in order to test the validity of measurements. Considering the factors of fiber orientation and haemoglobin content, we chose some fresh bulk animal tissues in vitro which were bovine adipose, bovine muscle, porcine adipose, porcine muscle, porcine kidney, porcine liver, mutton and chicken breast. The basic assumption is that in vitro samples are a reasonable representation of the in vivo situation. We have gained numbers of experimental data of Intralipid and some tissues. Particularly, we have set up the close relationships among six optical parameters involving μa, μs', μs, g, n and μt. The experimental results show that for animal tissues, μa, μs' or μs and n rely deeply on muscle fiber orientations. Both of μs and μt range from 10mm-1 to 20mm-1. μa ranges from 10-2 mm-1 to 10-3 mm-1 and g from 0.95 to 0.99. The results of this study will be helpful in further understanding of optical properties of tissues.

Codimension-2 Brane Black Holes

NASA Astrophysics Data System (ADS)

Zamorano, Nelson; Arias, Cesar; Ordenes, Ariel; Guzman, Francisco

2012-03-01

We analyze the geometry associated to a six dimensional solution of the Einstein's equations. It describes a Schwarzschild de-Sitter black hole on a 3-brane, surrounded by a two dimensional compact bulk. A four dimensional effective cosmological constant and a Planck mass are matched to their six dimensional counterpart. Deviation from Newton's law are computed in both of the solutions found. To learn about the geometry of the bulk, we study the geodesics in this sector. At least, in our opinion, there are some features of these solutions that makes worth to pursue this analysis. The singularity associated to the warped bulk is controlled by the mass M of the black hole. It vanishes if we set M=0. In the same context, it makes an interesting problem to study the Gregory-Laflamme instability in this context [1]. Another feature is the rugby ball type of geometry exhibited by these solutions [2]. They end up in two conical singularities at its respective poles. The branes are located precisely at the poles. Besides, a Wick's rotation generates a connection between different solutions. [4pt] [1] R. Gregory and R. Laflamme, Phys. Rev Lett., 70,2837 (1993)[0pt] [2] S. M. Carroll and M. M. Guica, arXiv:hep-th/0302067

Injectable silk-based biomaterials for cervical tissue augmentation: an in vitro study.

PubMed

Brown, Joseph E; Partlow, Benjamin P; Berman, Alison M; House, Michael D; Kaplan, David L

2016-01-01

Cerclage therapy is an important treatment option for preterm birth prevention. Several patient populations benefit from cerclage therapy including patients with a classic history of cervical insufficiency; patients who present with advanced cervical dilation prior to viability; and patients with a history of preterm birth and cervical shortening. Although cerclage is an effective treatment option in some patients, it can be associated with limited efficacy and procedure complications. Development of an alternative to cerclage therapy would be an important clinical development. Here we report on an injectable, silk protein-based biomaterial for cervical tissue augmentation. The rationale for the development of an injectable biomaterial is to restore the native properties of cervical tissue. While cerclage provides support to the tissue, it does not address excessive tissue softening, which is a central feature of the pathogenesis of cervical insufficiency. Silk protein-based hydrogels, which are biocompatible and naturally degrade in vivo, are suggested as a platform for restoring the native properties of cervical tissue and improving cervical function. We sought to study the properties of an injectable, silk-based biomaterial for potential use as an alternative treatment for cervical insufficiency. These biomaterials were evaluated for mechanical tunability, biocompatibility, facile injection, and in vitro degradation. Silk protein solutions were cross-linked by an enzyme catalyzed reaction to form elastic biomaterials. Biomaterials were formulated to match the native physical properties of cervical tissue during pregnancy. The cell compatibility of the materials was assessed in vitro using cervical fibroblasts, and biodegradation was evaluated using concentrated protease solution. Tissue augmentation or bulking was demonstrated using human cervical tissue from nonpregnant hysterectomy specimens. Mechanical compression tests measured the tissue stiffness as a function of the volume of injected biomaterial. Silk protein concentration, molecular weight, and concentration of cross-linking agent were varied to generate biomaterials that functioned from hard gels to viscous fluids. Biomaterials that matched the mechanical features of cervical tissues were chosen for further study. Cervical fibroblasts cultured on these biomaterials were proliferative and metabolically active over 6 days. Biomaterials were degraded in protease solution, with rate of mass loss dependent on silk protein molecular weight. Injection of cervical tissue samples with 100 μL of the biomaterial resulted in a significant volume increase (22.6% ± 8.8%, P < .001) with no significant change in tissue stiffness. Cytocompatible, enzyme cross-linked silk protein biomaterials show promise as a tissue bulking agent. The biomaterials were formulated to match the native mechanical properties of human cervical tissue. These biomaterials should be explored further as a possible alternative to cerclage for providing support to the cervix during pregnancy. Copyright © 2016 Elsevier Inc. All rights reserved.

Fibrin structural and diffusional analysis suggests that fibers are permeable to solute transport.

PubMed

Leonidakis, Kimon Alexandros; Bhattacharya, Pinaki; Patterson, Jennifer; Vos, Bart E; Koenderink, Gijsje H; Vermant, Jan; Lambrechts, Dennis; Roeffaers, Maarten; Van Oosterwyck, Hans

2017-01-01

Fibrin hydrogels are promising carrier materials in tissue engineering. They are biocompatible and easy to prepare, they can bind growth factors and they can be prepared from a patient's own blood. While fibrin structure and mechanics have been extensively studied, not much is known about the relation between structure and diffusivity of solutes within the network. This is particularly relevant for solutes with a size similar to that of growth factors. A novel methodological approach has been used in this study to retrieve quantitative structural characteristics of fibrin hydrogels, by combining two complementary techniques, namely confocal fluorescence microscopy with a fiber extraction algorithm and turbidity measurements. Bulk rheological measurements were conducted to determine the impact of fibrin hydrogel structure on mechanical properties. From these measurements it can be concluded that variations in the fibrin hydrogel structure have a large impact on the rheological response of the hydrogels (up to two orders of magnitude difference in storage modulus) but only a moderate influence on the diffusivity of dextran solutes (up to 25% difference). By analyzing the diffusivity measurements by means of the Ogston diffusion model we further provide evidence that individual fibrin fibers can be semi-permeable to solute transport, depending on the average distance between individual protofibrils. This can be important for reducing mass transport limitations, for modulating fibrinolysis and for growth factor binding, which are all relevant for tissue engineering. Fibrin is a natural biopolymer that has drawn much interest as a biomimetic carrier in tissue engineering applications. We hereby use a novel combined approach for the structural characterization of fibrin networks based on optical microscopy and light scattering methods that can also be applied to other fibrillar hydrogels, like collagen. Furthermore, our findings on the relation between solute transport and fibrin structural properties can lead to the optimized design of fibrin hydrogel constructs for controlled release applications. Finally, we provide new evidence for the fact that fibrin fibers may be permeable for solutes with a molecular weight comparable to that of growth factors. This finding may open new avenues for tailoring mass transport properties of fibrin carriers. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Solution-processing of chalcogenide materials for device applications

NASA Astrophysics Data System (ADS)

Zha, Yunlai

Chalcogenide glasses are well-known for their desirable optical properties, which have enabled many infrared applications in the fields of photonics, medicine, environmental sensing and security. Conventional deposition methods such as thermal evaporation, chemical vapor deposition, sputtering or pulse laser deposition are efficient for fabricating structures on flat surfaces. However, they have limitations in deposition on curved surfaces, deposition of thick layers and component integration. In these cases, solution-based methods, which involve the dissolution of chalcogenide glasses and processing as a liquid, become a better choice for their flexibility. After proper treatment, the associated structures can have similar optical, chemical and physical properties to the bulk. This thesis presents an in-depth study of solution-processing chalcogenide glasses, starting from the "solution state" to the "film state" and the "structure state". Firstly, chalcogenide dissolution is studied to reveal the mechanisms at molecular level and build a foundation for material processing. Dissolution processes for various chalcogenide solvent pairs are reviewed and compared. Secondly, thermal processing, in the context of high temperature annealing, is explained along with the chemical and physical properties of the annealed films. Another focus is on nanopore formation in propylamine-processed arsenic sulfide films. Pore density changes with respect to annealing temperatures and durations are characterized. Base on a proposed vacancy coalescence theory, we have identified new dissolution strategies and achieved the breakthrough of pore-free film deposition. Thirdly, several solution methods developed along with the associated photonic structures are demonstrated. The first example is "spin-coating and lamination", which produces thick (over 10 mum) chalcogenide structures. Both homogeneous thick chalcogenide structures and heterogeneous layers of different chalcogenide glasses or metals can be fabricated. Second, "micro-molding in capillaries" (MIMIC) and "micro-transfer molding" (muTM) methods are introduced for fabricating waveguides on flat and curved surfaces. The flexibility of the solution process allows waveguides to be patterned, for the first time, on a curved surface. Third, "micro channel filling" is demonstrated to produce the lowest loss among solution-processed chalcogenide waveguides. These results contribute to the advancement of chalcogenide processing technologies and help move closer towards the ultimate goal of fabricating reliable IR sensors.

Salinity index determination of porous materials using open-ended probes

NASA Astrophysics Data System (ADS)

Szypłowska, Agnieszka; Kafarski, Marcin; Wilczek, Andrzej; Lewandowski, Arkadiusz; Skierucha, Wojciech

2017-01-01

The relations among soil water content, bulk electrical conductivity and electrical conductivity of soil solution can be described by a number of theoretical and empirical models. The aim of the paper is to examine the performance of open-ended coaxial probes with and without a short antenna in determination of complex dielectric permittivity spectra, moisture and salinity of porous materials using the salinity index approach. Glass beads of 0.26 and 1.24 mm average diameters moistened to various water contents with distilled water and KCl solutions were used to model the soil material. Due to the larger sensitivity zone, only the probe with the antenna enabled determination of bulk electrical conductivity and salinity index of the samples. The relations between bulk electrical conductivity and dielectric permittivity of the samples were highly linear, which was consistent with the salinity index model. The slope of the relation between salinity index and electrical conductivity of moistening solutions closely matched the value for 100 % sand presented in literature.

Effect of pH and interaction between egg white protein and hydroxypropymethylcellulose in bulk aqueous medium on foaming properties.

PubMed

Sadahira, Mitie S; Lopes, Fernanda C Rezende; Rodrigues, Maria I; Yamada, Aureo T; Cunha, Rosiane L; Netto, Flavia M

2015-07-10

Egg white protein (EW) is used as surface-active ingredient in aerated food and hydroxypropylmethylcellulose (HPMC) is a polysaccharide that behaves as a surfactant. This study aimed at investigating the effects of process parameters biopolymer concentration (2.0-5.0%, w/w), EW:HPMC ratio (2:1-18:1), pH (3.0-6.0), and the influence of biopolymers' behavior in aqueous solution at different pH on the foaming properties (overrun, drainage, and bubble growth rate). Process parameters had effect on foaming properties. The pH was the major factor influencing the type of EW/HPMC interaction and affected the foaming properties of biopolymer mixture. At pH 3.0, EW and HPMC showed thermodynamic compatibility leading to better foaming properties, higher foaming capacity, and stability than without HPMC addition whereas at pH 4.5 and 6.0, EW and HPMC are incompatible that causes lower stability concerning the disproportionation comparing to foam without HPMC. At pH between 3.0 and 4.5, HPMC improves foaming properties of aerated products. Copyright © 2015 Elsevier Ltd. All rights reserved.

Synthesis of highly elastic biocompatible polyurethanes based on bio-based isosorbide and poly(tetramethylene glycol) and their properties

PubMed Central

Kim, Hyo-Jin; Kang, Min-Sil; Knowles, Jonathan C

2014-01-01

Bio-based high elastic polyurethanes were prepared from hexamethylene diisocyanate and various ratios of isosorbide to poly(tetramethylene glycol) as a diol by a simple one-shot bulk polymerization without a catalyst. Successful synthesis of the polyurethanes was confirmed by Fourier transform-infrared spectroscopy and 1H nuclear magnetic resonance. Thermal properties were determined by differential scanning calorimetry and thermogravimetric analysis. The glass transition temperature was −47.8℃. The test results showed that the poly(tetramethylene glycol)/isosorbide-based elastomer exhibited not only excellent stress–strain properties but also superior resilience to the existing polyether-based polyurethane elastomers. The static and dynamic properties of the polyether/isosorbide-based thermoplastic elastomer were more suitable for dynamic applications. Moreover, such rigid diols impart biocompatible and bioactive properties to thermoplastic polyurethane elastomers. Degradation tests performed at 37℃ in phosphate buffer solution showed a mass loss of 4–9% after 8 weeks, except for the polyurethane with the lowest isosorbide content, which showed an initial rapid weight loss. These polyurethanes offer significant promise due to soft, flexible and biocompatible properties for soft tissue augmentation and regeneration. PMID:24812276

Nanomaterials in the forest products industry

Treesearch

Robert J. Moon

2008-01-01

Nanotechnology is the study and engineering of matter at the dimensions of 1-100 nm where physical, chemical, or biological properties are fundamentally different from those of the bulk material. The nanotechnology paradigm is to modify bulk properties and functionality by controlled manipulations at the nanoscale. Nanotechnology research has dramatically grown within...

Properties and durability of the passive films on a nickel-chromium-molybdenum alloy and an iron-based bulk metallic glass

NASA Astrophysics Data System (ADS)

Pharkya, Pallavi

Alloy 22, a Ni-Cr-Mo-W alloy, and SAM1651, an Fe-Cr-Mo-B-Y-C bulk metallic glass are highly corrosion-resistant alloys. The high corrosion resistance of these alloys is due to the formation of tenacious oxide films on their surfaces. This study examines the reformation behavior of the passive films as a function of the corrosion resistance of the alloys and the corrosivity of the environment. The main tasks of this study were (i) to determine the chemical durability of passive films on these highly corrosion-resistant alloys in aggressive environments, (ii) to investigate the durability after mechanically damaging the passive films either locally or over the entire surface area and to study the reformation kinetics, (iii) to compare the durability of the passive films of the aforementioned highly corrosion resistant alloys with an alloy of intermediate corrosion resistance, AL6XN, and an alloy of less corrosion resistance, 316L SS, (iv) to examine the evolution of the electronic properties of the passive films on alloy 22 and SAM1651 under different environmental conditions such as concentrated chloride solution, acidic solution, temperature, potential and oxyanions, and (v) to develop an understanding of the relationship between the passive films' composition, electronic and electrochemical properties and the performance. A combination of techniques was utilized to meet the above mentioned objectives. Cyclic potentiodynamic polarization (CPP) was used to determine the electrochemical parameters such as freely corroding, breakdown and repassivation potentials. Electrochemical impedance spectroscopy (EIS) was used to determine the electronic properties such as impedance, thickness and capacitance of the passive films. Mott-Schottky (M-S) analysis was used to determine the type and the density of the defects in the passive films. The mechanical durability and reformation kinetics of the passive films was investigated using a scratch-repassivation method. The quality and the protectiveness of the reformed passive films after scribing were examined using EIS, M-S analysis, and AES. The results show that the passive films on alloy 22 and SAM1651 possess high chemical and mechanical durability. The reformed passive films acquired the same electronic and elemental properties as the passive films which were undamaged. The passive films on SAM1651 and alloy 22 showed better corrosion resistance and durability than did the passive films on AL6XN and 316L SS. The results also showed that the passive film behavior depends on the inherent corrosion resistance of an alloy and the corrosivity of the environment. The inherent corrosion resistance depends on the concentration of the passivity-providing elements such as Cr and Mo in the bulk composition of the alloy (and passive film), and the corrosivity of the environment which is influenced by chloride concentration, oxyanions, temperature, pH, and oxidizing potential.

Spatial Variability of Soil Physical Properties Obtained with Laboratory Methods and Their Relation to Field Electrical Resistivity Measurements

NASA Astrophysics Data System (ADS)

Dathe, A.; Nemes, A.; Bloem, E.; Patterson, M.; Gimenez, D.; Angyal, A.; Koestel, J. K.; Jarvis, N.

2017-12-01

Soil spatial heterogeneity plays a critical role for describing water and solute transport processes in the unsaturated zone. Although we have a sound understanding of the physical properties underlying this heterogeneity (like macropores causing preferential water flow), their quantification in a spatial context is still a challenge. To improve existing knowledge and modelling approaches we established a field experiment on an agriculturally used silty clay loam (Stagnosol) in SE Norway. Centimeter to decimeter scale heterogeneities were investigated in the field using electrical resistivity tomography (ERT) in a quasi-3D and a real 3D approach. More than 100 undisturbed soil samples were taken in the 2x1x1 m3plot investigated with 3D ERT to determine soil water retention, saturated and unsaturated hydraulic conductivities and bulk density in the laboratory. A subset of these samples was scanned at the computer tomography (CT) facility at the Swedish University of Agricultural Sciences in Uppsala, Sweden, with special emphasis on characterizing macroporosity. Results show that the ERT measurements captured the spatial distribution of bulk densities and reflected soil water contents. However, ERT could not resolve the large variation observed in saturated hydraulic conductivities from the soil samples. Saturated hydraulic conductivity was clearly related to the macroporosity visible in the CT scans obtained from the respective soil cores. Hydraulic conductivities close to saturation mainly changed with depths in the soil profile and therefore with bulk density. In conclusion, to quantify the spatial heterogeneity of saturated hydraulic conductivities scanning methods with a resolution smaller than the size of macropores have to be used. This is feasible only when the information obtained from for example CT scans of soil cores would be upscaled in a meaningful way.

A Single Molecular Diels-Alder Crosslinker for Achieving Recyclable Cross-Linked Polymers.

PubMed

Chen, Shengli; Wang, Fenfen; Peng, Yongjin; Chen, Tiehong; Wu, Qiang; Sun, Pingchuan

2015-09-01

A triol-functional crosslinker combining the thermoreversible properties of Diels-Alder (DA) adducts in one molecule is designed, synthesized, and used as an ideal substitute of a traditional crosslinker to prepare thermal recyclable cross-linked polyurethanes with excellent mechanical properties and recyclability in a very simple and efficient way. The recycle property of these materials achieved by the DA/retro-DA reaction at a suitable temperature is verified by differential scanning calorimetry and in situ variable temperature solid-state NMR experiments during the cyclic heating and cooling processes. The thermal recyclability and remending ability of the bulk polyurethanes is demonstrated by three polymer processing methods, including hot-press molding, injection molding, and solution casting. It is notable that all the recycled cross-linked polymers display nearly invariable elongation/stress at break compared to the as-synthesized samples. Further end-group functionalization of this single molecular DA crosslinker provides the potential in preparing a wide range of recyclable cross-linked polymers. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anomalous bulk behavior in the free parafermion Z (N ) spin chain

NASA Astrophysics Data System (ADS)

Alcaraz, Francisco C.; Batchelor, Murray T.

2018-06-01

We demonstrate using direct numerical diagonalization and extrapolation methods that boundary conditions have a profound effect on the bulk properties of a simple Z (N ) model for N ≥3 for which the model Hamiltonian is non-Hermitian. For N =2 the model reduces to the well-known quantum Ising model in a transverse field. For open boundary conditions, the Z (N ) model is known to be solved exactly in terms of free parafermions. Once the ends of the open chain are connected by considering the model on a ring, the bulk properties, including the ground-state energy per site, are seen to differ dramatically with increasing N . Other properties, such as the leading finite-size corrections to the ground-state energy, the mass gap exponent, and the specific-heat exponent, are also seen to be dependent on the boundary conditions. We speculate that this anomalous bulk behavior is a topological effect.

Electronic, transport, and optical properties of bulk and mono-layer PdSe 2

DOE PAGES

Sun, Jifeng; Shi, Hongliang; Siegrist, Theo; ...

2015-10-13

In this study, the electronic and optical properties of bulk and monolayer PdSe 2 are investigated using firstprinciples calculations. Using the modified Becke-Johnson potential, we find semiconductor behavior for both bulk and monolayer PdSe 2 with indirect gap values of 0.03 eV for bulk and 1.43 eV for monolayer, respectively. Our sheet optical conductivity results support this observation and show similar anisotropic feature in the 2D plane. We further study the thermoelectric properties of the 2D PdSe 2 using Blotzmann transport model and find interestingly high Seebeck coefficients (>200 μV/K) for both p- and n-type up to high doping levelmore » (–2 x 10 13 cm 2) with an anisotropic character in an electrical conductivity suggesting better thermoelectric performance along y direction in the plane.V« less

Ab initio study of perovskite type oxide materials for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Lee, Yueh-Lin

2011-12-01

Perovskite type oxides form a family of materials of significant interest for cathodes and electrolytes of solid oxide fuel cells (SOFCs). These perovskites not only are active catalysts for surface oxygen reduction (OR) reactions but also allow incorporating the spilt oxygen monomers into their bulk, an unusual and poorly understood catalytic mechanism that couples surface and bulk properties. The OR mechanisms can be influenced strongly by defects in perovskite oxides, composition, and surface defect structures. This thesis work initiates a first step in developing a general strategy based on first-principles calculations for detailed control of oxygen vacancy content, transport rates of surface and bulk oxygen species, and surface/interfacial reaction kinetics. Ab initio density functional theory methods are used to model properties relevant for the OR reactions on SOFC cathodes. Three main research thrusts, which focus on bulk defect chemistry, surface defect structures and surface energetics, and surface catalytic properties, are carried to investigate different level of material chemistry for improved understanding of key physics/factors that govern SOFC cathode OR activity. In the study of bulk defect chemistry, an ab initio based defect model is developed for modeling defect chemistry of LaMnO 3 under SOFC conditions. The model suggests an important role for defect interactions, which are typically excluded in previous defect models. In the study of surface defect structures and surface energetics, it is shown that defect energies change dramatically (1˜2 eV lower) from bulk values near surfaces. Based on the existing bulk defect model with the calculated ab initio surface defect energetics, we predict the (001) MnO 2 surface oxygen vacancy concentration of (La0.9Sr0.1 )MnO3 is about 5˜6 order magnitude higher than that of the bulk under typical SOFC conditions. Finally, for surface catalytic properties, we show that area specific resistance, oxygen exchange rates, and key OR energetics of the SOFC cathode perovskites, can be described by a single descriptor, either the bulk O p-band or the bulk oxygen vacancy formation energy. These simple descriptors will further enable first-principles optimization/design of new SOFC cathodes.

Mechanical Properties of Air Plasma Sprayed Environmental Barrier Coating (EBC) Materials

NASA Technical Reports Server (NTRS)

Richards, Bradley; Zhu, Dongming; Ghosn, Louis; Wadley, Haydn

2015-01-01

Development work in Environmental Barrier Coatings (EBCs) for Ceramic Matrix Composites (CMCs) has focused considerably on the identification of materials systems and coating architectures to meet application needs. The evolution of these systems has occurred so quickly that modeling efforts and requisite data for modeling lag considerably behind development. Materials property data exists for many systems in the bulk form, but the effects of deposition on the critical properties of strength and fracture behavior are not well studied. We have plasma sprayed bulk samples of baseline EBC materials (silicon, ytterbium disilicate) and tested the mechanical properties of these materials to elicit differences in strength and toughness. We have also endeavored to assess the mixed-mode fracture resistance, Gc, of silicon in a baseline EBC applied to SiCSiC CMC via four point bend test. These results are compared to previously determined properties of the comparable bulk material.

Predicting Hidden bulk phases in Sr3Ru2O7 from surface phases

NASA Astrophysics Data System (ADS)

Rivero, Pablo; Chen, Chen; Jin, Roying; Meunier, Vincent; Plummer, E. W.; Shelton, William

Double-layered Sr3Ru2O7 has received phenomenal attention as it exhibits an overabundance of exotic phases when perturbed. Recently it has been shown that the surface of this material displays significantly different properties than in the bulk due to the surface induced tilt of the RuO6 octahedra. Here we report detailed first principles calculations of the surface structure, and the structure property relationship. Tilt of the octahedra drive the surface into a much less conducting state than in the bulk due in part to the different electronic properties of the two Ru atoms in the first RuO2 layer of the bilayer. The broken symmetry at the surface causes a tilt and enhanced rotation of the octahedra only present in the first (surface) bilayer. Theoretically the surface is ferromagnetically ordered but the stability with respect to the antiferromagnetic phase is small ( = 11 meV). We have calculated the bulk properties under uniaxial pressure, which induces a tilt and drives the bulk into an antiferromagnetic-insulating state. Support of this project came from DoE contract No. DE-SCOO12432 and the Louisiana Board of Regents. V. M. acknowledges support from New York State under NYSTAR program C080117.

Quantifying yield behaviour in metals by X-ray nanotomography

PubMed Central

Mostafavi, M.; Bradley, R.; Armstrong, D. E. J.; Marrow, T. J.

2016-01-01

Nanoindentation of engineering materials is commonly used to study, at small length scales, the continuum mechanical properties of elastic modulus and yield strength. However, it is difficult to measure strain hardening via nanoindentation. Strain hardening, which describes the increase in strength with plastic deformation, affects fracture toughness and ductility, and is an important engineering material property. The problem is that the load-displacement data of a single nanoindentation do not provide a unique solution for the material’s plastic properties, which can be described by its stress-strain behaviour. Three-dimensional mapping of the displacement field beneath the indentation provides additional information that can overcome this difficulty. We have applied digital volume correlation of X-ray nano-tomographs of a nanoindentation to measure the sub-surface displacement field and so obtain the plastic properties of a nano-structured oxide dispersion strengthened steel. This steel has potential applications in advanced nuclear energy systems, and this novel method could characterise samples where proton irradiation of the surface simulates the effects of fast neutron damage, since facilities do not yet exist that can replicate this damage in bulk materials. PMID:27698472

Fibrillization kinetics of insulin solution in an interfacial shearing flow

NASA Astrophysics Data System (ADS)

Balaraj, Vignesh; McBride, Samantha; Hirsa, Amir; Lopez, Juan

2015-11-01

Although the association of fibril plaques with neurodegenerative diseases like Alzheimer's and Parkinson's is well established, in-depth understanding of the roles played by various physical factors in seeding and growth of fibrils is far from well known. Of the numerous factors affecting this complex phenomenon, the effect of fluid flow and shear at interfaces is paramount as it is ubiquitous and the most varying factor in vivo. Many amyloidogenic proteins have been found to denature upon contact at hydrophobic interfaces due to the self-assembling nature of protein in its monomeric state. Here, fibrillization kinetics of insulin solution is studied in an interfacial shearing flow. The transient surface rheological response of the insulin solution to the flow and its effect on the bulk fibrillization process has been quantified. Minute differences in hydrophobic characteristics between two variants of insulin- Human recombinant and Bovine insulin are found to result in very different responses. Results presented will be in the form of fibrillization assays, images of fibril plaques formed, and changes in surface rheological properties of the insulin solution. The interfacial velocity field, measured from images (via Brewster Angle Microscopy), is compared with computations. Supported by NNX13AQ22G, National Aeronautics and Space Administration.

The respective roles of bulk friction and slip velocity during a granular mass flow

NASA Astrophysics Data System (ADS)

Staron, Lydie

2016-04-01

Catastrophic granular mass flows form an important natural hazard. Mitigation has motivated numerous studies on the properties of natural granular flows, and in particular, their ability to travel long distances away from the release point. The mobility of granular flows is commonly characterised through the definition of rheological properties and effective friction. Yet, it is widely accepted that the description in term of effective friction may include various lubrication effects, softening at the base of the flow and large slip velocities being a most likely one. In this case, flow bulk properties may obliterate the flow boundary conditions. In this contribution, we investigate how disentangling bulk properties from boundary conditions may improve our understanding of the flow. Using discrete simulations, we induce increasing slip velocities in different flow configurations. We show that increased mobility may be achieved without changing bulk properties. The results are interpreted in terms of a Robin-Navier slip condition and implemented in a continuum Navier-Stokes solver. We quantify the respective role of rheological bulk properties and boundary conditions in the general behaviour of a transient mass flow. We show that omitting the description of boundary conditions leads to misinterpretation of the flow properties. The outcome is discussed in terms of models reliability. References P.-Y. Lagrée et al, The granular column collapse as a continuum: validity of a two-dimensional Navier-Stokes model with the mu(I) rheology, J. Fluid Mech. 686, 378-408 (2011) L. Staron and E. Lajeunesse, Understanding how the volume affects the mobility of dry debris flows, Geophys. Res. Lett. 36, L12402 (2009) L. Staron, Mobility of long-runout rock flows: a discrete numerical investigation, Geophys. J. Int. 172, 455-463 (2008)

Transport properties of C and O in UN fuels

NASA Astrophysics Data System (ADS)

Schuler, Thomas; Lopes, Denise Adorno; Claisse, Antoine; Olsson, Pär

2017-03-01

Uranium nitride fuel is considered for fast reactors (GEN-IV generation and space reactors) and for light water reactors as a high-density fuel option. Despite this large interest, there is a lack of information about its behavior for in-pile and out-of-pile conditions. From the present literature, it is known that C and O impurities have significant influence on the fuel performance. Here we perform a systematic study of these impurities in the UN matrix using electronic-structure calculations of solute-defect interactions and microscopic jump frequencies. These quantities were calculated in the DFT +U approximation combined with the occupation matrix control scheme, to avoid convergence to metastable states for the 5 f levels. The transport coefficients of the system were evaluated with the self-consistent mean-field theory. It is demonstrated that carbon and oxygen impurities have different diffusion properties in the UN matrix, with O atoms having a higher mobility, and C atoms showing a strong flux coupling anisotropy. The kinetic interplay between solutes and vacancies is expected to be the main cause for surface segregation, as incorporation energies show no strong thermodynamic segregation preference for (001) surfaces compared with the bulk.

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

Smith, Jacob W.; Lam, Royce K.; Saykally, Richard J., E-mail: saykally@berkeley.edu

Nitrate and nitrite ions are of considerable interest, both for their widespread use in commercial and research contexts and because of their central role in the global nitrogen cycle. The chemistry of atmospheric aerosols, wherein nitrate is abundant, has been found to depend on the interfacial behavior of ionic species. The interfacial behavior of ions is determined largely by their hydration properties; consequently, the study of the hydration and interfacial behavior of nitrate and nitrite comprises a significant field of study. In this work, we describe the study of aqueous solutions of sodium nitrate and nitrite via X-ray absorption spectroscopymore » (XAS), interpreted in light of first-principles density functional theory electronic structure calculations. Experimental and calculated spectra of the nitrogen K-edge XA spectra of bulk solutions exhibit a large 3.7 eV shift between the XA spectra of nitrate and nitrite resulting from greater stabilization of the nitrogen 1s energy level in nitrate. A similar shift is not observed in the oxygen K-edge XA spectra of NO{sub 3}{sup −} and NO{sub 2}{sup −}. The hydration properties of nitrate and nitrite are found to be similar, with both anions exhibiting a similar propensity towards ion pairing.« less

Effects of inoculum type and bulk dissolved oxygen concentration on achieving partial nitrification by entrapped-cell-based reactors.

PubMed

Rongsayamanont, Chaiwat; Limpiyakorn, Tawan; Khan, Eakalak

2014-07-01

An entrapment of nitrifiers into gel matrix is employed as a tool to fulfill partial nitrification under non-limiting dissolved oxygen (DO) concentrations in bulk solutions. This study aims to clarify which of these two attributes, inoculum type and DO concentration in bulk solutions, is the decisive factor for partial nitrification in an entrapped-cell based system. Four polyvinyl alcohol entrapped inocula were prepared to have different proportions of nitrite-oxidizing bacteria (NOB) and nitrite-oxidizing activity. At a DO concentration of 3 mg l(-1), the number of active NOB cells in an inoculum was the decisive factor for partial nitrification enhancement. However, when the DO concentration was reduced to 2 mg l(-1), all entrapped cell inocula showed similar degrees of partial nitrification. The results suggested that with the lower bulk DO concentration, the preparation of entrapped cell inocula is not useful as the DO level becomes the decisive factor for achieving partial nitrification. Copyright © 2014 Elsevier Ltd. All rights reserved.

Low temperature reduction of free-standing graphene oxide papers with metal iodides for ultrahigh bulk conductivity.

PubMed

Liu, Chenyang; Hao, Feng; Zhao, Xiaochong; Zhao, Qiancheng; Luo, Songping; Lin, Hong

2014-02-05

Here we report a green and facile route for highly efficient reduction of free-standing graphene oxide (GO) papers with metal iodide aqueous solutions at low cost. The metal iodides (MgI2, AlI3, ZnI2, FeI2) were synthesized directly from metal and iodine powder with water as a catalyzer. An extremely high bulk conductivity of 55088 S/m for reduced graphene oxide (rGO) papers were obtained with FeI2 solution of which pH = 0 at 95°C for 6 hours. The catalytic effect of strong Lewis acid for the promotion of the nucleophilic substitution reaction is responsible for the greatly improved bulk conductivity. Furthermore, it was found that the layer-to-layer distance (dL) and the crystallinity of the rGO papers are regarded as two main factors affecting the bulk conductivity rather than C/O ratio and defect concentration.

PREFACE: Water at interfaces Water at interfaces

NASA Astrophysics Data System (ADS)

Gallo, P.; Rovere, M.

2010-07-01

This special issue is devoted to illustrating important aspects and significant results in the field of modeling and simulation of water at interfaces with solutes or with confining substrates, focusing on a range of temperatures from ambient to supercooled. Understanding the behavior of water, in contact with different substrates and/or in solutions, is of pivotal importance for a wide range of applications in physics, chemistry and biochemistry. Simulations of confined and/or interfacial water are also relevant for testing how different its behavior is with respect to bulk water. Simulations and modeling in this field are of particular importance when studying supercooled regions where water shows anomalous properties. These considerations motivated the organization of a workshop at CECAM in the summer of 2009 which aimed to bring together scientists working with computer simulations on the properties of water in various environments with different methodologies. In this special issue, we collected a variety of interesting contributions from some of the speakers of the workshop. We have roughly classified the contributions into four groups. The papers of the first group address the properties of interfacial and confined water upon supercooling in an effort to understand the relation with anomalous behavior of supercooled bulk water. The second group deals with the specific problem of solvation. The next group deals with water in different environments by considering problems of great importance in technological and biological applications. Finally, the last group deals with quantum mechanical calculations related to the role of water in chemical processes. The first group of papers is introduced by the general paper of Stanley et al. The authors discuss recent progress in understanding the anomalies of water in bulk, nanoconfined, and biological environments. They present evidence that liquid water may display 'polymorphism', a property that can be present in other liquids also. Recent evidence of a close relation between thermodynamical properties and dynamical behaviour of water are also discussed. Gallo et al present the results of a computer simulation of water confined in a cylindrical pore of MCM-41 silica material. The mobile portion of the confined water shows a fragile to strong dynamic transition similar to the bulk. In the bound water, an anomalous diffusion connected to the residence time distribution is found. Franzese et al report calculations on lattice models adapted to describe general properties of water in contact with protein surfaces. The results of Monte Carlo and mean field calculations show the presence of two-dynamical crossovers. Corradini et al investigate the supercooled region of ionic aqueous solutions in order to study the effect of ions on the limit of mechanical stability, the lines of maximum density and the liquid-liquid critical point for different ionic concentrations. The paper by Vallauri et al deals with the dynamical behavior of water close to the liquid-liquid transition by considering the velocity correlation functions calculated in three supercooled states. Suffritti et al study water adsorbed in zeolites with a new empirical potential, structural and dynamical properties are studied in the supercooled region. The second group starts with a paper on the problem of solvation by Lynden-Bell. The author shows how the properties of water and, in particular, solvation properties are modified by changes in the site-site interaction potential of water. Henchman et al derive equations for different thermodynamical quantities like partial enthalpy and partial entropy for dilute solutions of noble gases. The third group starts with Buldyrev et al who study the swelling of bead-on-a-string polymers in Jagla water-like particles, finding similarities with respect to cold denaturation of protein in water. Pellenq et al consider water confined in pores of different materials with different size scales. Silicalite and tobermorite, a layered calcio-silicate model of cement and Vycor are analyzed. Gordillo and Martí consider structural and dynamical properties of water confined or close to carbon nanotubes or inside a slit pore of a single graphene sheet. Jedlovszky et al introduce a new method to determine the molecules located right at the boundary of two phases in a computer simulation. The new method is applied to the analysis of the interface of water with different apolar phases. Melchionna et al consider phenomena related to water in contact with thermophilic protein interfaces. In particular, they discuss the role of water in stabilizing these proteins. Rotenberg et al report results on the structure and dynamics of water at a clay surface. They analyze, in particular, the influence on the H-bond network of the surface oxygens and ions and investigate the surface H-bond formation and dissociation dynamics. Smirnov and Bougeard present examples of the spatial organization of molecules and of the short- and long-time dynamical behaviour of water confined in the pores of crystalline aluminosilicates, such as zeolites and clays, and in nanostructured materials. The last group opens with Sulpizi and Sprik who present density functional calculations of the dissociation constant of liquid water, implemented with a proton insertion/removal method. Jung and Marcus consider, more specifically, the properties of water in organic catalysis and discuss theoretical models and results obtained with quantum mechanical calculations. As organizers of the CECAM workshop 'Modeling and Simulation of Water at Interfaces from Ambient to Supercooled Conditions' we would like to thank CECAM, ESF-Simbioma, Wanda Andreoni, Emilie Bernard and Jordi Brusa. As guest editors of this special issue we would like to thank Gerhard Kahl and Philip Semple.

Transient finite element analysis of electric double layer using Nernst-Planck-Poisson equations with a modified Stern layer.

PubMed

Lim, Jongil; Whitcomb, John; Boyd, James; Varghese, Julian

2007-01-01

A finite element implementation of the transient nonlinear Nernst-Planck-Poisson (NPP) and Nernst-Planck-Poisson-modified Stern (NPPMS) models is presented. The NPPMS model uses multipoint constraints to account for finite ion size, resulting in realistic ion concentrations even at high surface potential. The Poisson-Boltzmann equation is used to provide a limited check of the transient models for low surface potential and dilute bulk solutions. The effects of the surface potential and bulk molarity on the electric potential and ion concentrations as functions of space and time are studied. The ability of the models to predict realistic energy storage capacity is investigated. The predicted energy is much more sensitive to surface potential than to bulk solution molarity.

46 CFR Table 2 to Part 153 - Cargoes Not Regulated Under Subchapters D or O of This Chapter When Carried in Bulk on Non...

Code of Federal Regulations, 2014 CFR

2014-10-01

...) (with 52% Chlorine) III 2-Chloro-4-ethylamino-6-isopropylamino-5-triazine solution # Choline chloride...-5-triazine solution # 4-Chloro-2-methylphenoxyacetic acid, dimethylamine salt solution * Y Choline...

Microstructurally tailored ceramics for advanced energy applications by thermoreversible gelcasting

NASA Astrophysics Data System (ADS)

Shanti, Noah Omar

Thermoreversible gelcasting (TRG) is an advantageous technique for rapidly producing bulk, net-shape ceramics and laminates. In this method, ceramic powder is suspended in warm acrylate triblock copolymer/alcohol solutions that reversibly gel upon cooling by the formation of endblock aggregates, to produce slurries which are cast into molds. Gel properties can be tailored by controlling the endblock and midblock lengths of the copolymer network-former and selecting an appropriate alcohol solvent. This research focuses on expanding and improving TRG techniques, focusing specifically on advanced energy applications including the solid oxide fuel cell (SOFC). Rapid drying of filled gels can lead to warping and cracking caused by high differential capillary stresses. A new drying technique using concentrated, alcohol-based solutions as liquid desiccants (LDs) to greatly reduce warping is introduced. The optimal LD is a poly(tert-butyl acrylate)/isopropyl alcohol solution with 5 mol% tert-butyl acrylate units. Alcohol emissions during drying are completely eliminated by combining initial drying in an LD with final stage drying in a vacuum oven having an in-line solvent trap. Porous ceramics are important structures for many applications, including SOFCs. Pore network geometries are tailored by the addition of fugitive fillers to TRG slurries. Uniform spherical, bimodal spherical and uniform fibrous fillers are used. Three-dimensional pore structures are visualized by X-ray computed tomography, allowing for direct measurements of physical parameters such as concentration and morphology as well as transport properties such as tortuosity. Tortuosity values as low as 1.52 are achieved when 60 vol% of solids are uniform spherical filler. Functionally graded laminates with layers ranging from 10 mum to > 1 mm thick are produced with a new technique that combines TRG with tape casting. Gels used for bulk casting are not suitable for use with tape casting, and appropriate base gels are selected for this technique. Each layer is cast in a single pass, and the layers are directly laminated. The anode support, anode functional layer, and electrolyte of anode-supported SOFCs are produced using this technique. The performance of SOFCs produced this way is not yet equal to that of traditionally processed cells, but shows the promise of this technique.

Dielectric properties-based method for rapid and nondestructive moisture sensing in almonds

USDA-ARS?s Scientific Manuscript database

A dielectric-based method is presented for moisture determination in almonds independent of bulk density. The dielectric properties of almond were measured between 5 and 15 GHz, with a 1-GHz increments, for samples with moisture contents ranging from 4.8% to 16.5%, wet basis, bulk densities ranging ...

Macromolecular crowding gives rise to microviscosity, anomalous diffusion and accelerated actin polymerization

NASA Astrophysics Data System (ADS)

Rashid, Rafi; Chee, Stella Min Ling; Raghunath, Michael; Wohland, Thorsten

2015-05-01

Macromolecular crowding (MMC) has been used in various in vitro experimental systems to mimic in vivo physiology. This is because the crowded cytoplasm of cells contains many different types of solutes dissolved in an aqueous medium. MMC in the extracellular microenvironment is involved in maintaining stem cells in their undifferentiated state (niche) as well as in aiding their differentiation after they have travelled to new locations outside the niche. MMC at physiologically relevant fractional volume occupancies (FVOs) significantly enhances the adipogenic differentiation of human bone marrow-derived mesenchymal stem cells during chemically induced adipogenesis. The mechanism by which MMC produces this enhancement is not entirely known. In the context of extracellular collagen deposition, we have recently reported the importance of optimizing the FVO while minimizing the bulk viscosity. Two opposing properties will determine the net rate of a biochemical reaction: the negative effect of bulk viscosity and the positive effect of the excluded volume, the latter being expressed by the FVO. In this study we have looked more closely at the effect of viscosity on reaction rates. We have used fluorimetry to measure the rate of actin polymerization and fluorescence correlation spectroscopy (FCS) to measure diffusion of various probes in solutions containing the crowder Ficoll at physiological concentrations. Similar to its effect on collagen, Ficoll enhanced the actin polymerization rate despite increasing the bulk viscosity. Our FCS measurements reveal a relatively minor component of anomalous diffusion. In addition, our measurements do suggest that microviscosity becomes relevant in a crowded environment. We ruled out bulk viscosity as a cause of the rate enhancement by performing the actin polymerization assay in glycerol. These opposite effects of Ficoll and glycerol led us to conclude that microviscosity becomes relevant at the length scale of the reacting molecules within a crowded microenvironment. The excluded volume effect (arising from crowding) increases the effective concentration of actin, which increases the reaction rate, while the microviscosity does not increase sufficiently to lower the reaction rate. This study reveals finer details about the mechanism of MMC.

Macromolecular crowding gives rise to microviscosity, anomalous diffusion and accelerated actin polymerization.

PubMed

Rashid, Rafi; Chee, Stella Min Ling; Raghunath, Michael; Wohland, Thorsten

2015-04-30

Macromolecular crowding (MMC) has been used in various in vitro experimental systems to mimic in vivo physiology. This is because the crowded cytoplasm of cells contains many different types of solutes dissolved in an aqueous medium. MMC in the extracellular microenvironment is involved in maintaining stem cells in their undifferentiated state (niche) as well as in aiding their differentiation after they have travelled to new locations outside the niche. MMC at physiologically relevant fractional volume occupancies (FVOs) significantly enhances the adipogenic differentiation of human bone marrow-derived mesenchymal stem cells during chemically induced adipogenesis. The mechanism by which MMC produces this enhancement is not entirely known. In the context of extracellular collagen deposition, we have recently reported the importance of optimizing the FVO while minimizing the bulk viscosity. Two opposing properties will determine the net rate of a biochemical reaction: the negative effect of bulk viscosity and the positive effect of the excluded volume, the latter being expressed by the FVO. In this study we have looked more closely at the effect of viscosity on reaction rates. We have used fluorimetry to measure the rate of actin polymerization and fluorescence correlation spectroscopy (FCS) to measure diffusion of various probes in solutions containing the crowder Ficoll at physiological concentrations. Similar to its effect on collagen, Ficoll enhanced the actin polymerization rate despite increasing the bulk viscosity. Our FCS measurements reveal a relatively minor component of anomalous diffusion. In addition, our measurements do suggest that microviscosity becomes relevant in a crowded environment. We ruled out bulk viscosity as a cause of the rate enhancement by performing the actin polymerization assay in glycerol. These opposite effects of Ficoll and glycerol led us to conclude that microviscosity becomes relevant at the length scale of the reacting molecules within a crowded microenvironment. The excluded volume effect (arising from crowding) increases the effective concentration of actin, which increases the reaction rate, while the microviscosity does not increase sufficiently to lower the reaction rate. This study reveals finer details about the mechanism of MMC.

Mass production of bulk artificial nacre with excellent mechanical properties.

PubMed

Gao, Huai-Ling; Chen, Si-Ming; Mao, Li-Bo; Song, Zhao-Qiang; Yao, Hong-Bin; Cölfen, Helmut; Luo, Xi-Sheng; Zhang, Fu; Pan, Zhao; Meng, Yu-Feng; Ni, Yong; Yu, Shu-Hong

2017-08-18

Various methods have been exploited to replicate nacre features into artificial structural materials with impressive structural and mechanical similarity. However, it is still very challenging to produce nacre-mimetics in three-dimensional bulk form, especially for further scale-up. Herein, we demonstrate that large-sized, three-dimensional bulk artificial nacre with comprehensive mimicry of the hierarchical structures and the toughening mechanisms of natural nacre can be facilely fabricated via a bottom-up assembly process based on laminating pre-fabricated two-dimensional nacre-mimetic films. By optimizing the hierarchical architecture from molecular level to macroscopic level, the mechanical performance of the artificial nacre is superior to that of natural nacre and many engineering materials. This bottom-up strategy has no size restriction or fundamental barrier for further scale-up, and can be easily extended to other material systems, opening an avenue for mass production of high-performance bulk nacre-mimetic structural materials in an efficient and cost-effective way for practical applications.Artificial materials that replicate the mechanical properties of nacre represent important structural materials, but are difficult to produce in bulk. Here, the authors exploit the bottom-up assembly of 2D nacre-mimetic films to fabricate 3D bulk artificial nacre with an optimized architecture and excellent mechanical properties.

Nanoparticle stability in semidilute and concentrated polymer solutions.

PubMed

Dutta, Nupur; Green, David

2008-05-20

The wetting of PDMS-grafted silica spheres (PDMS- g-silica) is connected to their depletion restabilization in semidilute and concentrated PDMS/cyohexane polymer solutions. Specifically, we found that a wetting diagram of chemically identical graft and free homopolymers predicts stability of hard, semisoft, and soft spheres as a function of the bulk free polymer volume fraction, graft density, and the graft and free polymer chain lengths. The transition between stable and aggregated regions is determined optically and with dynamic light scattering. The point of demarcation between the regions occurs when the graft and free polymer chains are equal in length. When graft chains are longer than free chains, the particles are stable; in contrast, the particles are unstable when the opposite is true. The regions of particle stability and instability are corroborated with theoretical self-consistent mean-field calculations, which not only show that the grafted brush is responsible for particle dispersion in the complete wetting region but also aggregation in the incomplete wetting region. Ultimately, our results indicate that depletion restabilization depends on the interfacial properties of the nanoparticles in semidilute and concentrated polymer solutions.

Fracture Toughness Properties of Gd123 Superconducting Bulks

NASA Astrophysics Data System (ADS)

Fujimoto, H.; Murakami, A.

Fracture toughness properties of melt growth GdBa2Cu3Ox (Gd123) large single domain superconducting bulks with Ag2O of 10 wt% and Pt of 0.5 wt%; 45 mm in diameter and 25 mm in thickness with low void density were evaluated at 77 K through flexural tests of specimens cut from the bulks, and compared to those of a conventional Gd123 with voids. The densified Gd123 bulks were prepared with a seeding and temperature gradient method; first melt processed in oxygen, then crystal growth in air; two-step regulated atmosphere heat treatment. The plane strain fracture toughness, KIC was obtained by the three point flexure test of the specimens with through precrack, referring to the single edge pre-cracked beam (SEPB) method, according to the JIS-R-1607, Testing Methods for Fracture Toughness of High Performance Ceramics. The results show that the fracture toughness of the densified Gd123 bulk with low void density was higher than that of the standard Gd123 bulk with voids, as well as the flexural strength previously reported. We also compared the fracture toughness of as-grown bulks with that of annealed bulks. The relation between the microstructure and the fracture toughness of the Gd123 bulk was clearly shown.

The Effects of Salt Water on Mechanical Properties of Glacial Ice

NASA Astrophysics Data System (ADS)

Holt, R. A.; McCarthy, C.

2017-12-01

An improved understanding of the mechanical properties of glacial ice, including factors that may change them, is essential for understanding vulnerability of ice sheets to climate change. It is understood that the temperature of intruding subglacial seawater affects the melting of glacial ice and therefore destabilizes ice shelves, but we hypothesize that seawater bathing the bottom of the glacier may also influence mechanical properties such as friction and elastic modulus. We undertook experiments to determine how the presence of saline solution at grain boundaries of ice might lead to weaker behavior. We created an ice sample by finely grinding and sieving seed ice, pressing it into a rectangular mold, and flooding with a 3.5wt% saline solution. We then quickly brought it to subsolidus (-22°) to completely freeze. The bulk composition of the sample was determined by refractive index to be 0.28wt%. Microstructural characterization of the sample indicates that, above the solidus, the melt phase was located at grain triple junctions and along grain boundaries. To test the frictional behavior of ice with saline sliding against rock, we used a cryo-biaxial apparatus designed to simulate the basal sliding of glacial ice. The experiments were run in the double direct configuration at 100 KPa normal stress and at T=-5°. The results demonstrate that ice containing a liquid saline solution has lower steady state friction than pure ice at the same conditions, and therefore can slip at a faster velocity. In addition to the bi-axial experiment we determined the elastic properties using an ultrasonic velocity testing system. P waves velocities through the saline ice sample were consistent with published values (Spencer et al., 1968, JGR). We also used both measured and estimated values to calculate the Young's modulus. We found that ice containing salt water has a lower Young's modulus than that of pure ice. Salt water significantly changes the mechanical properties of glacial ice and this should be considered in models of glacial stability.

Porous 3D graphene-based bulk materials with exceptional high surface area and excellent conductivity for supercapacitors

PubMed Central

Zhang, Long; Zhang, Fan; Yang, Xi; Long, Guankui; Wu, Yingpeng; Zhang, Tengfei; Leng, Kai; Huang, Yi; Ma, Yanfeng; Yu, Ao; Chen, Yongsheng

2013-01-01

Until now, few sp2 carbon materials simultaneously exhibit superior performance for specific surface area (SSA) and electrical conductivity at bulk state. Thus, it is extremely important to make such materials at bulk scale with those two outstanding properties combined together. Here, we present a simple and green but very efficient approach using two standard and simple industry steps to make such three-dimensional graphene-based porous materials at the bulk scale, with ultrahigh SSA (3523 m2/g) and excellent bulk conductivity. We conclude that these materials consist of mainly defected/wrinkled single layer graphene sheets in the dimensional size of a few nanometers, with at least some covalent bond between each other. The outstanding properties of these materials are demonstrated by their superior supercapacitor performance in ionic liquid with specific capacitance and energy density of 231 F/g and 98 Wh/kg, respectively, so far the best reported capacitance performance for all bulk carbon materials. PMID:23474952

Thermoelectric properties of Tl and I dual-doped Bi2Te3-based alloys

NASA Astrophysics Data System (ADS)

Wu, Fang; He, Qinglin; Tang, Mingsheng; Song, Hongzhang

2018-04-01

TlxBi2‑xTe3‑xIx (x = 0, 0.05, 0.1 and 0.2) flower-like nanopowders were prepared successfully by the hydrothermal method. Then, the synthesized nanoparticles were pressed into bulks by hot-pressing. The thermoelectric (TE) properties of the TlxBi2‑xTe3‑xIx bulk samples were investigated and discussed. The results showed that the influences of Tl doping on the electrical resistivity and Seebeck coefficients of the Bi2Te3 is over that of I doping. Thus, the power factors of the dual-doped bulks are all less than that of the Bi2Te3 bulk. The thermal conductivities of the TlxBi2‑xTe3‑xIx bulk samples also remain at lower values. As a result, the ZT value of the optimized doped bulk Tl0.1Bi1.9Te2.9I0.1 attains a value of 1.1 at 398 K.

Bulk-edge correspondence in topological transport and pumping

NASA Astrophysics Data System (ADS)

Imura, Ken-Ichiro; Yoshimura, Yukinori; Fukui, Takahiro; Hatsugai, Yasuhiro

2018-03-01

The bulk-edge correspondence (BEC) refers to a one-to-one relation between the bulk and edge properties ubiquitous in topologically nontrivial systems. Depending on the setup, BEC manifests in different forms and govern the spectral and transport properties of topological insulators and semimetals. Although the topological pump is theoretically old, BEC in the pump has been established just recently [1] motivated by the state-of-the-art experiments using cold atoms [2, 3]. The center of mass (CM) of a system with boundaries shows a sequence of quantized jumps in the adiabatic limit associated with the edge states. Despite that the bulk is adiabatic, the edge is inevitably non-adiabatic in the experimental setup or in any numerical simulations. Still the pumped charge is quantized and carried by the bulk. Its quantization is guaranteed by a compensation between the bulk and edges. We show that in the presence of disorder the pumped charge continues to be quantized despite the appearance of non-quantized jumps.

Effect of Soft Phase on Magnetic Properties of Bulk Sm-Co/alpha-Fe Nanocomposite Magnets (Postprint)

DTIC Science & Technology

2012-11-01

plasma sintering , and warm compaction [4][5]–[9]. In our previous study [10], bulk Sm–Co –Fe nanocomposite magnets were fabricated by hot pressing of...no. 5, pp. 2974–2976, Jul. 2003. [8] T. Saito and H. Miyoshi, “Magnetic properties of Sm5Fe17/Fe com- posite magnets produces by spark plasma ...Fe and Fe-Co. Bulk composite magnets have been prepared using compaction techniques such as hot pressing/deforma- tion, dynamic shock compaction, spark

Non-equilibrium freezing behaviour of aqueous systems.

PubMed

MacKenzie, A P

1977-03-29

The tendencies to non-equilibrium freezing behaviour commonly noted in representative aqueous systems derive from bulk and surface properties according to the circumstances. Supercooling and supersaturation are limited by heterogeneous nucleation in the presence of solid impurities. Homogeneous nucleation has been observed in aqueous systems freed from interfering solids. Once initiated, crystal growth is ofter slowed and, very frequently, terminated with increasing viscosity. Nor does ice first formed always succeed in assuming its most stable crystalline form. Many of the more significant measurements on a given systeatter permitting the simultaneous representation of thermodynamic and non-equilibrium properties. The diagram incorporated equilibrium melting points, heterogeneous nucleation temperatures, homogeneous nucleation temperatures, glass transition and devitrification temperatures, recrystallization temperatures, and, where appropriate, solute solubilities and eutectic temperatures. Taken together, the findings on modle systems aid the identification of the kinetic and thermodynamic factors responsible for the freezing-thawing survival of living cells.

Electronic Properties and Photovoltaic Performances of a Series of Oligothiophene Copolymers Incorporating Both Thieno[3,2-b]thiophene and 2,1,3-Benzothiadiazole Moieties.

PubMed

Biniek, Laure; Chochos, Christos L; Hadziioannou, Georges; Leclerc, Nicolas; Lévêque, Patrick; Heiser, Thomas

2010-04-06

A series of donor-acceptor alternated conjugated copolymers, composed of thiophene, bithiophene, thieno[3,2-b]thiophene, and 2,1,3-benzothiadiazole units and differing from each other by the nature and the number of 3-alkylthiophene in the backbone, have been synthesized by Stille cross-coupling polymerization. The material's optical and electrochemical properties, in solution and in thin films, have been investigated using UV-Visible absorption and cyclic voltammetry. Bulk heterojunction solar cells using blends of the newly synthesized copolymers, as electron donor, and C60-PCBM or C70-PCBM, as electron transporting material, have been elaborated. A maximum power conversion efficiency of 1.8% is achieved with a 1:4 PPBzT(2) -C12:C70-PCBM weight ratio. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In situ multi-length scale approach to understand the mechanics of soft and rigid binder in composite lithium ion battery electrodes

NASA Astrophysics Data System (ADS)

Jäckel, Nicolas; Dargel, Vadim; Shpigel, Netanel; Sigalov, Sergey; Levi, Mikhael D.; Daikhin, Leonid; Aurbach, Doron; Presser, Volker

2017-12-01

Intercalation-induced dimensional changes of composite battery electrodes containing either a stiff or a soft polymeric binder is one of the many factors determining the cycling performance and ageing. Herein, we report dimensional changes in bulk composite electrodes by in situ electrochemical dilatometry (eD) combined with electrochemical quartz-crystal microbalance with dissipation monitoring (EQCM-D). The latter tracks the mechanical properties on the level of the electrode particle size. Lithium iron phosphate (LiFePO4, LFP) electrodes with a stiff binder (PVdF) and a soft binder (NaCMC) were investigated by cycling in lithium sulfate (Li2SO4) aqueous solution. The electrochemical and mechanical electrode performances depend on the electrode cycling history. Based on combined eD and EQCM-D measurements we provide evidence which properties are preferred for a binder used for a composite Li-ion battery electrode.

Antioxidant Properties of Aqueous Extract of Roasted Hulled Barley in Bulk Oil or Oil-in-Water Emulsion Matrix.

PubMed

Oh, Sumi; Kim, Mi-Ja; Park, Kye Won; Lee, Jae Hwan

2015-11-01

Antioxidant properties of the aqueous extracts of hulled barley (Hordeum vulgare L.) that had been roasted at 210 °C for 20 min were determined in bulk oil and oil-in-water (O/W) emulsions. Bulk oils were heated at 60, 100, and 180 °C, and O/W emulsions were oxidized under riboflavin photosensitization. The content of phenolic compounds was analyzed by high-performance liquid chromatography, and in vitro antioxidant assays were also conducted. The major phenolics contained in the aqueous extract of roasted hulled barley (AERB) were p-coumaric, ferulic, protocatechuic, chlorogenic, 4-hydroxybenzoic, and vanillic acids. Depending on the concentration and oxidation temperature, AERB had antioxidant or prooxidant properties in bulk oil. At 60 °C, AERB at a concentration of 0.5% acted as a prooxidant, whereas at 1.0% it acted as an antioxidant. At 100 °C, AERB acted as an antioxidant irrespective of concentration. In 180 °C conditions, 0.5% AERB acted as a prooxidant, whereas other concentrations of AERB acted as antioxidants. In the case of riboflavin photosensitized O/W emulsions, AERB showed antioxidant properties irrespective of concentration. Antioxidant abilities of AERB are affected by the food matrix, including bulk oil and O/W emulsions, and concentrations of AERB, even though diverse phenolic compounds may display high antioxidant properties in in vitro assays. Roasted barley has been widely used as a tea ingredient in East Asian countries such as Korea, China, and Japan. The highly antioxidative properties of the aqueous extracts of roasted barley have been confirmed in bulk oil and O/W emulsions as well as in vitro assays because of the presence of phenolic compounds. The results of this study can contribute to the development of antioxidant-rich beverages using roasted barley by aiding in the selection of proper food matrix-containing extracts of high phenolic compounds, as well as by expanding consumers’ choices for healthy beverages. © 2015 Institute of Food Technologists®

Chondritic Models of 4 Vesta: Comparison of Data from the Dawn Mission with Predicted Internal Structure and Surface Composition/Mineralogy

NASA Technical Reports Server (NTRS)

Toplis, M. J.; Mizzon, H.; Forni, O.; Monnereau, M.; Barrat, J-A.; Prettyman, T. H.; McSween, H. Y.; McCoy, T. J.; Mittlefehldt, D. W.; De Sanctis, M. C.;

Milk whey proteins and xanthan gum interactions in solution and at the air-water interface: a rheokinetic study.

PubMed

Perez, Adrián A; Sánchez, Cecilio Carrera; Patino, Juan M Rodríguez; Rubiolo, Amelia C; Santiago, Liliana G

2010-11-01

In this contribution, we present experimental information about the effect of xanthan gum (XG) on the adsorption behaviour of two milk whey protein samples (MWP), beta-lactoglobulin (beta-LG) and whey protein concentrate (WPC), at the air-water interface. The MWP concentration studied corresponded to the protein bulk concentration which is able to saturate the air-water interface (1.0 wt%). Temperature, pH and ionic strength of aqueous systems were kept constant at 20 degrees C, pH 7 and 0.05 M, respectively, while the XG bulk concentration varied in the range 0.00-0.25 wt%. Biopolymer interactions in solution were analyzed by extrinsic fluorescence spectroscopy using 1-anilino-8-naphtalene sulphonic acid (ANS) as a protein fluorescence probe. Interfacial biopolymer interactions were evaluated by dynamic tensiometry and surface dilatational rheology. Adsorption behaviour was discussed from a rheokinetic point of view in terms of molecular diffusion, penetration and conformational rearrangement of adsorbed protein residues at the air-water interface. Differences in the interaction magnitude, both in solution and at the interface vicinity, and in the adsorption rheokinetic parameters were observed in MWP/XG mixed systems depending on the protein type (beta-LG or WPC) and biopolymer relative concentration. beta-LG adsorption in XG presence could be promoted by mechanisms based on biopolymer segregative interactions and thermodynamic incompatibility in the interface vicinity, resulting in better surface and viscoelastic properties. The same mechanism could be responsible of WPC interfacial adsorption in the presence of XG. The interfacial functionality of WPC was improved by the synergistic interactions with XG, although WPC chemical complexity might complicate the elucidation of molecular events that govern adsorption dynamics of WPC/XG mixed systems at the air-water interface. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Electrokinetics of diffuse soft interfaces. 1. Limit of low Donnan potentials.

PubMed

Duval, Jérôme F L; van Leeuwen, Herman P

2004-11-09

The current theoretical approaches to electrokinetics of gels or polyelectrolyte layers are based on the assumption that the position of the very interface between the aqueous medium and the gel phase is well defined. Within this assumption, spatial profiles for the volume fraction of polymer segments (phi), the density of fixed charges in the porous layer (rho fix), and the coefficient modeling the friction to hydrodynamic flow (k) follow a step-function. In reality, the "fuzzy" nature of the charged soft layer is intrinsically incompatible with the concept of a sharp interface and therefore necessarily calls for more detailed spatial representations for phi, rho fix, and k. In this paper, the notion of diffuse interface is introduced. For the sake of illustration, linear spatial distributions for phi and rho fix are considered in the interfacial zone between the bulk of the porous charged layer and the bulk electrolyte solution. The corresponding distribution for k is inferred from the Brinkman equation, which for low phi reduces to Stokes' equation. Linear electrostatics, hydrodynamics, and electroosmosis issues are analytically solved within the context of streaming current and streaming potential of charged surface layers in a thin-layer cell. The hydrodynamic analysis clearly demonstrates the physical incorrectness of the concept of a discrete slip plane for diffuse interfaces. For moderate to low electrolyte concentrations and nanoscale spatial transition of phi from zero (bulk electrolyte) to phi o (bulk gel), the electrokinetic properties of the soft layer as predicted by the theory considerably deviate from those calculated on the basis of the discontinuous approximation by Ohshima.

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

Shukla, Vaishali; Singh, Man

Currently, the development of micelles route is thrust area of research in nanoscience for the control particle size and remarkable properties through chemical co-precipitation method. A 0.9 mM aqueous CTAB micellar solution plays a role as capping agent in the homogeneous solution of 0.5 M ZnSO{sub 4} and 0.5 M Na{sub 2}S for synthesis, further precipitates purified with centrifugation in cold ethanol and millipore water to remove unreacted reagents and ionic salt particles. A resultant, white colored luminescent ZnS nanoparticle out with ∼95% yield is reported. The ZnS nanoparticles have been examined by their luminescence properties, optical properties and crystal structure.more » The mean particle size of ZnS nanoparticles is found to be ∼10 nm in various technical results and UV-absorption was 80 nm blue shifts moved from 345 nm (bulk material) to 265 nm, showing a quantum size impact. The X-ray diffraction (XRD) pattern shows the immaculate cubic phase. Photoluminescence (PL) investigates the recombination mechanism with blue emission from shallow electron traps at 490 nm in ZnS nanoparticles. An FTIR spectrum and Thermal gravimetric analysis (TGA) gives confirmation of CTAB – cationic surfactant on surface of ZnS nanoparticle as capping agent as well thermal stability of CTAB capped ZnS nanoparticles with respect to temperature.« less

A kinetic model for beta-amyloid adsorption at the air/solution interface and its implication to the beta-amyloid aggregation process.

PubMed

Jiang, Dianlu; Dinh, Kim Lien; Ruthenburg, Travis C; Zhang, Yi; Su, Lei; Land, Donald P; Zhou, Feimeng

2009-03-12

At the air/buffer solution interface the kinetics of adsorption of amyloid beta peptide, Abeta(1-42), whose bulk concentration (submicromolar) is more than 2 orders of magnitude lower than that typically used in other in vitro aggregation studies, has been studied using a Langmuir-Blodgett trough. The pressure-time curves exhibit a lag phase, wherein the surface pressure essentially remains at zero, and a rising phase, corresponding to the Abeta adsorption at the interface. The duration of the lag phase was found to be highly dependent on both the Abeta bulk concentration and the solution temperature. A large activation energy (62.2 +/- 4.1 KJ/mol) was determined and the apparent adsorption rate constant was found to be linearly dependent on the Abeta bulk concentration. Attenuated total reflection-IR spectra of the adsorbed Abeta transferred to a solid substrate and circular dichroism measurements of Abeta in the solution layer near the interface reveal that the natively unstructured Abeta in the bulk undergo a conformation change (folding) to mainly the alpha-helical structure. The results suggest that, prior to the adsorption step, an equilibrium between Abeta conformations is established within the subsurface. The kinetic equation derived from this model confirms that the overall Abeta adsorption is kinetically controlled and the apparent rate constant is proportional to the Abeta bulk concentration. This model also indicates that interfaces such as cell membranes and lipid bilayers may facilitate Abeta aggregation/ fibrillation by providing a thin hydrophobic layer adjacent to the interface for the initial A/beta conformation change (misfolding) and accumulation. Such a preconcentration effect offers a plausible explanation of the fact that Abeta fibrillation occurs in vivo at nanomolar concentrations. Another important biological implication from our work is that Abeta misfolding may occur before its adsorption onto a cell membrane. This general kinetic model should also find applications in adsorption studies of other types of biomolecules whose overall kinetics exhibits a lag phase that is dependent on the bulk concentration of the adsorbate.

A Kinetic Model for β-Amyloid Adsorption at the Air/Solution Interface and Its Implication to the β-Amyloid Aggregation Process

PubMed Central

Jiang, Dianlu; Dinh, Kim Lien; Ruthenburg, Travis; Zhang, Yi; Su, Lei; Land, Donald; Zhou, Feimeng

2011-01-01

The kinetics of adsorption at the air/buffer solution interface of amyloid beta peptide, Aβ(1–42), whose bulk concentration (submicromolar) is more than two orders of magnitude lower than that typically used in other in vitro aggregation studies, has been studied using a Langmuir-Blodgett trough. The pressure–time curves exhibit a lag phase, wherein the surface pressure essentially remains at zero, and a rising phase, corresponding to the Aβ adsorption at the interface. The duration of the lag phase was found to be highly dependent on both the Aβ bulk concentration and the solution temperature. A large activation energy (62.2 ± 4.1 KJ/mol) was determined and the apparent adsorption rate constant was found to be linearly dependent on the Aβ bulk concentration. Attenuated total reflection-IR spectra of the adsorbed Aβ transferred to a solid substrate and circular dichroism measurements of Aβ in the solution layer near the interface reveal that the natively unstructured Aβ in the bulk undergo a conformation change (folding) to mainly the α-helical structure. The results suggest that, prior to the adsorption step, an equilibrium between Aβ conformations is established within the subsurface. The kinetic equation derived from this model confirms that the overall Aβ adsorption is kinetically controlled and the apparent rate constant is proportional to the Aβ bulk concentration. This model also indicates that interfaces such as cell membranes and lipid bilayers may facilitate Aβ aggregation/fibrillation by providing a thin hydrophobic layer adjacent to the interface for the initial Aβ conformation change (misfolding) and accumulation. Such a preconcentration effect offers a plausible explanation of the fact that Aβ fibrillation occurs in vivo at nanomolar concentrations. Another important biological implication from our work is that Aβ misfolding may occur before its adsorption onto a cell membrane. This general kinetic model should also find applications in adsorption studies of other types of biomolecules whose overall kinetics exhibits a lag phase that is dependent on the bulk concentration of the adsorbate. PMID:19260715

Characterization, liquid crystalline behavior, electrochemical and optoelectrical properties of new poly(azomethine)s and a poly(imide) with siloxane linkages

NASA Astrophysics Data System (ADS)

Iwan, Agnieszka; Schab-Balcerzak, Ewa; Pociecha, Damian; Krompiec, Michal; Grucela, Marzena; Bilski, Pawel; Kłosowski, Mariusz; Janeczek, Henryk

2011-11-01

New siloxane-containing poly(azomethine)s and a six-membered poly(imide) have been developed from siloxane-containing diamine with four different dialdehydes and 3,4,9,10-perylenetetracarboxylic dianhydride, and their thermotropic behavior, optoelectrical and electrochemical properties were examined. Mesomorphic behavior of the polymers was investigated via differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and X-ray diffraction (WAXRD, SAXRD) studies. The electrochemical behavior of poly(azomethine)s and poly(imide) was studied by differential pulse voltammetry (DPV). The HOMO levels of these polymers were in the range of -5.13 to -5.90 eV. UV-vis properties of the polymers were investigated in solid state as thin films and in chloroform solution. Optical energy band gap ( Egopt.) was calculated from absorption spectra and absorption coefficients α. The photoluminescence properties (PL) of obtained polymers were studied in chloroform solution. The investigated poly(azomethine)s emitted blue light, while the poly(imide) emitted green light. The polymers were irradiated with a test dose of 1 Gy Co-60 gamma-rays to detect their thermoluminescence properties in the temperature range of 50-200 °C. Polymer monolayer (ITO/polymer/Al) and bulk heterojunction (BHJ) (ITO/polymer:PCBM/Al and ITO/PEDOT:PSS/polymer:PCBM/Al) devices were prepared with PAZ and PI used as active layers and I- U curves were measured in the dark and during irradiation with light (under illumination of 1000 W/m 2). Poly(azomethine)s were blended with [6,6]-phenyl C 61 butyric acid methyl ester (PCBM). Selected properties of the investigated polymers with siloxane linkages were compared with the polymers ( PAZ1a- PAZ3a, PIa) prepared from the same dialdehydes or dianhydride and poly(1,4-butanediol)bis(4-aminobenzoate).

Multi-scale mechanical response of freeze-dried collagen scaffolds for tissue engineering applications.

PubMed

Offeddu, Giovanni S; Ashworth, Jennifer C; Cameron, Ruth E; Oyen, Michelle L

2015-02-01

Tissue engineering has grown in the past two decades as a promising solution to unresolved clinical problems such as osteoarthritis. The mechanical response of tissue engineering scaffolds is one of the factors determining their use in applications such as cartilage and bone repair. The relationship between the structural and intrinsic mechanical properties of the scaffolds was the object of this study, with the ultimate aim of understanding the stiffness of the substrate that adhered cells experience, and its link to the bulk mechanical properties. Freeze-dried type I collagen porous scaffolds made with varying slurry concentrations and pore sizes were tested in a viscoelastic framework by macroindentation. Membranes made up of stacks of pore walls were indented using colloidal probe atomic force microscopy. It was found that the bulk scaffold mechanical response varied with collagen concentration in the slurry consistent with previous studies on these materials. Hydration of the scaffolds resulted in a more compliant response, yet lesser viscoelastic relaxation. Indentation of the membranes suggested that the material making up the pore walls remains unchanged between conditions, so that the stiffness of the scaffolds at the scale of seeded cells is unchanged; rather, it is suggested that thicker pore walls or more of these result in the increased moduli for the greater slurry concentration conditions. Copyright © 2014 The Authors. Published by Elsevier Ltd.. All rights reserved.

Sodium metasilicate based fiber opening for greener leather processing.

PubMed

Saravanabhavan, Subramani; Thanikaivelan, Palanisamy; Rao, Jonnalagadda Raghava; Nair, Balachandran Unni; Ramasamit, Thirumalachari

2008-03-01

Growing environmental regulations propound the need for a transformation in the current practice of leather making. The conventional dehairing and fiber opening process results in high negative impact on the environment because of its uncleanliness. This process accounts for most of the biochemical oxygen demand and chemical oxygen demand in tannery wastewater and generation of H2S gas. Hence, this study explores the use of a biological material and a nontoxic chemical for performing the above process more cleanly. In this study, the dehairing and fiber opening processes has been designed using enzyme and sodium metasilicate. The amount of sodium metasilicate required for fiber opening is standardized through the removal of proteoglycan, increase in weight, and bulk properties of leathers. It has been found that the extent of opening up of fiber bundles is comparable to that of conventionally processed leathers using a 2% sodium metasilicate solution. This has been substantiated through scanning electron microscopic analysis and softness measurements. The presence of silica in the crust leather enhances the bulk properties of the leather. This has been confirmed from the energy dispersive X-ray analysis. Performance of the leathers is shown to be on par with conventionally processed leathers through physical and hand evaluation. The process also exhibits significant reduction in chemical oxygen demand and total solid loads by 55 and 24%, respectively. Further, this newly developed process seems to be economically beneficial.

Synthesis of Multishell Nanoplates by Consecutive Epitaxial Growth of Bi2Se3 and Bi2Te3 Nanoplates and Enhanced Thermoelectric Properties.

PubMed

Min, Yuho; Park, Gyeongbae; Kim, Bongsoo; Giri, Anupam; Zeng, Jie; Roh, Jong Wook; Kim, Sang Il; Lee, Kyu Hyoung; Jeong, Unyong

2015-07-28

We herein demonstrate the successive epitaxial growth of Bi2Te3 and Bi2Se3 on seed nanoplates for the scalable synthesis of heterostructured nanoplates (Bi2Se3@Bi2Te3) and multishell nanoplates (Bi2Se3@Bi2Te3@Bi2Se3, Bi2Se3@Bi2Te3@Bi2Se3@Bi2Te3). The relative dimensions of the constituting layers are controllable via the molar ratios of the precursors added to the seed nanoplate solution. Reduction of the precursors produces nanoparticles that attach preferentially to the sides of the seed nanoplates. Once attached, the nanoparticles reorganize epitaxially on the seed crystal lattices to form single-crystalline core-shell nanoplates. The nanoplates, initially 100 nm wide, grew laterally to 620 nm in the multishell structure, while their thickness increased more moderately, from 5 to 20 nm. The nanoplates were pelletized into bulk samples by spark plasma sintering and their thermoelectric properties are compared. A peak thermoelectric figure of merit (ZT) ∼0.71 was obtained at 450 K for the bulk of Bi2Se3@Bi2Te3 nanoplates by simultaneous modulation of electronic and thermal transport in the presence of highly dense grain and phase boundaries.

Two-dimensional Coupled Petrological-tectonic Modelling of Extensional Basins

NASA Astrophysics Data System (ADS)

Kaus, B. J. P.; Podladchikov, Y. Y.; Connolly, J. A. D.

Most numerical codes that simulate the deformation of a lithosphere assume the den- sity of the lithosphere to be either constant or depend only on temperature and pres- sure. It is, however, well known that rocks undergo phase transformations in response to changes in pressure and temperature. Such phase transformations may substantially alter the bulk properties of the rock (i.e., density, thermal conductivity, thermal ex- pansivity and elastic moduli). Several previous studies demonstrated that the density effects due to phase transitions are indeed large enough to have an impact on the litho- sphere dynamics. These studies were however oversimplified in that they accounted for only one or two schematic discontinuous phase transitions. The current study there- fore takes into account all the reactions that occur for a realistic lithospheric composi- tion. Calculation of the phase diagram and bulk physical properties of the stable phase assemblages for the crust and mantle within the continental lithosphere was done ac- counting for mineral solution behaviour using a free energy minimization program for natural rock compositions. The results of these calculations provide maps of the varia- tions in rock properties as a function of pressure and temperature that are easily incor- porated in any dynamic model computations. In this contribution we implemented a density map in the two-dimensional basin code TECMOD2D. We compare the results of the model with metamorphic reactions with a model without reactions and define some effective parameters that allow the use of a simpler model that still mimics most of the density effects of the metamorphic reactions.

Optical properties of non-spherical desert dust particles in the terrestrial infrared - An asymptotic approximation approach

NASA Astrophysics Data System (ADS)

Klüser, Lars; Di Biagio, Claudia; Kleiber, Paul D.; Formenti, Paola; Grassian, Vicki H.

2016-07-01

Optical properties (extinction efficiency, single scattering albedo, asymmetry parameter and scattering phase function) of five different desert dust minerals have been calculated with an asymptotic approximation approach (AAA) for non-spherical particles. The AAA method combines Rayleigh-limit approximations with an asymptotic geometric optics solution in a simple and straightforward formulation. The simulated extinction spectra have been compared with classical Lorenz-Mie calculations as well as with laboratory measurements of dust extinction. This comparison has been done for single minerals and with bulk dust samples collected from desert environments. It is shown that the non-spherical asymptotic approximation improves the spectral extinction pattern, including position of the extinction peaks, compared to the Lorenz-Mie calculations for spherical particles. Squared correlation coefficients from the asymptotic approach range from 0.84 to 0.96 for the mineral components whereas the corresponding numbers for Lorenz-Mie simulations range from 0.54 to 0.85. Moreover the blue shift typically found in Lorenz-Mie results is not present in the AAA simulations. The comparison of spectra simulated with the AAA for different shape assumptions suggests that the differences mainly stem from the assumption of the particle shape and not from the formulation of the method itself. It has been shown that the choice of particle shape strongly impacts the quality of the simulations. Additionally, the comparison of simulated extinction spectra with bulk dust measurements indicates that within airborne dust the composition may be inhomogeneous over the range of dust particle sizes, making the calculation of reliable radiative properties of desert dust even more complex.

Analytical Solutions for the Surface States of Bi1-xSbx (0 ≤ x ≲ 0.1)

NASA Astrophysics Data System (ADS)

Fuseya, Yuki; Fukuyama, Hidetoshi

2018-04-01

Analytical solutions for the surface state (SS) of an extended Wolff Hamiltonian, which is a common Hamiltonian for strongly spin-orbit coupled systems, are obtained both for semi-infinite and finite-thickness boundary conditions. For the semi-infinite system, there are two types of SS solutions: (I-a) linearly crossing SSs in the direct bulk band gap, and (I-b) SSs with linear dispersions entering the bulk conduction or valence bands away from the band edge. For the finite-thickness system, a gap opens in the SS of solution I-a. Numerical solutions for the SS are also obtained based on the tight-binding model of Liu and Allen [Phys. Rev. B 52, 1566 (1995)] for Bi1-xSbx (0 ≤ x ≤ 0.1). A perfect correspondence between the analytic and numerical solutions is obtained around the \\bar{M} point including their thickness dependence. This is the first time that the character of the SS numerically obtained is identified with the help of analytical solutions. The size of the gap for I-a SS can be larger than that of bulk band gap even for a "thick" films ( ≲ 200 bilayers ≃ 80 nm) of pure bismuth. Consequently, in such a film of Bi1-xSbx, there is no apparent change in the SSs through the band inversion at x ≃ 0.04, even though the nature of the SS is changed from solution I-a to I-b. Based on our theoretical results, the experimental results on the SS of Bi1-xSbx (0 ≤ x ≲ 0.1) are discussed.

Thermal conductivity and phonon transport properties of silicon using perturbation theory and the environment-dependent interatomic potential

NASA Astrophysics Data System (ADS)

Pascual-Gutiérrez, José A.; Murthy, Jayathi Y.; Viskanta, Raymond

2009-09-01

Silicon thermal conductivities are obtained from the solution of the linearized phonon Boltzmann transport equation without the use of any parameter-fitting. Perturbation theory is used to compute the strength of three-phonon and isotope scattering mechanisms. Matrix elements based on Fermi's golden rule are computed exactly without assuming either average or mode-dependent Grüeisen parameters, and with no underlying assumptions of crystal isotropy. The environment-dependent interatomic potential is employed to describe the interatomic force constants and the perturbing Hamiltonians. A detailed methodology to accurately find three-phonon processes satisfying energy- and momentum-conservation rules is also described. Bulk silicon thermal conductivity values are computed across a range of temperatures and shown to match experimental data very well. It is found that about two-thirds of the heat transport in bulk silicon may be attributed to transverse acoustic modes. Effective relaxation times and mean free paths are computed in order to provide a more complete picture of the detailed transport mechanisms and for use with carrier transport models based on the Boltzmann transport equation.

Nonlinear fractional waves at elastic interfaces

NASA Astrophysics Data System (ADS)

Kappler, Julian; Shrivastava, Shamit; Schneider, Matthias F.; Netz, Roland R.

2017-11-01

We derive the nonlinear fractional surface wave equation that governs compression waves at an elastic interface that is coupled to a viscous bulk medium. The fractional character of the differential equation comes from the fact that the effective thickness of the bulk layer that is coupled to the interface is frequency dependent. The nonlinearity arises from the nonlinear dependence of the interface compressibility on the local compression, which is obtained from experimental measurements and reflects a phase transition at the interface. Numerical solutions of our nonlinear fractional theory reproduce several experimental key features of surface waves in phospholipid monolayers at the air-water interface without freely adjustable fitting parameters. In particular, the propagation distance of the surface wave abruptly increases at a threshold excitation amplitude. The wave velocity is found to be of the order of 40 cm/s in both experiments and theory and slightly increases as a function of the excitation amplitude. Nonlinear acoustic switching effects in membranes are thus shown to arise purely based on intrinsic membrane properties, namely, the presence of compressibility nonlinearities that accompany phase transitions at the interface.

Evaluating the multimedia fate of organic chemicals: A level III fugacity model

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

Mackay, D.; Paterson, S.

A multimedia model is developed and applied to selected organic chemicals in evaluative and real regional environments. The model employs the fugacity concept and treats four bulk compartments: air, water, soil, and bottom sediment, which consist of subcompartments of varying proportions of air, water, and mineral and organic matter. Chemical equilibrium is assumed to apply within (but not between) each bulk compartment. Expressions are included for emissions, advective flows, degrading reactions, and interphase transport by diffusive and non-diffusive processes. Input to the model consists of a description of the environment, the physical-chemical and reaction properties of the chemical, and emissionmore » rates. For steady-state conditions the solution is a simple algebraic expression. The model is applied to six chemicals in the region of southern Ontario and the calculated fate and concentrations are compared with observations. The results suggest that the model may be used to determine the processes that control the environmental fate of chemicals in a region and provide approximate estimates of relative media concentrations.« less

Magnetic nanoparticles through organometallic synthesis: evolution of the magnetic properties from isolated nanoparticles to organised nanostructures.

PubMed

Dumestre, Fréderic; Martinez, Susana; Zitoun, David; Fromen, Marie-Claire; Casanove, Marie-José; Lecante, Pierre; Respaud, Marc; Serres, Arnaud; Benfield, Robert E; Amiens, Catherine; Chaudret, Bruno

2004-01-01

Co and NiFe nanoparticles (2.7 to 3.3 nm mean diameter) of narrow size distribution have been obtained through the decomposition of organometallic precursors in organic solutions of long alkyl chain ligands, namely oleic acid and hexadecylamine. Materials of various volume fractions were produced. The particles have been structurally characterised by WAXS. Both adopt the bulk structure: HCP in the case of cobalt; a mixture of FCC and BCC for NiFe. Their aptitude to self-assemble either on flat supports or in bulk solid state has been investigated by means of TEM and SAXS. This study suggests the crystallisation of the nanoparticles upon solvent evaporation, especially a local FCC arrangement was observed for the NiFe material. Magnetic measurements (SQUID) confirm this tendency. The blocking temperature depends on the metal volume fraction, i.e. on the anisotropy generated by the dipolar couplings (Ki). We show that, for dense samples, the particles of high intrinsic anisotropy, Ku, (Co) still display an individual behaviour while the soft ones (NiFe) display a collective behaviour.

The dynamic crossover in water does not require bulk water.

PubMed

Turton, David A; Corsaro, Carmelo; Martin, David F; Mallamace, Francesco; Wynne, Klaas

2012-06-14

Many of the anomalous properties of water may be explained by invoking a second critical point that terminates the coexistence line between the low- and high-density amorphous states in the liquid. Direct experimental evidence of this point, and the associated polyamorphic liquid-liquid transition, is elusive as it is necessary for liquid water to be cooled below its homogeneous-nucleation temperature. To avoid crystallization, water in the eutectic LiCl solution has been studied but then it is generally considered that "bulk" water cannot be present. However, recent computational and experimental studies observe cooperative hydration in which case it is possible that sufficient hydrogen-bonded water is present for the essential characteristics of water to be preserved. For femtosecond optical Kerr-effect and nuclear magnetic resonance measurements, we observe in each case a fractional Stokes-Einstein relation with evidence of the dynamic crossover appearing near 220 K and 250 K respectively. Spectra obtained in the glass state also confirm the complex nature of the hydrogen-bonding modes reported for neat room-temperature water and support predictions of anomalous diffusion due to "worm-hole" structure.

Theoretical study on the spectroscopic properties of CO3(*-).nH2O clusters: extrapolation to bulk.

PubMed

Pathak, Arup K; Mukherjee, Tulsi; Maity, Dilip K

2008-10-24

Vertical detachment energies (VDE) and UV/Vis absorption spectra of hydrated carbonate radical anion clusters, CO(3)(*-).nH(2)O (n=1-8), are determined by means of ab initio electronic structure theory. The VDE values of the hydrated clusters are calculated with second-order Moller-Plesset perturbation (MP2) and coupled cluster theory using the 6-311++G(d,p) set of basis functions. The bulk VDE value of an aqueous carbonate radical anion solution is predicted to be 10.6 eV from the calculated weighted average VDE values of the CO(3)(*-).nH(2)O clusters. UV/Vis absorption spectra of the hydrated clusters are calculated by means of time-dependent density functional theory using the Becke three-parameter nonlocal exchange and the Lee-Yang-Parr nonlocal correlation functional (B3LYP). The simulated UV/Vis spectrum of the CO(3)(*-).8H(2)O cluster is in excellent agreement with the reported experimental spectrum for CO(3)(*-) (aq), obtained based on pulse radiolysis experiments.

Holography and quantum states in elliptic de Sitter space

NASA Astrophysics Data System (ADS)

Halpern, Illan F.; Neiman, Yasha

2015-12-01

We outline a program for interpreting the higher-spin dS/CFT model in terms of physics in the causal patch of a dS observer. The proposal is formulated in "elliptic" de Sitter space d{S}_4/{Z}_2 , obtained by identifying antipodal points in dS 4. We discuss recent evidence that the higher-spin model is especially well-suited for this, since the antipodal symmetry of bulk solutions has a simple encoding on the boundary. For context, we test some other (free and interacting) theories for the same property. Next, we analyze the notion of quantum field states in the non-time-orientable d{S}_4/{Z}_2 . We compare the physics seen by different observers, with the outcome depending on whether they share an arrow of time. Finally, we implement the marriage between higher-spin holography and observers in d{S}_4/{Z}_2 , in the limit of free bulk fields. We succeed in deriving an observer's operator algebra and Hamiltonian from the CFT, but not her S-matrix. We speculate on the extension of this to interacting higher-spin theory.

Separating Bulk and Surface Contributions to Electronic Excited-State Processes in Hybrid Mixed Perovskite Thin Films via Multimodal All-Optical Imaging

DOE PAGES

Simpson, Mary Jane; Doughty, Benjamin; Das, Sanjib; ...

2017-07-04

A comprehensive understanding of electronic excited-state phenomena underlying the impressive performance of solution-processed hybrid halide perovskite solar cells requires access to both spatially resolved electronic processes and corresponding sample morphological characteristics. In this paper, we demonstrate an all-optical multimodal imaging approach that enables us to obtain both electronic excited-state and morphological information on a single optical microscope platform with simultaneous high temporal and spatial resolution. Specifically, images were acquired for the same region of interest in thin films of chloride containing mixed lead halide perovskites (CH 3NH 3PbI 3–xCl x) using femtosecond transient absorption, time-integrated photoluminescence, confocal reflectance, and transmissionmore » microscopies. Comprehensive image analysis revealed the presence of surface- and bulk-dominated contributions to the various images, which describe either spatially dependent electronic excited-state properties or morphological variations across the probed region of the thin films. Finally, these results show that PL probes effectively the species near or at the film surface.« less

Bulk Group-III Nitride Crystal Growth in Supercritical Ammonia-Sodium Solutions

NASA Astrophysics Data System (ADS)

Griffiths, Steven Herbert

Gallium nitride (GaN) and its alloys with indium nitride (InGaN) and aluminum nitride (AlGaN), collectively referred to as Group-III Nitride semiconductors, have enabled white solid-state lighting (SSL) sources and power electronic devices. While these technologies have already made a lasting, positive impact on society, improvements in design and efficiency are anticipated by shifting from heteroepitaxial growth on foreign substrates (such as sapphire, Si, SiC, etc.) to homoepitaxial growth on native, bulk GaN substrates. Bulk GaN has not supplanted foreign substrate materials due to the extreme conditions required to achieve a stoichiometric GaN melt (temperatures and pressures in excess of 2200°C and 6 GPa, respectively). The only method used to produce bulk GaN on an industrial scale is hydride vapor phase epitaxy (HVPE), but the high cost of gaseous precursors and relatively poor crystal quality have limited the adoption of this technology. A solution growth technique known as the ammonothermal method has attracted interest from academia and industry alike for its ability to produce bulk GaN boules of exceedingly high crystal quality. The ammonothermal method employs supercritical ammonia (NH3) solutions to dissolve, transport, and crystallize GaN. However, ammonothermal growth pressures are still relatively high (˜200 MPa), which has thus far prevented the acquisition of fundamental crystal growth knowledge needed to efficiently (i.e. through data-driven approaches) advance the field. This dissertation focused on addressing the gaps in the literature through two studies employing in situ fluid temperature analysis. The first study focused on identifying the solubility of GaN in supercritical NH3-Na solutions. The design and utilization of in situ and ex situ monitoring equipment enabled the first reports of the two-phase nature of supercritical NH3-Na solutions, and of Ga-alloying of Ni-containing autoclave components. The effects of these error sources on the gravimetric determination of GaN solubility were explored in detail. The second study was aimed at correlating autoclave dissolution and growth zone fluid temperatures with bulk GaN crystal growth kinetics, crystal quality, and impurity incorporation. The insights resulting from this analysis include the identification of the barrier between mass transport and surface integration-limited GaN growth regimes, GaN crystal shape evolution with fluid temperature, the sensitivity of (0001)-orientation crystal quality with fluid temperature, and impurity-specific incorporation activated from the dissolution and growth zones of the autoclave. The results of the aforementioned studies motivated a paradigm-shift in ammonothermal growth. To address this need, a fundamentally different crystal growth approach involving isothermal solutions and tailor-made Group-III alloy source materials was developed/demonstrated. This growth method enabled impurity incorporation reduction compared to traditional ammonothermal GaN growth, and the realization of bulk, ternary Group-III Nitride crystals.

Carbon nanotubes grown on bulk materials and methods for fabrication

DOEpatents

Menchhofer, Paul A [Clinton, TN; Montgomery, Frederick C [Oak Ridge, TN; Baker, Frederick S [Oak Ridge, TN

2011-11-08

Disclosed are structures formed as bulk support media having carbon nanotubes formed therewith. The bulk support media may comprise fibers or particles and the fibers or particles may be formed from such materials as quartz, carbon, or activated carbon. Metal catalyst species are formed adjacent the surfaces of the bulk support material, and carbon nanotubes are grown adjacent the surfaces of the metal catalyst species. Methods employ metal salt solutions that may comprise iron salts such as iron chloride, aluminum salts such as aluminum chloride, or nickel salts such as nickel chloride. Carbon nanotubes may be separated from the carbon-based bulk support media and the metal catalyst species by using concentrated acids to oxidize the carbon-based bulk support media and the metal catalyst species.

Redox properties of undoped 5 nm diamond nanoparticles.

PubMed

Holt, Katherine B; Ziegler, Christoph; Caruana, Daren J; Zang, Jianbing; Millán-Barrios, Enrique J; Hu, Jingping; Foord, John S

2008-01-14

This paper demonstrates the promoting effects of 5 nm undoped detonation diamond nanoparticles on redox reactions in solution. An enhancement in faradaic current for the redox couples Ru(NH(3))(6)(3+/2+) and Fe(CN)(6)(4-/3-) was observed for a gold electrode modified with a drop-coated layer of nanodiamond (ND), in comparison to the bare gold electrode. The ND layer was also found to promote oxygen reduction. Surface modification of the ND powders by heating in air or in a hydrogen flow resulted in oxygenated and hydrogenated forms of the ND, respectively. Oxygenated ND was found to exhibit the greatest electrochemical activity and hydrogenated ND the least. Differential pulse voltammetry of electrode-immobilised ND layers in the absence of solution redox species revealed oxidation and reduction peaks that could be attributed to direct electron transfer (ET) reactions of the ND particles themselves. It is hypothesised that ND consists of an insulating sp(3) diamond core with a surface that has significant delocalised pi character due to unsatisfied surface atoms and C[double bond, length as m-dash]O bond formation. At the nanoscale surface properties of the particles dominate over those of the bulk, allowing ET to occur between these essentially insulating particles and a redox species in solution or an underlying electrode. We speculate that reversible reduction of the ND may occur via electron injection into available surface states at well-defined reduction potentials and allow the ND particles to act as a source and sink of electrons for the promotion of solution redox reactions.

Quinacridone-based molecular donors for solution processed bulk-heterojunction organic solar cells.

PubMed

Chen, John Jun-An; Chen, Teresa L; Kim, BongSoo; Poulsen, Daniel A; Mynar, Justin L; Fréchet, Jean M J; Ma, Biwu

2010-09-01

New soluble quinacridone-based molecules have been developed as electron donor materials for solution-processed organic solar cells. By functionalizing the pristine pigment core of quinacridone with solubilizing alkyl chains and light absorbing/charge transporting thiophene units, i.e., bithiophene (BT) and thienylbenzo[c][1,2,5]thiadiazolethienyl (BTD), we prepared a series of multifunctional quinacridone-based molecules. These molecular donors show intense absorption in the visible spectral region, and the absorption range and intensity are well-tuned by the interaction between the quinacridone core and the incorporated thiophene units. The thin film absorption edge extends with the expansion of molecular conjugation, i.e., 552 nm for N,N'-di(2-ethylhexyl)quinacridone (QA), 592 nm for 2,9-Bis(5'-hexyl-2,2'-bithiophene)-N,N'-di(2-ethylhexyl)quinacridone (QA-BT), and 637 nm for 4-(5-hexylthiophen-2-yl)-7-(thiophen-2-yl)benzo[c][1,2,5]thiadiazole (QA-BTD). The change of molecular structure also influences the electrochemical properties. Observed from cyclic voltammetry measurements, the oxidation and reduction potentials (vs ferrocene) are 0.7 and -1.83 V for QA, 0.54 and -1.76 V for QA-BT, and 0.45 and -1.68 V for QA-BTD. Uniform thin films can be generated from both single component molecular solutions and blend solutions of these molecules with [6,6]-phenyl C70-butyric acid methyl ester (PC70BM). The blend films exhibit space-charge limited current (SCLC) hole mobilities on the order of 1×10(-4) cm(2) V(-1) S(-1). Bulk heterojunction (BHJ) solar cells using these soluble molecules as donors and PC70BM as the acceptor were fabricated. Power conversion efficiencies (PCEs) of up to 2.22% under AM 1.5 G simulated 1 sun solar illumination have been achieved and external quantum efficiencies (EQEs) reach as high as ∼45%.

Hydration shell parameters of aqueous alcohols: THz excess absorption and packing density.

PubMed

Matvejev, V; Zizi, M; Stiens, J

2012-12-06

Solvation in water requires minimizing the perturbations in its hydrogen bonded network. Hence solutes distort water molecular motions in a surrounding domain, forming a molecule-specific hydration shell. The properties of those hydration shells impact the structure and function of the solubilized molecules, both at the single molecule and at higher order levels. The size of the hydration shell and the picoseconds time-scale water dynamics retardation are revealed by terahertz (THz) absorption coefficient measurements. Room-temperature absorption coefficient at f = 0.28 [THz] is measured as a function of alcohol concentration in aqueous methanol, ethanol, 1,2-propanol, and 1-butanol solutions. Highly diluted alcohol measurements and enhanced overall measurement accuracy are achieved with a THz absorption measurement technique of nL-volume liquids in a capillary tube. In the absorption analysis, bulk and interfacial molecular domains of water and alcohol are considered. THz ideal and excess absorption coefficients are defined in accordance with thermodynamics mixing formulations. The parameter extraction method is developed based on a THz excess absorption model and hydrated solute molecule packing density representation. First, the hydration shell size is deduced from the hydrated solute packing densities at two specific THz excess absorption nonlinearity points: at infinite alcohol dilution (IAD) and at the THz excess absorption extremum (EAE). Consequently, interfacial water and alcohol molecular domain absorptions are deduced from the THz excess absorption model. The hydration shell sizes obtained at the THz excess absorption extremum are in excellent agreement with other reports. The hydration shells of methanol, ethanol, 1- and 2-propanol consist of 13.97, 22.94, 22.99, and 31.10 water molecules, respectively. The hydration shell water absorption is on average 0.774 ± 0.028 times the bulk water absorption. The hydration shell parameters might shed light on hydration dynamics of biomolecules.

Driving force for hydrophobic interaction at different length scales.

PubMed

Zangi, Ronen

2011-03-17

We study by molecular dynamics simulations the driving force for the hydrophobic interaction between graphene sheets of different sizes down to the atomic scale. Similar to the prediction by Lum, Chandler, and Weeks for hard-sphere solvation [J. Phys. Chem. B 1999, 103, 4570-4577], we find the driving force to be length-scale dependent, despite the fact that our model systems do not exhibit dewetting. For small hydrophobic solutes, the association is purely entropic, while enthalpy favors dissociation. The latter is demonstrated to arise from the enhancement of hydrogen bonding between the water molecules around small hydrophobes. On the other hand, the attraction between large graphene sheets is dominated by enthalpy which mainly originates from direct solute-solute interactions. The crossover length is found to be inside the range of 0.3-1.5 nm(2) of the surface area of the hydrophobe that is eliminated in the association process. In the large-scale regime, different thermodynamic properties are scalable with this change of surface area. In particular, upon dimerization, a total and a water-induced stabilization of approximately 65 and 12 kJ/mol/nm(2) are obtained, respectively, and on average around one hydrogen bond is gained per 1 nm(2) of graphene sheet association. Furthermore, the potential of mean force between the sheets is also scalable except for interplate distances smaller than 0.64 nm which corresponds to the region around the barrier for removing the last layer of water. It turns out that, as the surface area increases, the relative height of the barrier for association decreases and the range of attraction increases. It is also shown that, around small hydrophobic solutes, the lifetime of the hydrogen bonds is longer than in the bulk, while around large hydrophobes it is the same. Nevertheless, the rearrangement of the hydrogen-bond network for both length-scale regimes is slower than in bulk water. © 2011 American Chemical Society

Crystalline structures, thermal properties and crystallizing mechanism of polyamide 6 nanotubes in confined space

NASA Astrophysics Data System (ADS)

Li, Xiaoru; Peng, Zhi; Yang, Chao; Han, Ping; Song, Guojun; Cong, Longliang

2016-09-01

The polyamide 6 (PA6) nanotubes were prepared by infiltrating the anodic aluminum oxide templates with polymer solution. Crystalline regions in the nanotube walls were detected by high-resolution transmission electron microscopy (HRTEM). X-ray diffraction (XRD), Fast Fourier Transform (FFT) and differential scanning calorimetry (DSC) techniques were employed to investigate crystallization, crystal faces and thermodynamics. It was found that the crystals were transformed from α-form in bulk to γ-form in nanotubes. It was made a detailed analysis in this article. Moreover, schematic diagram for the crystallizing mechanism of PA6 nanotubes was given to explain PA6 molecules how to crystallize in the nano-pores.

Sol-gel derived ZnO as an electron transport layer (ETL) for inverted organic solar cells

NASA Astrophysics Data System (ADS)

Tiwari, D. C.; Dwivedi, Shailendra Kumar; Dipak, Phukhrambam; Chandel, Tarun; Sharma, Rishi

2017-05-01

In this work, we present the study of the fabrication process of the sol-gel derived zinc oxide (ZnO) as an electron transport layer (ETL.). The solution processed inverted bulk heterojunction organic solar cells based on a thin film blend of poly (3-hexylthiophene 2, 5-diyl) and [6,6]-phenyl-C61-butyric acid methyl ester is prepared. ZnO thin films are annealed at different temperature to optimize the solar cell performance and their characterization for their structural and optical properties are carried out. We have observed Voc=70mV, Jsc=1.33 µA/cm2 and FF=26% from the inverted heterojunction solar cell.

Characterization of cobalt(II) chloride-modified condensation polyimide films

NASA Technical Reports Server (NTRS)

Rancourt, J. D.; Taylor, L. T.

1988-01-01

The effect of solvent extraction on the properties of cobalt(II) chloride-modified polyimide films was investigated. Solvent-cast films were prepared from solutions of cobalt chloride in poly(amide acid)/N,N-dimethylacetamide (DMAc) and were subsequently dried and cured in static air, forced air, or inert gas ovens with controlled humidity. The films were extracted by either of the three processes (1) soaking in a tray with distilled water at room temperature, (2) soxhlett extraction with distilled water, or (3) soxhell extraction with DMAc. Extraction with DMAc was found to remove both cobalt and chlorine from the films and to slightly increase bulk thermal stability and both surface resistivity and electrical resistivity.

Thermodynamics of Surfactants, Block Copolymers and Their Mixtures in Water: The Role of the Isothermal Calorimetry

PubMed Central

De Lisi, Rosario; Milioto, Stefania; Muratore, Nicola

2009-01-01

The thermodynamics of conventional surfactants, block copolymers and their mixtures in water was described to the light of the enthalpy function. The two methodologies, i.e. the van’t Hoff approach and the isothermal calorimetry, used to determine the enthalpy of micellization of pure surfactants and block copolymers were described. The van’t Hoff method was critically discussed. The aqueous copolymer+surfactant mixtures were analyzed by means of the isothermal titration calorimetry and the enthalpy of transfer of the copolymer from the water to the aqueous surfactant solutions. Thermodynamic models were presented to show the procedure to extract straightforward molecular insights from the bulk properties. PMID:19742173

High Pressure X-Ray Diffraction Studies of Bi2-xSbxTe3 (x = 0,1,2)

NASA Astrophysics Data System (ADS)

Jacobsen, M. K.; Kumar, R. S.; Cornelius, A. L.; Sinogeiken, S. V.; Nico, M. F.

2007-12-01

Recently, pressure tuning of the thermoelectric figure of merit has been reported for several materials Bi2Te3 based thermoelectric materials [2],[10],[12]. In order to investigate the bulk properties of Bi2Te3, Sb2Te3, and their solid solution in detail, we have performed structural studies up to 20 GPa. Our diffraction results show that all three compounds transform from the ambient pressure structure to a high pressure phase between 7 and 10 GPa. In addition, these diffraction results have been converted to Vinet and Holzapfel equations of state to test the claim of electronic topological transitions in these structures [3].

Probing the micro-rheological properties of aerosol particles using optical tweezers

NASA Astrophysics Data System (ADS)

Power, Rory M.; Reid, Jonathan P.

2014-07-01

The use of optical trapping techniques to manipulate probe particles for performing micro-rheological measurements on a surrounding fluid is well-established. Here, we review recent advances made in the use of optical trapping to probe the rheological properties of trapped particles themselves. In particular, we review observations of the continuous transition from liquid to solid-like viscosity of sub-picolitre supersaturated solution aerosol droplets using optical trapping techniques. Direct measurements of the viscosity of the particle bulk are derived from the damped oscillations in shape following coalescence of two particles, a consequence of the interplay between viscous and surface forces and the capillary driven relaxation of the approximately spheroidal composite particle. Holographic optical tweezers provide a facile method for the manipulation of arrays of particles allowing coalescence to be controllably induced between two micron-sized aerosol particles. The optical forces, while sufficiently strong to confine the composite particle, are several orders of magnitude weaker than the capillary forces driving relaxation. Light, elastically back-scattered by the particle, is recorded with sub-100 ns resolution allowing measurements of fast relaxation (low viscosity) dynamics, while the brightfield image can be used to monitor the shape relaxation extending to times in excess of 1000 s. For the slowest relaxation dynamics studied (particles with the highest viscosity) the presence and line shape of whispering gallery modes in the cavity enhanced Raman spectrum can be used to infer the relaxation time while serving the dual purpose of allowing the droplet size and refractive index to be measured with accuracies of ±0.025% and ±0.1%, respectively. The time constant for the damped relaxation can be used to infer the bulk viscosity, spanning from the dilute solution limit to a value approaching that of a glass, typically considered to be >1012 Pa s, whilst the frequencies of the normal modes of the oscillations of the particle can be used to infer surface properties. We will review the use of optical tweezers for studying the viscosity of aerosol particles and discuss the potential use of this micro-rheological tool for probing the fundamental concepts of phase, thermodynamic equilibrium and metastability.

Solution processing of chalcogenide materials using thiol-amine "alkahest" solvent systems.

PubMed

McCarthy, Carrie L; Brutchey, Richard L

2017-05-02

Macroelectronics is a major focus in electronics research and is driven by large area applications such as flat panel displays and thin film solar cells. Innovations for these technologies, such as flexible substrates and mass production, will require efficient and affordable semiconductor processing. Low-temperature solution processing offers mild deposition methods, inexpensive processing equipment, and the possibility of high-throughput processing. In recent years, the discovery that binary "alkahest" mixtures of ethylenediamine and short chain thiols possess the ability to dissolve bulk inorganic materials to yield molecular inks has lead to the wide study of such systems and the straightforward recovery of phase pure crystalline chalcogenide thin films upon solution processing and mild annealing of the inks. In this review, we recount the work that has been done toward elucidating the scope of this method for the solution processing of inorganic materials for use in applications such as photovoltaic devices, electrocatalysts, photodetectors, thermoelectrics, and nanocrystal ligand exchange. We also take stock of the wide range of bulk materials that can be used as soluble precursors, and discuss the work that has been done to reveal the nature of the dissolved species. This method has provided a vast toolbox of over 65 bulk precursors, which can be utilized to develop new routes to functional chalcogenide materials. Future studies in this area should work toward a better understanding of the mechanisms involved in the dissolution and recovery of bulk materials, as well as broadening the scope of soluble precursors and recoverable functional materials for innovative applications.

Nucleation and Growth of Insulin Fibrils in Bulk Solution and at Hydrophobic Polystyrene Surfaces

PubMed Central

Smith, M. I.; Sharp, J. S.; Roberts, C. J.

2007-01-01

A technique was developed for studying the nucleation and growth of fibrillar protein aggregates. Fourier transform infrared and attenuated total reflection spectroscopy were used to measure changes in the intermolecular β-sheet content of bovine pancreatic insulin in bulk solution and on model polystyrene (PS) surfaces at pH 1. The kinetics of β-sheet formation were shown to evolve in two stages. Combined Fourier transform infrared, dynamic light scattering, atomic force microscopy, and thioflavin-T fluorescence measurements confirmed that the first stage in the kinetics was related to the formation of nonfibrillar aggregates that have a radius of 13 ± 1 nm. The second stage was found to be associated with the growth of insulin fibrils. The β-sheet kinetics in this second stage were used to determine the nucleation and growth rates of fibrils over a range of temperatures between 60°C and 80°C. The nucleation and growth rates were shown to display Arrhenius kinetics, and the associated energy barriers were extracted for fibrils formed in bulk solution and at PS surfaces. These experiments showed that fibrils are nucleated more quickly in the presence of hydrophobic PS surfaces but that the corresponding fibril growth rates decrease. These observations are interpreted in terms of the differences in the attempt frequencies and energy barriers associated with the nucleation and growth of fibrils. They are also discussed in the context of differences in protein concentration, mobility, and conformational and colloidal stability that exist between insulin molecules in bulk solution and those that are localized at hydrophobic PS interfaces. PMID:17496011

A model for homeopathic remedy effects: low dose nanoparticles, allostatic cross-adaptation, and time-dependent sensitization in a complex adaptive system

PubMed Central

2012-01-01

Background This paper proposes a novel model for homeopathic remedy action on living systems. Research indicates that homeopathic remedies (a) contain measurable source and silica nanoparticles heterogeneously dispersed in colloidal solution; (b) act by modulating biological function of the allostatic stress response network (c) evoke biphasic actions on living systems via organism-dependent adaptive and endogenously amplified effects; (d) improve systemic resilience. Discussion The proposed active components of homeopathic remedies are nanoparticles of source substance in water-based colloidal solution, not bulk-form drugs. Nanoparticles have unique biological and physico-chemical properties, including increased catalytic reactivity, protein and DNA adsorption, bioavailability, dose-sparing, electromagnetic, and quantum effects different from bulk-form materials. Trituration and/or liquid succussions during classical remedy preparation create “top-down” nanostructures. Plants can biosynthesize remedy-templated silica nanostructures. Nanoparticles stimulate hormesis, a beneficial low-dose adaptive response. Homeopathic remedies prescribed in low doses spaced intermittently over time act as biological signals that stimulate the organism’s allostatic biological stress response network, evoking nonlinear modulatory, self-organizing change. Potential mechanisms include time-dependent sensitization (TDS), a type of adaptive plasticity/metaplasticity involving progressive amplification of host responses, which reverse direction and oscillate at physiological limits. To mobilize hormesis and TDS, the remedy must be appraised as a salient, but low level, novel threat, stressor, or homeostatic disruption for the whole organism. Silica nanoparticles adsorb remedy source and amplify effects. Properly-timed remedy dosing elicits disease-primed compensatory reversal in direction of maladaptive dynamics of the allostatic network, thus promoting resilience and recovery from disease. Summary Homeopathic remedies are proposed as source nanoparticles that mobilize hormesis and time-dependent sensitization via non-pharmacological effects on specific biological adaptive and amplification mechanisms. The nanoparticle nature of remedies would distinguish them from conventional bulk drugs in structure, morphology, and functional properties. Outcomes would depend upon the ability of the organism to respond to the remedy as a novel stressor or heterotypic biological threat, initiating reversals of cumulative, cross-adapted biological maladaptations underlying disease in the allostatic stress response network. Systemic resilience would improve. This model provides a foundation for theory-driven research on the role of nanomaterials in living systems, mechanisms of homeopathic remedy actions and translational uses in nanomedicine. PMID:23088629

A model for homeopathic remedy effects: low dose nanoparticles, allostatic cross-adaptation, and time-dependent sensitization in a complex adaptive system.

PubMed

Bell, Iris R; Koithan, Mary

2012-10-22

This paper proposes a novel model for homeopathic remedy action on living systems. Research indicates that homeopathic remedies (a) contain measurable source and silica nanoparticles heterogeneously dispersed in colloidal solution; (b) act by modulating biological function of the allostatic stress response network (c) evoke biphasic actions on living systems via organism-dependent adaptive and endogenously amplified effects; (d) improve systemic resilience. The proposed active components of homeopathic remedies are nanoparticles of source substance in water-based colloidal solution, not bulk-form drugs. Nanoparticles have unique biological and physico-chemical properties, including increased catalytic reactivity, protein and DNA adsorption, bioavailability, dose-sparing, electromagnetic, and quantum effects different from bulk-form materials. Trituration and/or liquid succussions during classical remedy preparation create "top-down" nanostructures. Plants can biosynthesize remedy-templated silica nanostructures. Nanoparticles stimulate hormesis, a beneficial low-dose adaptive response. Homeopathic remedies prescribed in low doses spaced intermittently over time act as biological signals that stimulate the organism's allostatic biological stress response network, evoking nonlinear modulatory, self-organizing change. Potential mechanisms include time-dependent sensitization (TDS), a type of adaptive plasticity/metaplasticity involving progressive amplification of host responses, which reverse direction and oscillate at physiological limits. To mobilize hormesis and TDS, the remedy must be appraised as a salient, but low level, novel threat, stressor, or homeostatic disruption for the whole organism. Silica nanoparticles adsorb remedy source and amplify effects. Properly-timed remedy dosing elicits disease-primed compensatory reversal in direction of maladaptive dynamics of the allostatic network, thus promoting resilience and recovery from disease. Homeopathic remedies are proposed as source nanoparticles that mobilize hormesis and time-dependent sensitization via non-pharmacological effects on specific biological adaptive and amplification mechanisms. The nanoparticle nature of remedies would distinguish them from conventional bulk drugs in structure, morphology, and functional properties. Outcomes would depend upon the ability of the organism to respond to the remedy as a novel stressor or heterotypic biological threat, initiating reversals of cumulative, cross-adapted biological maladaptations underlying disease in the allostatic stress response network. Systemic resilience would improve. This model provides a foundation for theory-driven research on the role of nanomaterials in living systems, mechanisms of homeopathic remedy actions and translational uses in nanomedicine.

A bulk superconducting MgB2 cylinder for holding transversely polarized targets

NASA Astrophysics Data System (ADS)

Statera, M.; Balossino, I.; Barion, L.; Ciullo, G.; Contalbrigo, M.; Lenisa, P.; Lowry, M. M.; Sandorfi, A. M.; Tagliente, G.

2018-02-01

An innovative solution is being pursued for the challenging magnetic problem of producing an internal transverse field around a polarized target, while shielding out an external longitudinal field from a detector. A hollow bulk superconductor can trap a transverse field that is present when cooled through its transition temperature, and also shield its interior from any subsequent field changes. A feasibility study with a prototype bulk MgB2 superconducting cylinder is described. Promising measurements taken of the interior field retention and exterior field exclusion, together with the corresponding long-term stability performance, are reported. In the context of an electron scattering experiment, such a solution minimizes beam deflection and the energy loss of reaction products, while also eliminating the heat load to the target cryostat from current leads that would be used with conventional electromagnets.

Pheromone discrimination by a pH-tuned polymorphism of the Bombyx mori pheromone-binding protein.

PubMed

Damberger, Fred F; Michel, Erich; Ishida, Yuko; Leal, Walter S; Wüthrich, Kurt

2013-11-12

The Bombyx mori pheromone-binding protein (BmorPBP) is known to adopt two different conformations. These are BmorPBP(A), where a regular helix formed by the C-terminal dodecapeptide segment, α7, occupies the ligand-binding cavity, and BmorPBP(B), where the binding site is free to accept ligands. NMR spectra of delipidated BmorPBP solutions at the physiological pH of the bulk sensillum lymph near pH 6.5 show only BmorPBP(A), and in mixtures, the two species are in slow exchange on the chemical shift frequency scale. This equilibrium has been monitored at variable pH and ligand concentrations, demonstrating that it is an intrinsic property of BmorPBP that is strongly affected by pH variation and ligand binding. This polymorphism tunes BmorPBP for optimal selective pheromone transport: Competition between α7 and lipophilic ligands for its binding cavity enables selective uptake of bombykol at the pore endings in the sensillum wall, whereas compounds with lower binding affinity can only be bound in the bulk sensillum lymph. After transport across the bulk sensillum lymph into the lower pH area near the dendritic membrane surface, bombykol is ejected near the receptor, whereas compounds with lower binding affinity are ejected before reaching the olfactory receptor, rendering them susceptible to degradation by enzymes present in the sensillum lymph.

Contribution of galloylation and polymerization to the antioxidant activity of polyphenols in fish lipid systems.

PubMed

Iglesias, Jacobo; Pazos, Manuel; Lois, Salomé; Medina, Isabel

2010-06-23

Polyphenolic fractions extracted from pine (Pinus pinaster) bark, grape (Vitis vinifera) pomace, and witch hazel (Hamamelis virginiana) bark were selected for investigating the influence of the number of phenolic units, polymerization, and the content of esterified galloyl residues (galloylation) on their efficacy for inhibiting lipid oxidation in fish lipid enriched foodstuffs. Experiments carried out with nongalloylated pine bark fractions with different polymerization degrees demonstrated that the number of catechin residues per molecule modulates their reducing and chelating properties in solution. In real food systems such as bulk fish oil and fish oil-in-water emulsions, the efficacy against lipid oxidation was highly dependent on the physical location of the antioxidant at the oxidative sensitive sites. The lowest polymerized fractions were the most efficient in bulk fish oil samples, whereas proanthocyanidins with an intermediate polymerization degree showed the highest activity in fish oil-in-water emulsions. Galloylation did not influence the antioxidant effectiveness of proanthocyanidins in bulk fish oils. The presence of galloyl groups favored the antioxidant activity of the polyphenols in emulsions, although results indicated that a high degree of galloylation did not improve significantly the activity found with medium galloylated proanthocyanidins. The results obtained in this research provide useful information about the relationship between structure and antioxidant activity in order to design antioxidant additives with application in fish oil-enriched functional foods.

Improving our understanding of hydraulic-electrical relations: A case study of the surficial aquifer in Emirate Abu Dhabi

USGS Publications Warehouse

Ikard, Scott; Kress, Wade

2016-01-01

Transmissivity is a bulk hydraulic property that can be correlated with bulk electrical properties of an aquifer. In aquifers that are electrically-resistive relative to adjacent layers in a horizontally stratified sequence, transmissivity has been shown to correlate with bulk transverse resistance. Conversely, in aquifers that are electrically-conductive relative to adjacent layers, transmissivity has been shown to correlate with bulk longitudinal conductance. In both cases, previous investigations have relied on small datasets (on average less than eight observations) that have yielded coefficients of determination (R2) that are typically in the range of 0.6 to 0.7 to substantiate these relations. Compared to previous investigations, this paper explores hydraulic-electrical relations using a much larger dataset. Geophysical data collected from 26 boreholes in Emirate Abu Dhabi, United Arab Emirates, are used to correlate transmissivity modeled from neutron porosity logs to the bulk electrical properties of the surficial aquifer that are computed from deep-induction logs. Transmissivity is found to be highly correlated with longitudinal conductance. An R2 value of 0.853 is obtained when electrical effects caused by variations in pore-fluid salinity are taken into consideration.

Pretreatment of Hanford medium-curie wastes by fractional crystallization.

PubMed

Nassif, Laurent; Dumont, George; Alysouri, Hatem; Rousseau, Ronald W

2008-07-01

Acceleration of the schedule for decontamination of the Hanford site using bulk vitrification requires implementation of a pretreatment operation. Medium-curie waste must be separated into two fractions: one is to go to a waste treatment and immobilization plant and a second, which is low-activity waste, is to be processed by bulk vitrification. The work described here reports research on using fractional crystallization for that pretreatment. Sodium salts are crystallized by evaporation of water from solutions simulating those removed from single-shell tanks, while leaving cesium in solution. The crystalline products are then recovered and qualified as low-activity waste, which is suitable upon redissolution for processing by bulk vitrification. The experimental program used semibatch operation in which a feed solution was continuously added to maintain a constant level in the crystallizer while evaporating water. The slurry recovered at the end of a run was filtered to recover product crystals, which were then analyzed to determine their composition. The results demonstrated that targets on cesium separation from the solids, fractional recovery of sodium salts, and sulfate content of the recovered salts can be achieved by the process tested.

The dissolution of calcite in CO2-saturated solutions at 25°C and 1 atmosphere total pressure

USGS Publications Warehouse

Plummer, Niel; Wigley, T.M.L.

1976-01-01

The dissolution of Iceland spar in CO2-saturated solutions at 25°C and 1 atm total pressure has been followed by measurement of pH as a function of time. Surface concentrations of reactant and product species have been calculated from bulk fluid data using mass transport theory and a model that accounts for homogeneous reactions in the bulk fluid. The surface concentrations are found to be close to bulk solution values. This indicates that calcite dissolution under the experimental conditions is controlled by the kinetics of surface reaction. The rate of calcite dissolution follows an empirical second order relation with respect to calcium and hydrogen ion from near the initial condition (pH 3.91) to approximately pH 5.9. Beyond pH 5.9 the rate of surface reaction is greatly reduced and higher reaction orders are observed. Calculations show that the rate of calcite dissolution in natural environments may be influenced by both transport and surface-reaction processes. In the absence of inhibition, relatively short times should be sufficient to establish equilibrium.

A robust, melting class bulk superhydrophobic material with heat-healing and self-cleaning properties

PubMed Central

Ramakrishna, S.; Santhosh Kumar, K. S.; Mathew, Dona; Reghunadhan Nair, C. P.

2015-01-01

Superhydrophobic (SH) materials are essential for a myriad of applications such as anti-icing and self-cleaning due to their extreme water repellency. A single, robust material simultaneously possessing melt-coatability, bulk water repellency, self-cleanability, self-healability, self-refreshability, and adhesiveness has been remaining an elusive goal. We demonstrate a unique class of melt-processable, bulk SH coating by grafting long alkyl chains on silica nanoparticle surface by a facile one-step method. The well-defined nanomaterial shows SH property in the bulk and is found to heal macro-cracks on gentle heating. It retains wettability characteristics even after abrading with a sand paper. The surface regenerates SH features (due to reversible self-assembly of nano structures) quickly at ambient temperature even after cyclic water impalement, boiling water treatment and multiple finger rubbing tests. It exhibits self-cleaning properties on both fresh and cut surfaces. This kind of coating, hitherto undisclosed, is expected to be a breakthrough in the field of melt-processable SH coatings. PMID:26679096

Worms under Pressure: Bulk Mechanical Properties of C. elegans Are Independent of the Cuticle

PubMed Central

Gilpin, William; Uppaluri, Sravanti; Brangwynne, Clifford P.

2015-01-01

The mechanical properties of cells and tissues play a well-known role in physiology and disease. The model organism Caenorhabditis elegans exhibits mechanical properties that are still poorly understood, but are thought to be dominated by its collagen-rich outer cuticle. To our knowledge, we use a novel microfluidic technique to reveal that the worm responds linearly to low applied hydrostatic stress, exhibiting a volumetric compression with a bulk modulus, κ = 140 ± 20 kPa; applying negative pressures leads to volumetric expansion of the worm, with a similar bulk modulus. Surprisingly, however, we find that a variety of collagen mutants and pharmacological perturbations targeting the cuticle do not impact the bulk modulus. Moreover, the worm exhibits dramatic stiffening at higher stresses—behavior that is also independent of the cuticle. The stress-strain curves for all conditions can be scaled onto a master equation, suggesting that C. elegans exhibits a universal elastic response dominated by the mechanics of pressurized internal organs. PMID:25902429

Study of phonon modes and elastic properties of Sc36Al24Co20Y20 and Gd36Al24Co20Y20 rare-earth bulk metallic glasses

NASA Astrophysics Data System (ADS)

Suthar, P. H.; Gajjar, P. N.; Thakore, B. Y.; Jani, A. R.

2013-04-01

A phonon modes and elastic properties of two different rare-earth based bulk metallic glasses Sc36Al24Co20Y20 and Gd36Al24Co20Y20 are computed using Hubbard-Beeby approach and our well established model potential. The local field correlation functions due to Hartree (H), Taylor (T), Ichimaru and Utsumi (IU), Farid et al (F) and Sarkar Sen et al (S) are employed to investigate the influence of the screening effects on the vibrational dynamics of Sc36Al24Co20Y20 and Gd36Al24Co20Y20 bulk metallic glasses. The results for bulk modulus BT, modulus of rigidity G, Poisson's ratio ξ, Young's modulus Y, Debye temperature ΘD, propagation velocity of elastic waves and dispersion curves are reported. The computed elastic properties are found to be in good agreement with experimental and other available data.

Interfacial and Electrode Modifications in P3HT:PC61BM based Organic Solar Cells: Devices, Processing and Characterization

NASA Astrophysics Data System (ADS)

Das, Sayantan

The inexorable upsurge in world’s energy demand has steered the search for newer renewable energy sources and photovoltaics seemed to be one of the best alternatives for energy production. Among the various photovoltaic technologies that emerged, organic/polymer photovoltaics based on solution processed bulk-heterojunctions (BHJ) of semiconducting polymers has gained serious attention owing to the use of inexpensive light-weight materials, exhibiting high mechanical flexibility and compatibility with low temperature roll-to-roll manufacturing techniques on flexible substrates. The most widely studied material to date is the blend of regioregular P3HT and PC61BM used as donor and acceptor materials. The object of this study was to investigate and improve the performance/stability of the organic solar cells by use of inexpensive materials. In an attempt to enhance the efficiency of organic solar cells, we have demonstrated the use of hexamethyldisilazane (HMDS) modified indium tin oxide (ITO) electrode in bulk heterojunction solar cell structure The device studies showed a significant enhancement in the short-circuit current as well as in the shunt resistance on use of the hexamethyldisilazane (HMDS) layer. In another approach a p-type CuI hole-transport layer was utilized that could possibly replace the acidic PEDOT:PSS layer in the fabrication of high-efficiency solar cells. The device optimization was done by varying the concentration of CuI in the precursor solution which played an important role in the efficiency of the solar cell devices. Recently a substantial amount of research has been focused on identifying suitable interfacial layers in organic solar cells which has efficient charge transport properties. It was illustrated that a thin layer of silver oxide interfacial layer showed a 28% increase in power conversion efficiency in comparison to that of the control cell. The optoelectronic properties and morphological features of indium-free ZnO/Ag/MoOx electrodes was also studied. Organic solar cells on these composite electrodes revealed good optical and electrical properties, making them a promising alternative indium free and PEDOT:PSS-free organic solar cells. Lastly, inverted solar cells utilizing zinc oxide and yttrium doped zinc oxide electron transport was also created and their device properties revealed that optimum annealing conditions and yttrium doping was essential to obtain high efficiency solar cells.

Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions.

PubMed

Marenich, Aleksandr V; Cramer, Christopher J; Truhlar, Donald G

2009-05-07

We present a new continuum solvation model based on the quantum mechanical charge density of a solute molecule interacting with a continuum description of the solvent. The model is called SMD, where the "D" stands for "density" to denote that the full solute electron density is used without defining partial atomic charges. "Continuum" denotes that the solvent is not represented explicitly but rather as a dielectric medium with surface tension at the solute-solvent boundary. SMD is a universal solvation model, where "universal" denotes its applicability to any charged or uncharged solute in any solvent or liquid medium for which a few key descriptors are known (in particular, dielectric constant, refractive index, bulk surface tension, and acidity and basicity parameters). The model separates the observable solvation free energy into two main components. The first component is the bulk electrostatic contribution arising from a self-consistent reaction field treatment that involves the solution of the nonhomogeneous Poisson equation for electrostatics in terms of the integral-equation-formalism polarizable continuum model (IEF-PCM). The cavities for the bulk electrostatic calculation are defined by superpositions of nuclear-centered spheres. The second component is called the cavity-dispersion-solvent-structure term and is the contribution arising from short-range interactions between the solute and solvent molecules in the first solvation shell. This contribution is a sum of terms that are proportional (with geometry-dependent proportionality constants called atomic surface tensions) to the solvent-accessible surface areas of the individual atoms of the solute. The SMD model has been parametrized with a training set of 2821 solvation data including 112 aqueous ionic solvation free energies, 220 solvation free energies for 166 ions in acetonitrile, methanol, and dimethyl sulfoxide, 2346 solvation free energies for 318 neutral solutes in 91 solvents (90 nonaqueous organic solvents and water), and 143 transfer free energies for 93 neutral solutes between water and 15 organic solvents. The elements present in the solutes are H, C, N, O, F, Si, P, S, Cl, and Br. The SMD model employs a single set of parameters (intrinsic atomic Coulomb radii and atomic surface tension coefficients) optimized over six electronic structure methods: M05-2X/MIDI!6D, M05-2X/6-31G, M05-2X/6-31+G, M05-2X/cc-pVTZ, B3LYP/6-31G, and HF/6-31G. Although the SMD model has been parametrized using the IEF-PCM protocol for bulk electrostatics, it may also be employed with other algorithms for solving the nonhomogeneous Poisson equation for continuum solvation calculations in which the solute is represented by its electron density in real space. This includes, for example, the conductor-like screening algorithm. With the 6-31G basis set, the SMD model achieves mean unsigned errors of 0.6-1.0 kcal/mol in the solvation free energies of tested neutrals and mean unsigned errors of 4 kcal/mol on average for ions with either Gaussian03 or GAMESS.

Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions

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

Marenich, Aleksandr; Cramer, Christopher J; Truhlar, Donald G

2009-04-30

We present a new continuum solvation model based on the quantum mechanical charge density of a solute molecule interacting with a continuum description of the solvent. The model is called SMD, where the “D” stands for “density” to denote that the full solute electron density is used without defining partial atomic charges. “Continuum” denotes that the solvent is not represented explicitly but rather as a dielectric medium with surface tension at the solute-solvent boundary. SMD is a universal solvation model, where “universal” denotes its applicability to any charged or uncharged solute in any solvent or liquid medium for which amore » few key descriptors are known (in particular, dielectric constant, refractive index, bulk surface tension, and acidity and basicity parameters). The model separates the observable solvation free energy into two main components. The first component is the bulk electrostatic contribution arising from a self-consistent reaction field treatment that involves the solution of the nonhomogeneous Poisson equation for electrostatics in terms of the integral-equation-formalism polarizable continuum model (IEF-PCM). The cavities for the bulk electrostatic calculation are defined by superpositions of nuclear-centered spheres. The second component is called the cavity-dispersion-solvent-structure term and is the contribution arising from short-range interactions between the solute and solvent molecules in the first solvation shell. This contribution is a sum of terms that are proportional (with geometry-dependent proportionality constants called atomic surface tensions) to the solvent-accessible surface areas of the individual atoms of the solute. The SMD model has been parametrized with a training set of 2821 solvation data including 112 aqueous ionic solvation free energies, 220 solvation free energies for 166 ions in acetonitrile, methanol, and dimethyl sulfoxide, 2346 solvation free energies for 318 neutral solutes in 91 solvents (90 nonaqueous organic solvents and water), and 143 transfer free energies for 93 neutral solutes between water and 15 organic solvents. The elements present in the solutes are H, C, N, O, F, Si, P, S, Cl, and Br. The SMD model employs a single set of parameters (intrinsic atomic Coulomb radii and atomic surface tension coefficients) optimized over six electronic structure methods: M05-2X/MIDI!6D, M05-2X/6-31G*, M05-2X/6-31+G**, M05-2X/cc-pVTZ, B3LYP/6-31G*, and HF/6-31G*. Although the SMD model has been parametrized using the IEF-PCM protocol for bulk electrostatics, it may also be employed with other algorithms for solving the nonhomogeneous Poisson equation for continuum solvation calculations in which the solute is represented by its electron density in real space. This includes, for example, the conductor-like screening algorithm. With the 6-31G* basis set, the SMD model achieves mean unsigned errors of 0.6-1.0 kcal/mol in the solvation free energies of tested neutrals and mean unsigned errors of 4 kcal/mol on average for ions with either Gaussian03 or GAMESS.« less

Molecular modeling of polymers 16. Gaseous diffusion in polymers: a quantitative structure-property relationship (QSPR) analysis.

PubMed

Patel, H C; Tokarski, J S; Hopfinger, A J

1997-10-01

The purpose of this study was to identify the key physicochemical molecular properties of polymeric materials responsible for gaseous diffusion in the polymers. Quantitative structure-property relationships, QSPRs were constructed using a genetic algorithm on a training set of 16 polymers for which CO2, N2, O2 diffusion constants were measured. Nine physicochemical properties of each of the polymers were used in the trial basis set for QSPR model construction. The linear cross-correlation matrices were constructed and investigated for colinearity among the members of the training sets. Common water diffusion measures for a limited training set of six polymers was used to construct a "semi-QSPR" model. The bulk modulus of the polymer was overwhelmingly found to be the dominant physicochemical polymer property that governs CO2, N2 and O2 diffusion. Some secondary physicochemical properties controlling diffusion, including conformational entropy, were also identified as correlation descriptors. Very significant QSPR diffusion models were constructed for all three gases. Cohesive energy was identified as the main correlation physicochemical property with aqueous diffusion measures. The dominant role of polymer bulk modulus on gaseous diffusion makes it difficult to develop criteria for selective transport of gases through polymers. Moreover, high bulk moduli are predicted to be necessary for effective gas barrier materials. This property requirement may limit the processing and packaging features of the material. Aqueous diffusion in polymers may occur by a different mechanism than gaseous diffusion since bulk modulus does not correlate with aqueous diffusion, but rather cohesive energy of the polymer.

Comment on "Horizontal aquifer movement in a theis-theim confined system, by Donald C. Helm

USGS Publications Warehouse

Hsieh, Paul A.; Cooley, Richard L.

1995-01-01

In a recent paper, Helm [1994] presents an analysis of horizontal aquifer movement induced by groundwater withdrawal from a confined aquifer in which fluid and grains are incompressible. The analysis considers the aquifer in isolation (ignoring overlying and underlying strata) and assumes that the aquifer deforms purely in the horizontal direction (with no vertical movement). Helm's solution for grain displacement is obtained through introduction of a quantity known as bulk flux, qb, defined asqb = nvw + (1 - n)vswhere n is porosity, vw is velocity of water, and vs is the velocity of the solid grains. On the basis of the bulk flux concept, Helm develops an explanation for the driving force on the bulk material.It is our view that Helm's analysis is subject to four limitations. First, Helm's assumption of zero vertical displacement is not supported by field observations and could result in over- estimation of radial displacement. Second, in ignoring the role of overlying and underlying strata, Helm's solution does not yield reliable estimates of aquifer deformation. Third, Helm's solution method works only for problems that involve one spatial coordinate (for example, x or r) but does not generally work for problems involving three-dimensional flow and de- formation. Fourth, Helm's explanation of the driving force on the bulk material is faulty for general three-dimensional problems. The purpose of our comment is to discuss these four issues.

Investigation of electrophoretic exclusion method for the concentration and differentiation of proteins.

PubMed

Meighan, Michelle M; Vasquez, Jared; Dziubcynski, Luke; Hews, Sarah; Hayes, Mark A

2011-01-01

This work presents a technique termed as "electrophoretic exclusion" that is capable of differentiation and concentration of proteins in bulk solution. In this method, a hydrodynamic flow is countered by the electrophoretic velocity to prevent a species from entering into a channel. The separation can be controlled by changing the flow rate or applied electric potential in order to exclude a certain species selectively while allowing others to pass through the capillary. The exclusion of various proteins is investigated using a flow-injection regime of the method. Concentration of myoglobin of up to 1200 times the background concentration in 60 s was demonstrated. Additionally, negatively charged myoglobin was separated from a solution containing negatively charged allophycocyanin. Cationic cytochrome c was also differentiated from a solution with allophycocyanin. The ability to differentially transport species in bulk solution enables parallel and serial separation modes not available with other separations schemes.

[Energy saving achieved by limited filamentous bulking under low dissolved oxygen: derivation, originality and theoretical basis].

PubMed

Peng, Yong-zhen; Guo, Jian-hua; Wang, Shu-ying; Chen, Ying

2008-12-01

How to prevent and control filamentous bulking sludge has being a research focus and attracted much attention. To date despite the extensive research that has been done on bulking sludge, filamentous bulking still occurs world-wide and a comprehensive solution does not seem to be available. Particularly, there are few studies about making use of the characteristics of filamentous bacteria and achieving energy saving by filamentous bulking. Limited filamentous bulking, a novel method for energy saving while equal or better treatment performance by allowing slight and controlled filamentous bulking sludge at low dissolved oxygen (DO), was proposed based on full-scale field observations. The practical operation showed that limited filamentous bulking resulted from a decline in DO concentration. COD, SS and TP removal could be enhanced and energy saving could be achieved by limited filamentous bulking at low DO. The derivation of limited filamentous bulking is introduced firstly, and then the theoretical fundamentals of the technique of limited filamentous bulking are presented and analyzed, including the occurrence of limited filamentous bulking caused by low DO, the enhanced effect of filamentous bacteria on pollutants removal and the energy saving mechanism by using limited filamentous bulking. Besides, the paper provides some new perspectives about the application and research direction of limited filamentous bulking in future.

Numerical simulation of crevice corrosion of titanium: Effect of the bold surface

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

Evitts, R.W.; Postlethwaite, J.; Watson, M.K.

1996-12-01

A rigorous crevice corrosion model has been developed that accounts for the bold metal surfaces exterior to the crevice. The model predicts the time change in concentration of all specified chemical species in the crevice and bulk solution, and has the ability to predict active corrosion. It is applied to the crevice corrosion of a small titanium crevice in both oxygenated and anaerobic sodium chloride solutions. The numerical predictions confirm that oxygen is the driving force for crevice corrosion. During the simulations where oxygen is initially present in both the crevice and bulk solution an acidic chloride solution is developed;more » this is the precursor required for crevice corrosion. The anaerobic case displays no tendency to form such a solution. It is also confirmed that those areas in the crevice that are deoxygenated become anodic and the bold metal surface becomes cathodic. As expected, active corrosion is not attained as the simulations are based on electrochemical and chemical parameters at 25 C.« less

Coatable Li4 SnS4 Solid Electrolytes Prepared from Aqueous Solutions for All-Solid-State Lithium-Ion Batteries.

PubMed

Choi, Young Eun; Park, Kern Ho; Kim, Dong Hyeon; Oh, Dae Yang; Kwak, Hi Ram; Lee, Young-Gi; Jung, Yoon Seok

2017-06-22

Bulk-type all-solid-state lithium-ion batteries (ASLBs) for large-scale energy-storage applications have emerged as a promising alternative to conventional lithium-ion batteries (LIBs) owing to their superior safety. However, the electrochemical performance of bulk-type ASLBs is critically limited by the low ionic conductivity of solid electrolytes (SEs) and poor ionic contact between the active materials and SEs. Herein, highly conductive (0.14 mS cm -1 ) and dry-air-stable SEs (Li 4 SnS 4 ) are reported, which are prepared using a scalable aqueous-solution process. An active material (LiCoO 2 ) coated by solidified Li 4 SnS 4 from aqueous solutions results in a significant improvement in the electrochemical performance of ASLBs. Side-effects of the exposure of LiCoO 2 to aqueous solutions are minimized by using predissolved Li 4 SnS 4 solution. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

In situ pH within particle beds of bioactive glasses.

PubMed

Zhang, Di; Hupa, Mikko; Hupa, Leena

2008-09-01

The in vitro behavior of three bioactive glasses with seven particle size distributions was studied by measuring the in situ pH inside the particle beds for 48h in simulated body fluid (SBF). After immersion, the surface of the particles was characterized with a field emission scanning electron microscope equipped with an energy-dispersive X-ray analyzer. In addition, the results were compared with the reactions of the same glasses formed as plates. A similar trend in pH as a function of immersion time was observed for all systems. However, the pH inside the particle beds was markedly higher than that in the bulk SBF of the plates. The pH decreased as power functions with increasing particle size, i.e. with decreasing surface area. The in vitro reactivity expressed as layer formation strongly depended on the particle size and glass composition. The average thickness of the total reaction layer decreased with the increase in sample surface area. Well-developed silica and calcium phosphate layers typically observed on glass plates could be detected only on some particles freely exposed to the solution. No distinct reaction layers were observed on the finest particles, possibly because the layers spread out on the large surface area. Differences in the properties of the bulk SBF and the solution inside the particle bed were negligible for particles larger than 800microm. The results enhance our understanding of the in vitro reactions of bioactive glasses in various product forms and sizes.

Supersaturated Electrolyte Solutions: Theory and Experiment

NASA Technical Reports Server (NTRS)

Izmailov, Alexander F.; Myerson, Allan S.; Na, Han-Soo

1995-01-01

Highly supersaturated electrolyte solutions can be prepared and studied employing an electrodynamic levitator trap (ELT) technique. The ELT technique involves containerless suspension of a microdroplet thus eliminating dust, dirt, and container walls which normally cause heterogeneous nucleation. This allows very high supersaturations to be achieved. A theoretical study of the experimental results obtained for the water activity in microdroplets of various electrolyte solutions is based on the development of the Cahn-Hilliard formalism for electrolyte solutions. In the approach suggested the metastable state for electrolyte solutions is described in terms of the conserved order parameter omega(r,t) associated with fluctuations of the mean solute concentration n(sub 0). Parameters of the corresponding Ginzburg-Landau free energy functional which defines the dynamics of metastable state relaxation are determined and expressed through the experimentally measured quantities. A correspondence of 96-99 % between theory and experiment for all solutions studied was achieved and allowed the determination of an analytical expression for the spinodal concentration n(sub spin), and its calculation for various electrolyte solutions at 298 K. The assumption that subcritical solute clusters consist of the electrically neutral Bjerrum pairs has allowed both analytical and numerical investigation of the number-size N(sub c) of nucleation monomers (aggregates of the Bjerrum pairs) which are elementary units of the solute critical clusters. This has also allowed estimations for the surface tension Alpha, and equilibrium bulk energy Beta per solute molecule in the nucleation monomers. The dependence of these properties on the temperature T and on the solute concentration n(sub 0) through the entire metastable zone (from saturation concentration n(sub sat) to spinodal n(sub spin) is examined. It has been demonstrated that there are the following asymptotics: N(sub c), = I at spinodal concentration and N(sub c) = infinity at saturation.

Hydroxyapatite degradation and biocompatibility

NASA Astrophysics Data System (ADS)

Wang, Haibo

Hydroxyapatite (HA) is widely used as a bioactive ceramics since it forms a chemical bonding to bone. The disadvantage of this material is its poor mechanical properties. HA can be degraded in body, which is the reason for its bioactivity, but too fast degradation rate could cause negative effects, such as macrophage present, particle generation, and even implant clinical failure. HA degradation rate will be greatly changed under many conditions: purity, HA form (i.e. bulk form, porous form, coating, or HA/polymer composites), microstructure, implant site, body conditions, etc. Although much work has been done in HA properties and application areas, the HA degradation behavior and mechanism under these different conditions are still not clear. In this research, three aspects of HA degradation have been studied: (1) Two very common impurities---Tri-Calcium Phosphate (TCP) and Calcium Oxide and their influences on HA degradation in vitro and in vivo, (2) influence of HA/polymer composite form on HA degradation, (3) HA material particle generation and related mechanism. From the in vitro and in vivo tests on bulk HA disks with various Ca/P ratios, HA degradation can clearly be found. The degradation level is different in different Ca/P ratio samples as well as in different test environments. In same test environment, non-stoichiometric HA samples have higher degradation rate than stoichiometric HA. HA/PMMA composite design successfully intensifies HA degradation both in vitro and in vivo. Grain boundary damage can be found on in vivo test samples, which has not been clearly seen on bulk HA degraded surface. HA particle generation is found in in vitro and in vivo HA/PMMA composite surface and in vivo bulk HA surface. Sintering temperature and time does affect HA grain size, and this affect HA degradation rate. Intergranular fracture is found in a several micron zone close to the Ca/P ratio 1.62 and 1.67 sample degraded surfaces. At Ca/P ratio greater than 1.667, after HA degradation in water, solution pH increases because of CaO presence.

Comparative study of the molecularly imprinted polymers prepared by reversible addition-fragmentation chain transfer "bulk" polymerization and traditional radical "bulk" polymerization.

PubMed

Ma, Yue; Pan, Guoqing; Zhang, Ying; Guo, Xianzhi; Zhang, Huiqi

2013-05-01

Bisphenol A (BPA) and propranolol-imprinted polymers have been prepared via both reversible addition-fragmentation chain transfer "bulk" polymerization (RAFTBP) and traditional radical "bulk" polymerization (TRBP) under similar reaction conditions, and their equilibrium binding properties were compared in detail for the first time. The chemical compositions, specific surface areas, equilibrium bindings, and selectivity of the obtained molecularly imprinted polymers (MIPs) were systematically characterized. The experimental results showed that the MIPs with molecular imprinting effects and quite fast binding kinetics could be readily prepared via RAFTBP, but they did not show improved template binding properties in comparison with those prepared via TRBP, which is in sharp contrast to many previous reports. This could be attributed to the heavily interrupted equilibrium between the dormant species and active radicals in the RAFT mechanism because of the occurrence of fast gelation during RAFTBP. The findings presented here strongly demonstrates that the application of controlled radical polymerizations (CRPs) in molecular imprinting does not always benefit the binding properties of the resultant MIPs, which is of significant importance for the rational use of CRPs in generating MIPs with improved properties. Copyright © 2013 John Wiley & Sons, Ltd.

BULK SYNTHESIS OF SILVER NANORODS IN POLY(ETHYLENE GLYCOL) USING MICROWAVE IRRADIATION

EPA Science Inventory

Microwave-assisted (MW), surfactantless, greener approach to bulk synthesis of silver nanorods employing poly (ethylene glycol) (PEG) is described. An aqueous solution of silver nitrate (AgNO-3,- 0.1 M, 4 mL) and 4 mL of PEG (molecular weight 300) were mixed at room temperature t...

Successful Treatment of Cerebral Toxoplasmosis Using Pyrimethamine Oral Solution Compounded From Inexpensive Bulk Powder.

PubMed

Hodgson, Hayley A; Sim, Taeyong; Gonzalez, Hemil; Aziz, Mariam; Rhee, Yoona; Lewis, Paul O; Jhobalia, Neel; Shields, Beth; Wang, Sheila K

2018-04-01

A price increase of pyrimethamine tablets in the United States has made the life-saving drug difficult to acquire for hospitalized patients who need it most. We report the successful use of a pyrimethamine oral suspension compounded from an economical bulk powder in a patient with acute toxoplasmic encephalitis.

MICROWAVE-ASSISTED SHAPE CONTROLLED BULK SYNTHESIS OF AG AND FE NANORODS IN POLY (ETHYLENE GLYCOL) SOLUTIONS

EPA Science Inventory

Bulk syntheses of silver (Ag) and iron (Fe) nanorods using poly (ethylene glycol), PEG, under microwave irradiation (MW) conditions are reported. Favorable conditions to make Ag nanorods were established and can be extended to make Fe nanorods with uniform size and shape. The nan...

Black holes in higher spin supergravity

NASA Astrophysics Data System (ADS)

Datta, Shouvik; David, Justin R.

2013-07-01

We study black hole solutions in Chern-Simons higher spin supergravity based on the superalgebra sl(3|2). These black hole solutions have a U(1) gauge field and a spin 2 hair in addition to the spin 3 hair. These additional fields correspond to the R-symmetry charges of the supergroup sl(3|2). Using the relation between the bulk field equations and the Ward identities of a CFT with {N} = 2 super- {{{W}}_3} symmetry, we identify the bulk charges and chemical potentials with those of the boundary CFT. From these identifications we see that a suitable set of variables to study this black hole is in terms of the charges present in three decoupled bosonic sub-algebras of the {N} = 2 super- {{{W}}_3} algebra. The entropy and the partition function of these R-charged black holes are then evaluated in terms of the charges of the bulk theory as well as in terms of its chemical potentials. We then compute the partition function in the dual CFT and find exact agreement with the bulk partition function.

Research on the synergistic doped effects and the catalysis properties of Cu2+ and Zn2+ co-doped CeO2 solid solutions

NASA Astrophysics Data System (ADS)

Zhang, Guofang; Li, Yiming; Hou, Zhonghui; Xv, Jianyi; Wang, Qingchun; Zhang, Yanghuan

2018-08-01

The Cu2+ and Zn2+ co-doped CeO2-based solid solutions were synthesized via hydrothermal method. The microstructure and the spectra features of the solid solutions were characterized systematically. The XRD results showed that the dopants were incorporated into the CeO2 lattice to form Ce1-xCu0.5xZn0.5xO2 solid solutions when x was lower than 0.14. The cell parameters and the crystalline size decreased linearly, and the lattice strain gradually increased with increasing the doping level. The TEM patterns showed that the particle size in the solid solution was lower than 10 nm which is in accordance with the XRD results. The ICP analysis indicated that the real doped content in the solid solution was close to the nominal proportion. XPS proved that the Ce3+ component was increased by doping. The Raman and PL spectra indicated that the lattice distortion and the oxygen vacancies also increased following the same trend. At the same time, the synergistic effects of two ions co-doped solid solutions were studied by comparing them with that of single ions doped samples. The catalysis effects of Cu2+ and Zn2+ co-doped CeO2-based solid solutions on the hydrogen storage electrochemical and kinetic properties of Mg2Ni alloys were detected. The electrochemistry properties of the Mg2Ni-Ni-5 wt% Ce1-xCu0.5xZn0.5xO2 composites indicated that the doped catalysts could provide better optimizations to improve the maximum discharge capacities and the discharge potentials. On the other hand, the charge transfer abilities on the surface and diffusion rate of H atoms in the bulk of alloys also got improved. The DSC measurements showed that the hydrogen desorption activation of the hydrogenated composites with Ce0.88Cu0.06Zn0.06O2 solid solutions decreased to 77.03 kJ mol-1, while that of the composites with pure CeO2 was 97.62 kJ mol-1. The catalysis effect was enhanced by the doped content increase that means that the catalysis mechanism had close links to the oxygen vacancy concentration and the lattice defects in the solid solutions. On the other hand, the doped Cu2+ and Zn2+ ions could also play an important role in the catalytic process.

Dynamics of aqueous binary glass-formers confined in MCM-41.

PubMed

Elamin, Khalid; Jansson, Helén; Swenson, Jan

2015-05-21

Dielectric permittivity measurements were performed on water solutions of propylene glycol (PG) and propylene glycol monomethyl ether (PGME) confined in 21 Å pores of the silica matrix MCM-41 C10 in wide frequency (10(-2)-10(6) Hz) and temperature (130-250 K) ranges. The aim was to elucidate how the formation of large hydrogen bonded structural entities, found in bulk solutions of PGME, was affected by the confined geometry, and to make comparisons with the dynamic behavior of the PG-water system. For all solutions the measurements revealed four almost concentration independent relaxation processes. The intensity of the fastest process is low compared to the other relaxation processes and might be caused by both hydroxyl groups of the pore surfaces and by local motions of water and solute molecules. The second fastest process contains contributions from both the main water relaxation as well as the intrinsic β-relaxation of the solute molecules. The third fastest process is the viscosity related α-relaxation. Its concentration independency is very different compared to the findings for the corresponding bulk systems, particularly for the PGME-water system. The experimental data suggests that the surface interactions induce a micro-phase separation of the two liquids, resulting in a full molecular layer of water molecules coordinating to the hydrophilic hydroxyl groups on the surfaces of the silica pores. This, in turn, increases the geometrical confinement effect for the remaining solution even more and prevents the building up of the same type of larger structural entities in the PGME-water system as in the corresponding bulk solutions. The slowest process is mainly hidden in the high conductivity contribution at low frequencies, but its temperature dependence can be extracted for the PGME-water system. However, its origin is not fully clear, as will be discussed.

Physical and Hydraulic Properties at Recently Burned and Long-Unburned Boreal Forest Areas in Interior Alaska, USA

NASA Astrophysics Data System (ADS)

Ebel, B. A.; Koch, J. C.; Walvoord, M. A.

2017-12-01

Boreal forest regions in interior Alaska, USA are subject to recurring wildfire disturbance and climate shifts. These "press" and "pulse" disturbances impact water, solute, carbon, and energy fluxes, with feedbacks and consequences that are not adequately characterized. The NASA Arctic Boreal Vulnerability Experiment (ABoVE) seeks to understand susceptibility to disturbance in boreal regions. Subsurface physical and hydraulic properties are among the largest uncertainties in cryohydrogeologic modeling aiming to predict impacts of disturbance in Arctic and boreal regions. We address this research gap by characterizing physical and hydraulic properties of soil across a gradient of sites covering disparate soil textures and wildfire disturbance in interior Alaska. Samples were collected in the field within the domain of the NASA ABoVE project and analyzed in the laboratory. Physical properties measured include soil organic matter fraction, soil-particle size distribution, dry bulk density, and saturated soil-water content. Hydraulic properties measured include soil-water retention and field-saturated hydraulic conductivity using tension infiltrometers (-1 cm applied pressure head). The physical and hydraulic properties provide the foundation for site conceptual model development, cryohydrogeologic model parameterization, and integration with geophysical data. This foundation contributes to the NASA ABoVE objectives of understanding the underlying physical processes that control vulnerability in Arctic and Boreal landscapes.

Synthesis of highly elastic biocompatible polyurethanes based on bio-based isosorbide and poly(tetramethylene glycol) and their properties.

PubMed

Kim, Hyo-Jin; Kang, Min-Sil; Knowles, Jonathan C; Gong, Myoung-Seon

2014-09-01

Bio-based high elastic polyurethanes were prepared from hexamethylene diisocyanate and various ratios of isosorbide to poly(tetramethylene glycol) as a diol by a simple one-shot bulk polymerization without a catalyst. Successful synthesis of the polyurethanes was confirmed by Fourier transform-infrared spectroscopy and (1)H nuclear magnetic resonance. Thermal properties were determined by differential scanning calorimetry and thermogravimetric analysis. The glass transition temperature was -47.8℃. The test results showed that the poly(tetramethylene glycol)/isosorbide-based elastomer exhibited not only excellent stress-strain properties but also superior resilience to the existing polyether-based polyurethane elastomers. The static and dynamic properties of the polyether/isosorbide-based thermoplastic elastomer were more suitable for dynamic applications. Moreover, such rigid diols impart biocompatible and bioactive properties to thermoplastic polyurethane elastomers. Degradation tests performed at 37℃ in phosphate buffer solution showed a mass loss of 4-9% after 8 weeks, except for the polyurethane with the lowest isosorbide content, which showed an initial rapid weight loss. These polyurethanes offer significant promise due to soft, flexible and biocompatible properties for soft tissue augmentation and regeneration. © The Author(s) 2014 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

Aerosol Particle Interfacial Thermodynamics and Phase Partitioning Measurements Using Biphasic Microfluidics

NASA Astrophysics Data System (ADS)

Dutcher, Cari; Metcalf, Andrew

2015-03-01

Secondary organic aerosol particles are nearly ubiquitous in the atmosphere and yet there remain large uncertainties in their formation processes and ambient properties. These particles are complex microenvironments, which can contain multiple interfaces due to internal aqueous-organic phase partitioning and to the external liquid-vapor surface. Interfacial properties affect the ambient aerosol morphology, or internal structure of the particle, which in turn can affect the way a particle interacts with an environment of condensable clusters and organic vapors. To improve our ability to accurately predict ambient aerosol morphology, we must improve our knowledge of aerosol interfaces and their interactions with the ambient environment. Unfortunately, many techniques employed to measure interfacial properties do so in bulk solutions or in the presence of a ternary (e.g. solid) phase. In this talk, a novel method using biphasic microscale flows will be introduced for generating, trapping, and perturbing complex interfaces at atmospherically relevant conditions. These microfluidic experiments utilize high-speed imaging to monitor interfacial phenomena at the microscale and are performed with phase contrast and fluorescence microscopy on a temperature-controlled inverted microscope stage. From these experiments, interfacial thermodynamic properties such as surface or interfacial tension, rheological properties such as interfacial moduli, and kinetic properties such as mass transfer coefficients can be measured or inferred.

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

Bunkin, N F; Shkirin, A V; Burkhanov, I S

Aqueous NaCl solutions with different concentrations have been investigated by dynamic scattering of laser radiation. It is experimentally shown that these solutions contain scattering particles with a wide size distribution in a range of ∼10 – 100 nm. The experimental results indirectly confirm the existence of quasi-stable gas nanobubbles in the bulk of aqueous ionic solutions. (light scattering)

Relationship of the Levitation Force Between Single and Multiple YBCO Bulks Above a Permanent Magnet Guideway Operating Dive-Lift Movement with Different Angles

NASA Astrophysics Data System (ADS)

Zeng, R.; Wang, S. Y.; Liao, X. L.; Deng, Z. G.; Wang, J. S.

2013-04-01

In practical applications, the acceleration and deceleration motions inevitably happen in the operation of high temperature superconducting (HTS) maglev trains. For further research of the maglev properties of YBaCuO bulk above a permanent magnet guideway (PMG), by moving a fixed vertical distance, this paper studies the relationship of the levitation force between single and multiple YBCO bulks above a PMG operating dive-lift movement with different angles. Experimental results show that the maximal levitation force increment of two bulks than one bulk is smaller than the maximal levitation force increment of three bulks than two bulks. With the degree decreasing, the maximal levitation force increment of three bulks is bigger than the maximal levitation force increment of two bulks and one bulk, and the hysteresis loop of the levitation force of the three-bulk arrangement is getting smaller.

Interstitial solute transport in 3D reconstructed neuropil occurs by diffusion rather than bulk flow.

PubMed

Holter, Karl Erik; Kehlet, Benjamin; Devor, Anna; Sejnowski, Terrence J; Dale, Anders M; Omholt, Stig W; Ottersen, Ole Petter; Nagelhus, Erlend Arnulf; Mardal, Kent-André; Pettersen, Klas H

2017-09-12

The brain lacks lymph vessels and must rely on other mechanisms for clearance of waste products, including amyloid [Formula: see text] that may form pathological aggregates if not effectively cleared. It has been proposed that flow of interstitial fluid through the brain's interstitial space provides a mechanism for waste clearance. Here we compute the permeability and simulate pressure-mediated bulk flow through 3D electron microscope (EM) reconstructions of interstitial space. The space was divided into sheets (i.e., space between two parallel membranes) and tunnels (where three or more membranes meet). Simulation results indicate that even for larger extracellular volume fractions than what is reported for sleep and for geometries with a high tunnel volume fraction, the permeability was too low to allow for any substantial bulk flow at physiological hydrostatic pressure gradients. For two different geometries with the same extracellular volume fraction the geometry with the most tunnel volume had [Formula: see text] higher permeability, but the bulk flow was still insignificant. These simulation results suggest that even large molecule solutes would be more easily cleared from the brain interstitium by diffusion than by bulk flow. Thus, diffusion within the interstitial space combined with advection along vessels is likely to substitute for the lymphatic drainage system in other organs.

Hydrothermal replacement of biogenic and abiogenic aragonite by Mg-carbonates - Relation between textural control on effective element fluxes and resulting carbonate phase

NASA Astrophysics Data System (ADS)

Jonas, Laura; Müller, Thomas; Dohmen, Ralf; Immenhauser, Adrian; Putlitz, Benita

2017-01-01

Dolomitization, i.e., the secondary replacement of calcite or aragonite (CaCO3) by dolomite (CaMg[CO3]2), is one of the most volumetrically important carbonate diagenetic processes. It occurs under near surface and shallow burial conditions and can significantly modify rock properties through changes in porosity and permeability. Dolomitization fronts are directly coupled to fluid pathways, which may be related to the initial porosity/permeability of the precursor limestone, an existing fault network or secondary porosity/permeability created through the replacement reaction. In this study, the textural control on the replacement of biogenic and abiogenic aragonite by Mg-carbonates, that are typical precursor phases in the dolomitization process, was experimentally studied under hydrothermal conditions. Aragonite samples with different textural and microstructural properties exhibiting a compact (inorganic aragonite single crystal), an intermediate (bivalve shell of Arctica islandica) and open porous structure (skeleton of coral Porites sp.) were reacted with a solution of 0.9 M MgCl2 and 0.015 M SrCl2 at 200 °C. The replacement of aragonite by a Ca-bearing magnesite and a Mg-Ca carbonate of non-stoichiometric dolomitic composition takes place via a dissolution-precipitation process and leads to the formation of a porous reaction front that progressively replaces the aragonite precursor. The reaction leads to the development of porosity within the reaction front and distinctive microstructures such as gaps and cavities at the reaction interface. The newly formed reaction rim consists of chemically distinct phases separated by sharp boundaries. It was found that the number of phases and their chemical variation decreases with increasing initial porosity and reactive surface area. This observation is explained by variations in effective element fluxes that result in differential chemical gradients in the fluid within the pore space of the reaction rim. Observed reaction rates are highest for the replacement of the initially highly porous coral and lowest for the compact structure of a single aragonite crystal. Therefore, the reaction progress equally depends on effective element fluxes between the fluid at the reaction interface and the bulk solution surrounding the test material as well as the reactive surface area. This study demonstrates that the textural and microstructural properties of the parent material have a significant influence on the chemical composition of the product phase. Moreover, our data highlight the importance of effective fluid-mediated element exchange between the fluid at the reaction interface and the bulk solution controlled by the local microstructure.

Hydration water and bulk water in proteins have distinct properties in radial distributions calculated from 105 atomic resolution crystal structures.

PubMed

Chen, Xianfeng; Weber, Irene; Harrison, Robert W

2008-09-25

Water plays a critical role in the structure and function of proteins, although the experimental properties of water around protein structures are not well understood. The water can be classified by the separation from the protein surface into bulk water and hydration water. Hydration water interacts closely with the protein and contributes to protein folding, stability, and dynamics, as well as interacting with the bulk water. Water potential functions are often parametrized to fit bulk water properties because of the limited experimental data for hydration water. Therefore, the structural and energetic properties of the hydration water were assessed for 105 atomic resolution (

Doping induced carrier and band-gap modulation in bulk versus nano for topological insulators: A test case of Stibnite

NASA Astrophysics Data System (ADS)

Maji, Tuhin Kumar; Pal, Samir Kumar; Karmakar, Debjani

2018-04-01

We aim at comparing the electronic properties of topological insulator Sb2S3 in bulk and Nanorod using density-functional scheme and investigating the effects of Se-doping at chalcogen-site. While going from bulk to nano, there is a drastic change in the band gap due to surface-induced strain. However, the trend of band gap modulation with increased Se doping is more prominent in bulk. Interestingly, Se-doping introduces different type of carriers in bulk and nano.

Solution-Processed Cu2Se Nanocrystal Films with Bulk-Like Thermoelectric Performance.

PubMed

Forster, Jason D; Lynch, Jared J; Coates, Nelson E; Liu, Jun; Jang, Hyejin; Zaia, Edmond; Gordon, Madeleine P; Szybowski, Maxime; Sahu, Ayaskanta; Cahill, David G; Urban, Jeffrey J

2017-06-05

Thermoelectric power generation can play a key role in a sustainable energy future by converting waste heat from power plants and other industrial processes into usable electrical power. Current thermoelectric devices, however, require energy intensive manufacturing processes such as alloying and spark plasma sintering. Here, we describe the fabrication of a p-type thermoelectric material, copper selenide (Cu 2 Se), utilizing solution-processing and thermal annealing to produce a thin film that achieves a figure of merit, ZT, which is as high as its traditionally processed counterpart, a value of 0.14 at room temperature. This is the first report of a fully solution-processed nanomaterial achieving performance equivalent to its bulk form and represents a general strategy to reduce the energy required to manufacture advanced energy conversion and harvesting materials.

Evaluation of Enzymatically Modified Soy Protein Isolate Film Forming Solution and Film at Different Manufacturing Conditions.

PubMed

Mohammad Zadeh, Elham; O'Keefe, Sean F; Kim, Young-Teck; Cho, Jin-Hun

2018-04-01

The effects of transglutaminase on soy protein isolate (SPI) film forming solution and films were investigated by rheological behavior and physicochemical properties based on different manufacturing conditions (enzyme treatments, enzyme incubation times, and protein denaturation temperatures). Enzymatic crosslinking reaction and changes in molecular weight distribution were confirmed by viscosity measurement and SDS-PAGE, respectively, compared to 2 controls: the nonenzyme treated and the deactivated enzyme treated. Films treated with both the enzyme and the deactivated enzyme showed significant increase in tensile strength (TS), percent elongation (%E), and initial contact angle of films compared to the nonenzyme control film due to the bulk stabilizers in the commercial enzyme. Water absorption property, protein solubility, Fourier transform infrared (FTIR) and X-ray diffraction (XRD) spectroscopy revealed that enzyme treated SPI film matrix in the molecular structure level, resulted in the changes in physicochemical properties. Based on our observation, the enzymatic treatment at appropriate conditions is a practical and feasible way to control the physical properties of protein based biopolymeric film for many different scientific and industrial areas. Enzymes can make bridges selectively among different amino acids in the structure of protein matrix. Therefore, protein network is changed after enzyme treatment. The behavior of biopolymeric materials is dependent on the network structure to be suitable in different applications such as bioplastics applied in food and pharmaceutical products. In the current research, transglutaminase, as an enzyme, applied in soy protein matrix in different types of forms, activated and deactivated, and different preparation conditions to investigate its effects on different properties of the new bioplastic film. © 2018 Institute of Food Technologists®.

A bulk superconducting MgB 2 cylinder for holding transversely polarized targets

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

Statera, M.; Balossino, I.; Barion, L.

An innovative solution is being pursued for the challenging magnetic problem of producing an internal transverse field around a polarized target, while shielding out an external longitudinal field from a detector. A hollow bulk superconductor can trap a transverse field that is present when cooled through its transition temperature, and also shield its interior from any subsequent field changes. Here, a feasibility study with a prototype bulk MgB 2 superconducting cylinder is described. Promising measurements taken of the interior field retention and exterior field exclusion, together with the corresponding long-term stability performance, are reported. In the context of an electronmore » scattering experiment, such a solution minimizes beam deflection and the energy loss of reaction products, while also eliminating the heat load to the target cryostat from current leads that would be used with conventional electromagnets.« less

A bulk superconducting MgB 2 cylinder for holding transversely polarized targets

DOE PAGES

Statera, M.; Balossino, I.; Barion, L.; ...

2017-11-06

An innovative solution is being pursued for the challenging magnetic problem of producing an internal transverse field around a polarized target, while shielding out an external longitudinal field from a detector. A hollow bulk superconductor can trap a transverse field that is present when cooled through its transition temperature, and also shield its interior from any subsequent field changes. Here, a feasibility study with a prototype bulk MgB 2 superconducting cylinder is described. Promising measurements taken of the interior field retention and exterior field exclusion, together with the corresponding long-term stability performance, are reported. In the context of an electronmore » scattering experiment, such a solution minimizes beam deflection and the energy loss of reaction products, while also eliminating the heat load to the target cryostat from current leads that would be used with conventional electromagnets.« less

Multichannel Boron Doped Nanocrystalline Diamond Ultramicroelectrode Arrays: Design, Fabrication and Characterization

PubMed Central

Kiran, Raphael; Rousseau, Lionel; Lissorgues, Gaëlle; Scorsone, Emmanuel; Bongrain, Alexandre; Yvert, Blaise; Picaud, Serge; Mailley, Pascal; Bergonzo, Philippe

2012-01-01

We report on the fabrication and characterization of an 8 × 8 multichannel Boron Doped Diamond (BDD) ultramicro-electrode array (UMEA). The device combines both the assets of microelectrodes, resulting from conditions in mass transport from the bulk solution toward the electrode, and of BDD's remarkable intrinsic electrochemical properties. The UMEAs were fabricated using an original approach relying on the selective growth of diamond over pre-processed 4 inches silicon substrates. The prepared UMEAs were characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results demonstrated that the electrodes have exhibited a very fast electrode transfer rate (k0) up to 0.05 cm·s−1 (in a fast redox couple) and on average, a steady state limiting current (in a 0.5 M potassium chloride aqueous solution containing 1 mM Fe(CN)64− ion at 100 mV·s−1) of 1.8 nA. The UMEAs are targeted for electrophysiological as well as analytical applications. PMID:22969367

p-Type CuRhO 2 as a Self-Healing Photoelectrode for Water Reduction under Visible Light

DOE PAGES

Gu, Jing; Krizan, Jason W.; Gibson, Quinn D.; ...

2013-12-30

Polycrystalline CuRhO 2 is investigated as a photocathode for the splitting of water under visible irradiation. The band edge positions of this material straddle the water oxidation and reduction redox potentials. Thus, photogenerated conduction band electrons are sufficiently energetic to reduce water, while the associated valence band holes are energetically able to oxidize water to O 2. Under visible illumination, H 2 production is observed with ~0.2 V underpotential in an air-saturated solution. In contrast, H 2 production in an Ar-saturated solution was found to be unstable. This instability is associated with the reduction of the semiconductor forming Cu(s). However,more » in the presence of air or O 2, bulk Cu(s) was not detected, implying that CuRhO 2 is self-healing when air is present. Here, this property allows for the stable formation of H 2 with ca. 80% Faradaic efficiency.« less

p-Type CuRhO 2 as a Self-Healing Photoelectrode for Water Reduction under Visible Light

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

Gu, Jing; Krizan, Jason W.; Gibson, Quinn D.

Polycrystalline CuRhO 2 is investigated as a photocathode for the splitting of water under visible irradiation. The band edge positions of this material straddle the water oxidation and reduction redox potentials. Thus, photogenerated conduction band electrons are sufficiently energetic to reduce water, while the associated valence band holes are energetically able to oxidize water to O 2. Under visible illumination, H 2 production is observed with ~0.2 V underpotential in an air-saturated solution. In contrast, H 2 production in an Ar-saturated solution was found to be unstable. This instability is associated with the reduction of the semiconductor forming Cu(s). However,more » in the presence of air or O 2, bulk Cu(s) was not detected, implying that CuRhO 2 is self-healing when air is present. Here, this property allows for the stable formation of H 2 with ca. 80% Faradaic efficiency.« less

Corrosion Behavior and Microstructure Influence of Glass-Ceramic Nuclear Waste Forms

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

Matthew Asmussen, R.; Neeway, James J.; Kaspar, Tiffany C.

Glass ceramic waste forms present a potentially viable technology for the long term immobilization and disposal of liquid nuclear wastes. Through control of chemistry during fabrication, such waste forms can have designed secondary crystalline phases within a borosilicate glass matrix. In this work, a glass ceramic containing powellite and oxyapatite secondary phases was tested for its corrosion properties in dilute conditions using single pass flow through testing (SPFT). Three glass ceramic samples were prepared using different cooling rates to produce samples with varying microstructure sizes. In testing at 90 °C in buffered pH 7 and pH 9 solutions, it wasmore » found that increasing pH and decreasing microstructure size (resulting from rapid cooling during fabrication) both led to a reduction in overall corrosion rate. The phases of the glass ceramic were found, using a combination of solutions analysis, SEM and AFM, to corrode preferably in the order of powellite > bulk glass matrix > oxyapatite.« less

Restoration with pioneer plants changes soil properties and remodels the diversity and structure of bacterial communities in rhizosphere and bulk soil of copper mine tailings in Jiangxi Province, China.

PubMed

Sun, Xiaoyan; Zhou, Yanling; Tan, Yinjing; Wu, Zhaoxiang; Lu, Ping; Zhang, Guohua; Yu, Faxin

2018-05-25

To unravel the ecological function played by pioneer plants in the practical restoration of mine tailings, it is vital to explore changes of soil characteristics and microbial communities in rhizosphere and bulk soil following the adaptation and survival of plants. In the present study, the diversity and structure of rhizospheric bacterial communities of three pioneer plants in copper mine tailings were investigated by Illumina MiSeq sequencing, and the effects of pioneer plants on soil properties were also evaluated. Significant soil improvement was detected in rhizospheric samples, and Alnus cremastogyne showed higher total organic matter, total nitrogen, and available phosphorus than two other herbaceous plants. Microbial diversity indices in rhizosphere and bulk soil of reclaimed tailings were significantly higher than bare tailings, even the soil properties of bulk soil in reclaimed tailings were not significantly different from those of bare tailings. A detailed taxonomic composition analysis demonstrated that Alphaproteobacteria and Deltaproteobacteria, Chloroflexi, Acidobacteria, and Gemmatimonadetes showed significantly higher relative abundance in rhizosphere and bulk soil. In contrast, Gammaproteobacteria and Firmicutes were abundant in bare tailings, in which Bacillus, Pseudomonas, and Lactococcus made up the majority of the bacterial community (63.04%). Many species within known heavy metal resistance and nutrient regulatory microorganism were identified in reclaimed tailings, and were more abundant among rhizospheric microbes. Hierarchical clustering and principal coordinate analysis (PCoA) analysis demonstrated that the bacterial profiles in the rhizosphere clustered strictly together according to plant types, and were distinguishable from bulk soil. However, we also identified a large shared OTUs that occurred repeatedly and was unaffected by highly diverse soil properties in rhizosphere and bulk samples. Redundancy analysis indicated that water content and Cu and As concentrations were the main environmental regulators of microbial composition. These results suggest that the interactive effect of pioneer plants and harsh soil environmental conditions remodel the specific bacterial communities in rhizosphere and bulk soil in mine tailings. And A. cremastogyne might be approximate candidate for phytoremediation of mine tailings for better soil amelioration effect and relative higher diversity of bacterial community in rhizosphere.

Immediate impact on the rim zone of cement based materials due to chemical attack

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

Schwotzer, M., E-mail: matthias.schwotzer@kit.edu; Scherer, T.; Gerdes, A.

2015-01-15

Cement based materials are in their widespread application fields exposed to various aqueous environments. This can lead to serious chemical changes affecting the durability of the materials. In particular in the context of service life prediction a detailed knowledge of the reaction mechanisms is a necessary base for the evaluation of the aggressivity of an aqueous medium and this is deduced commonly from long term investigations. However, these processes start immediately at the material/water-interface, when a cementitious system comes into contact with an aqueous solution, altering here the chemical composition and microstructure. This rim zone represents the first hurdle thatmore » has to be overcome by an attacking aqueous solution. Therefore, the properties of the surface near area should be closely associated with the further course of deterioration processes by reactive transport. In this context short term exposure experiments with hardened cement paste over 4 and 48 h have been carried out with demineralized water, hard tap water and different sulfate solutions. In order to investigate immediate changes in the near-surface region, depth profile cuts have been performed on the cement paste samples by means of focused ion beam preparation techniques. A scanning beam of Gallium ions is applied to cut a sharp edge in the cement paste surface, providing insights into the composition and microstructure of the upper ten to hundred microns. Electron microscopic investigations on such a section of the rim zone, together with surface sensitive X-ray diffraction accompanied by a detailed characterization of the bulk composition confirm that the properties of the material/water interface are of relevance for the durability of cement based systems in contact with aqueous solutions. In this manner, focused ion beam investigations constitute auspicious tools to contribute to a more sophisticated understanding of the reaction mechanisms. - Highlights: • The chemical stability is related to the properties of material/water interface. • Properties of the rim zone readjust quickly, triggered by hydrochemical conditions. • Durability research can be improved by combining FIB techniques and common analytics.« less

Laboratory studies of aqueous-phase oxidation of polyols in submicron particles

NASA Astrophysics Data System (ADS)

Daumit, K. E.; Carrasquillo, A. J.; Hunter, J. F.; Kroll, J. H.

2013-12-01

Aqueous-phase oxidation has received recent attention as a potential pathway for the formation of highly oxidized organic aerosol. However most aqueous oxidation studies are performed in bulk solutions rather than aqueous droplets. Here we describe experiments in which aqueous oxidation is carried out within submicron particles, allowing for gas-particle partitioning of reactants, intermediates, and products. Using Fenton chemistry as a source of hydroxyl radicals, and a high-resolution aerosol mass spectrometer (AMS) for online characterization of particle composition, we find that aqueous oxidation can be quite rapid. The formation of high concentrations of oxalic acid is observed in the particle phase with some loss of carbon to the gas phase, indicating the formation of volatile products. We see a rapid degradation of condensed-phase oxidation products upon exposure to ultraviolet lights (centered at 350 nm) suggesting that these products may exist as iron(III)-oxalate complexes. Similar results are also seen when oxidation is carried out in bulk solution (with AMS analysis of the atomized solution); however in some cases the mass loss is less than is observed for submicron particles, likely due to differences in partitioning of early-generation products. Such products can partition out of the aqueous phase at the low liquid water contents in the chamber but remain in solution for further aqueous processing in bulk oxidation experiments. This work suggests that the product distributions from oxidation in aqueous aerosol may be substantially different than those in bulk oxidation, pointing to the need to carry out aqueous oxidation studies under atmospherically relevant partitioning conditions (with liquid water contents mimicking those of cloud droplets or wet aerosol).

Gd Ba Cu O bulk superconductors fabricated by a seeded infiltration growth technique under reduced oxygen partial pressure

NASA Astrophysics Data System (ADS)

Iida, K.; Babu, N. H.; Shi, Y. H.; Cardwell, D. A.; Murakami, M.

2006-06-01

Single-grain Gd-Ba-Cu-O (GdBCO) bulk superconductors have been grown by a seeded infiltration and growth (SIG) technique under a 1% O2+N2 atmosphere using a generic MgO-doped Nd-Ba-Cu-O (MgO-NdBCO) seed placed on the sample surface at room temperature (the so-called the cold-seeding method). Partial melting of the MgO-NdBCO seeds fabricated in air under notionally identical thermal processing conditions, however, limited the reliability of this bulk GdBCO single-grain process. The observed seed decomposition is attributed to the dependence of the peritectic temperature Tp of MgO-doped Nd1+xBa2-xCu3Oy solid solution (MgO-doped Nd-123ss, where ss indicates solid solution) compounds on both oxygen partial pressure during the melt process and the level of solid solution (x). The peritectic decomposition temperature of MgO-doped Nd-123ss, with x ranging from 0 to 0.5 under p(O2) = 1.00 atm, was observed to remain constant at 1120 °C. Tp was observed to decrease linearly as a function of solid solution level, on the other hand, under oxygen partial pressures of both p(O2) = 0.21 and 0.01 atm. Based on these results, MgO-doped NdBCO seed crystals should be grown under reduced oxygen partial pressure in order to obtain a stable MgO-doped NdBCO seed crystal suitable for cold-seeding processes of large-grain (RE)BCO bulk superconductors (where RE is a rare earth element).

Structure and dynamics of water in mixed solutions including laponite and PEO

NASA Astrophysics Data System (ADS)

Morikubo, Satoshi; Sekine, Yurina; Ikeda-Fukazawa, Tomoko

2011-01-01

To investigate the structure and dynamics of water in mixed solutions including laponite clay particles and poly(ethylene oxide) (PEO), we measured the Raman spectra of the mixed solutions in the temperature range 283-313 K. The results show that the vibrational energies of the O-H stretching modes in the mixed solutions depend on the water content and temperature. The energy shifts of the O-H stretching modes are attributed to changes in the water structure. By applying a structural model of bulk water to the spectra in the O-H stretching region, the local structures of water in the solutions were analyzed. The result shows that the formation probability of hydrogen bonds in the solutions decreases as the water content decreases. Laponite and PEO have effects to disrupt the network structure of hydrogen bonds between water molecules. Further, it was found that laponite and PEO cause increase in the strength of hydrogen bonds of surrounding water,although the strength of the hydrogen bonds increases with the order water-laponite < water-water < water-PEO. It is concluded that water in laponite-PEO mixed solutions has a less-networked structure with strong hydrogen bonds compared with bulk water.

Scalable Routes to Efficient Thermoelectric Materials

NASA Astrophysics Data System (ADS)

Feser, Joseph Patrick

Thermoelectrics are solid-state materials with the ability to directly convert heat to electricity and visa versa. Despite their advantages in power density and reliability, state-of-the-art bulk alloy materials have not been efficient enough or inexpensive enough to be deployed widely. Newer nanostructured materials show significantly improved efficiencies and could overcome these long-standing problems. This dissertation studies the conditions that govern efficiency improvements in nanostructured materials with particular attention paid to lattice thermal conductivity reductions as well as methods to make such materials inexpensively using solution processing. Measurements of a new p-type material system, In1-xGa xSb doped with epitaxially embedded metallic ErSb nanocrystals show that lattice thermal conductivity is reduced significantly below the alloy limit with as little as 1% nanocrystal loading by volume. Theoretical modeling based on the Boltzmann transport equation (BTE) is able to explain the reductions on the basis of an increased scattering cross section for long wavelength phonons which are scattered much less effectively by phonon-phonon and alloy impurity interactions. The optimal conditions for nanoparticle size, concentration, alloy composition are explored and the existence of an optimal nanocrystal size which depends on the alloy composition and temperature is predicted. A variety of colloidal nanocrystals are explored as inexpensive building blocks for nanostructured thermoelectric materials with tunable electronic and thermal properties. First, the electronic properties of superlattices of PbSe nanocrystals are studied in the limit of strong quantum confinement (d<10nm). PbSe quantum dot superlattices show size-dependent Seebeck coefficient which exceed that of the bulk material at equivalent carrier concentrations. Reversible control of the carrier concentration is shown by surface exposure of the superlattices to oxidizing and reducing agents and in-situ monitoring of the thermopower. Next, phonon transport in ultra-fine grained nanocomposites with tunable grain size are studied using colloidal nanocrystals. Particles of CdSe are coated with a hydrazine-based metal chalcogenide ligand which serves as a functional "glue." Composites with grain size between 3nm-6nm display ultra-low thermal conductivity approaching the theoretical limit for a crystalline solid, nearly 30 times lower than the bulk compound. Modeling shows that boundary scattering in the framework of BTE cannot adequately explain the measured properties and alternative mechanisms are discussed. Finally, a solution processable route to Bi2Te3-xSex thermoelectrics is developed by reacting Bi2S3 in hydrazine to form a universal precursor. The precursor is spin-coated in the presence of excess Se and Te and annealed to form a thermoelectrics material with a maximum ZT˜0.4 at room temperature, which is the highest for any spin-coated material currently reported.

Corrosion and wear properties of laser surface modified NiTi with Mo and ZrO 2

NASA Astrophysics Data System (ADS)

Ng, K. W.; Man, H. C.; Yue, T. M.

2008-08-01

Because of its biocompatibility, superelasticity and shape memory characteristics, NiTi alloys have been gaining immense interest in the medical field. However, there is still concern on the corrosion resistance of this alloy if it is going to be implanted in the human body for a long time. Titanium is not toxic but nickel is carcinogenic and is implicated in various reactions including allergic response and degeneration of muscle tissue. Debris from wear and the subsequent release of Ni + ions due to corrosion in the body system are fatal issues for long-term application of this alloy in the human body. This paper reports the corrosion and wear properties of laser surface modified NiTi using Mo and ZrO 2 as surface alloying elements, respectively. The modified layers which are free from microcracks and porosity, act as both physical barrier to nickel release and enhance the bulk properties, such as hardness, wear resistance, and corrosion resistance. The electrochemical performance of the surface modified alloy was studied in Hanks' solution. Electrochemical impedance spectroscopy was measured.

Electroactive Nanoporous Metal Oxides and Chalcogenides by Chemical Design

PubMed Central

2017-01-01

The archetypal silica- and aluminosilicate-based zeolite-type materials are renowned for wide-ranging applications in heterogeneous catalysis, gas-separation and ion-exchange. Their compositional space can be expanded to include nanoporous metal chalcogenides, exemplified by germanium and tin sulfides and selenides. By comparison with the properties of bulk metal dichalcogenides and their 2D derivatives, these open-framework analogues may be viewed as three-dimensional semiconductors filled with nanometer voids. Applications exist in a range of molecule size and shape discriminating devices. However, what is the electronic structure of nanoporous metal chalcogenides? Herein, materials modeling is used to describe the properties of a homologous series of nanoporous metal chalcogenides denoted np-MX2, where M = Si, Ge, Sn, Pb, and X = O, S, Se, Te, with Sodalite, LTA and aluminum chromium phosphate-1 structure types. Depending on the choice of metal and anion their properties can be tuned from insulators to semiconductors to metals with additional modification achieved through doping, solid solutions, and inclusion (with fullerene, quantum dots, and hole transport materials). These systems form the basis of a new branch of semiconductor nanochemistry in three dimensions. PMID:28572706

Elasticity of Deep-Earth Materials at High P and T: Implication for Earths Lower Mantle

NASA Astrophysics Data System (ADS)

Bass, Jay; Sinogeikin, S. V.; Mattern, Estelle; Jackson, J. M.; Matas, J.; Wang, J.; Ricard, Y.

2005-03-01

Brillouin spectroscopy allows measurements of sound velocities and elasticity on phases of geophysical interest at high Pressures and Temperatures. This technique was used to measure the properties of numerous important phases of Earths deep interior. Emphasis is now on measurements at elevated P-T conditions, and measurements on dense polycrystals. Measurements to 60 GPa were made using diamond anvil cells. High temperature is achieved by electrical resistance and laser heating. Excellent results are obtained for polycrystalline samples of dense oxides such as silicate spinels, and (Mg,Al)(Si,Al)O3 --perovskites. A wide range of materials can now be characterized. These and other results were used to infer Earths average lower mantle composition and thermal structure by comparing mineral properties at lower mantle P-T conditions to global Earth models. A formal inversion procedure was used. Inversions of density and bulk sound velocity do not provide robust compositional and thermal models. Including shear properties in the inversions is important to obtain unique solutions. We discuss the range of models consistent with present lab results, and data needed to further refine lower mantle models.

Evidence for anisotropic dielectric properties of monoclinic hafnia using valence electron energy-loss spectroscopy in high-resolution transmission electron microscopy and ab initio time-dependent density-functional theory

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

Guedj, C.; CEA, LETI, MINATEC Campus, F-38054 Grenoble; Hung, L.

2014-12-01

The effect of nanocrystal orientation on the energy loss spectra of monoclinic hafnia (m-HfO{sub 2}) is measured by high resolution transmission electron microscopy (HRTEM) and valence energy loss spectroscopy (VEELS) on high quality samples. For the same momentum-transfer directions, the dielectric properties are also calculated ab initio by time-dependent density-functional theory (TDDFT). Experiments and simulations evidence anisotropy in the dielectric properties of m-HfO{sub 2}, most notably with the direction-dependent oscillator strength of the main bulk plasmon. The anisotropic nature of m-HfO{sub 2} may contribute to the differences among VEELS spectra reported in literature. The good agreement between the complex dielectricmore » permittivity extracted from VEELS with nanometer spatial resolution, TDDFT modeling, and past literature demonstrates that the present HRTEM-VEELS device-oriented methodology is a possible solution to the difficult nanocharacterization challenges given in the International Technology Roadmap for Semiconductors.« less

Osmotic Pressure in Ionic Microgel Dispersions

NASA Astrophysics Data System (ADS)

Denton, Alan R.; Tang, Qiyun

2015-03-01

Microgels are microscopic gel particles, typically 10-1000 nm in size, that are swollen by a solvent. Hollow microgels (microcapsules) can encapsulate cargo, such as dye molecules or drugs, in their solvent-filled cavities. Their sensitive response to environmental conditions (e.g., temperature, pH) and influence on flow properties suit microgels to widespread applications in the chemical, pharmaceutical, food, and consumer care industries. When dispersed in water, polyelectrolyte gels become charged through dissociation of counterions. The electrostatic contribution to the osmotic pressure inside and outside of ionic microgels influences particle swelling and bulk materials properties, including thermodynamic, structural, optical, and rheological properties. Within the primitive and cell models of polyelectrolyte solutions, we derive an exact statistical mechanical formula for the contribution of mobile microions to the osmotic pressure within ionic microgels. Using Poisson-Boltzmann theory, we validate this result by explicitly calculating ion distributions across the surface of an ionic microgel and the electrostatic contribution to the osmotic pressure. Within a coarse-grained one-component model, we further chart the limits of the cell model for salty dispersions. This work was supported by the National Science Foundation under Grant No. DMR-1106331.

A simple and effective solution to the constrained QM/MM simulations

NASA Astrophysics Data System (ADS)

Takahashi, Hideaki; Kambe, Hiroyuki; Morita, Akihiro

2018-04-01

It is a promising extension of the quantum mechanical/molecular mechanical (QM/MM) approach to incorporate the solvent molecules surrounding the QM solute into the QM region to ensure the adequate description of the electronic polarization of the solute. However, the solvent molecules in the QM region inevitably diffuse into the MM bulk during the QM/MM simulation. In this article, we developed a simple and efficient method, referred to as the "boundary constraint with correction (BCC)," to prevent the diffusion of the solvent water molecules by means of a constraint potential. The point of the BCC method is to compensate the error in a statistical property due to the bias potential by adding a correction term obtained through a set of QM/MM simulations. The BCC method is designed so that the effect of the bias potential completely vanishes when the QM solvent is identical with the MM solvent. Furthermore, the desirable conditions, that is, the continuities of energy and force and the conservations of energy and momentum, are fulfilled in principle. We applied the QM/MM-BCC method to a hydronium ion(H3O+) in aqueous solution to construct the radial distribution function (RDF) of the solvent around the solute. It was demonstrated that the correction term fairly compensated the error and led the RDF in good agreement with the result given by an ab initio molecular dynamics simulation.

Effect of energy equation in one control-volume bulk-flow model for the prediction of labyrinth seal dynamic coefficients

NASA Astrophysics Data System (ADS)

Cangioli, Filippo; Pennacchi, Paolo; Vannini, Giuseppe; Ciuchicchi, Lorenzo

2018-01-01

The influence of sealing components on the rotordynamic stability of turbomachinery has become a key topic because the oil and gas market is increasingly demanding high rotational speeds and high efficiency. This leads the turbomachinery manufacturers to design higher flexibility ratios and to reduce the clearance of the seals. Accurate prediction of the effective damping of seals is critical to avoid instability problems; in recent years, "negative-swirl" swirl brakes have been used to reverse the circumferential direction of the inlet flow, which changes the sign of the cross-coupled stiffness coefficients and generates stabilizing forces. Experimental tests for a teeth-on-stator labyrinth seal were performed by manufacturers with positive and negative pre-swirl values to investigate the pre-swirl effect on the cross-coupled stiffness coefficient. Those results are used as a benchmark in this paper. To analyse the rotor-fluid interaction in the seals, the bulk-flow numeric approach is more time efficient than computational fluid dynamics (CFD). Although the accuracy of the coefficients prediction in bulk-flow models is satisfactory for liquid phase application, the accuracy of the results strongly depends on the operating conditions in the case of the gas phase. In this paper, the authors propose an improvement in the state-of-the-art bulk-flow model by introducing the effect of the energy equation in the zeroth-order solution to better characterize real gas properties due to the enthalpy variation along the seal cavities. The consideration of the energy equation allows for a better estimation of the coefficients in the case of a negative pre-swirl ratio, therefore, it extend the prediction fidelity over a wide range of operating conditions. The numeric results are also compared to the state-of-the-art bulk-flow model, which highlights the improvement in the model.

Superconducting NbTiN thin films for superconducting radio frequency accelerator cavity applications

DOE PAGES

Burton, Matthew C.; Beebe, Melissa R.; Yang, Kaida; ...

2016-02-12

Current superconducting radio frequency technology, used in various particle accelerator facilities across the world, is reliant upon bulk niobium superconducting cavities. Due to technological advancements in the processing of bulk Nb cavities, the facilities have reached accelerating fields very close to a material-dependent limit, which is close to 50 MV/m for bulk Nb. One possible solution to improve upon this fundamental limitation was proposed a few years ago by Gurevich [Appl. Phys. Lett. 88, 012511 (2006)], consisting of the deposition of alternating thin layers of superconducting and insulating materials on the interior surface of the cavities. The use of type-IImore » superconductors with Tc > Tc Nb and H c > HcNb, (e.g., Nb 3Sn, NbN, or NbTiN) could potentially greatly reduce the surface resistance (Rs) and enhance the accelerating field, if the onset of vortex penetration is increased above Hc Nb, thus enabling higher field gradients. Although Nb 3Sn may prove superior, it is not clear that it can be grown as a suitable thin film for the proposed multilayer approach, since very high temperature is typically required for its growth, hindering achieving smooth interfaces and/or surfaces. On the other hand, since NbTiN has a smaller lower critical field (H c1) and higher critical temperature (T c) than Nb and increased conductivity compared to NbN, it is a promising candidate material for this new scheme. Here, the authors present experimental results correlating filmmicrostructure with superconducting properties on NbTiN thin film coupon samples while also comparing filmsgrown with targets of different stoichiometry. In conclusion, it is worth mentioning that the authors have achieved thin films with bulk-like lattice parameter and transition temperature while also achieving H c1 values larger than bulk for films thinner than their London penetration depths.« less

Evaluation of the grand-canonical partition function using expanded Wang-Landau simulations. III. Impact of combining rules on mixtures properties

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

Desgranges, Caroline; Delhommelle, Jerome

2014-03-14

Combining rules, such as the Lorentz-Berthelot rules, are routinely used to calculate the thermodynamic properties of mixtures using molecular simulations. Here we extend the expanded Wang-Landau simulation approach to determine the impact of the combining rules on the value of the partition function of binary systems, and, in turn, on the phase coexistence and thermodynamics of these mixtures. We study various types of mixtures, ranging from systems of rare gases to biologically and technologically relevant mixtures, such as water-urea and water-carbon dioxide. Comparing the simulation results to the experimental data on mixtures of rare gases allows us to rank themore » performance of combining rules. We find that the widely used Lorentz-Berthelot rules exhibit the largest deviations from the experimental data, both for the bulk and at coexistence, while the Kong and Waldman-Hagler provide much better alternatives. In particular, in the case of aqueous solutions of urea, we show that the use of the Lorentz-Berthelot rules has a strong impact on the Gibbs free energy of the solute, overshooting the value predicted by the Waldman-Hagler rules by 7%. This result emphasizes the importance of the combining rule for the determination of hydration free energies using molecular simulations.« less

Density functional study on the structural and thermodynamic properties of aqueous DNA-electrolyte solution in the framework of cell model.

PubMed

Wang, Ke; Yu, Yang-Xin; Gao, Guang-Hua

2008-05-14

A density functional theory (DFT) in the framework of cell model is proposed to calculate the structural and thermodynamic properties of aqueous DNA-electrolyte solution with finite DNA concentrations. The hard-sphere contribution to the excess Helmholtz energy functional is derived from the modified fundamental measure theory, and the electrostatic interaction is evaluated through a quadratic functional Taylor expansion around a uniform fluid. The electroneutrality in the cell leads to a variational equation with a constraint. Since the reference fluid is selected to be a bulk phase, the Lagrange multiplier proves to be the potential drop across the cell boundary (Donnan potential). The ion profiles and electrostatic potential profiles in the cell are calculated from the present DFT-cell model. Our DFT-cell model gives better prediction of ion profiles than the Poisson-Boltzmann (PB)- or modified PB-cell models when compared to the molecular simulation data. The effects of polyelectrolyte concentration, ion size, and added-salt concentration on the electrostatic potential difference between the DNA surface and the cell boundary are investigated. The expression of osmotic coefficient is derived from the general formula of grand potential. The osmotic coefficients predicted by the DFT are lower than the PB results and are closer to the simulation results and experimental data.

Effects of a type I antifreeze protein (AFP) on the melting of frozen AFP and AFP+solute aqueous solutions studied by NMR microimaging experiment.

PubMed

Ba, Yong; Mao, Yougang; Galdino, Luiz; Günsen, Zorigoo

2013-01-01

The effects of a type I AFP on the bulk melting of frozen AFP solutions and frozen AFP+solute solutions were studied through an NMR microimaging experiment. The solutes studied include sodium chloride and glucose and the amino acids alanine, threonine, arginine, and aspartic acid. We found that the AFP is able to induce the bulk melting of the frozen AFP solutions at temperatures lower than 0 °C and can also keep the ice melted at higher temperatures in the AFP+solute solutions than those in the corresponding solute solutions. The latter shows that the ice phases were in super-heated states in the frozen AFP+solute solutions. We have tried to understand the first experimental phenomenon via the recent theoretical prediction that type I AFP can induce the local melting of ice upon adsorption to ice surfaces. The latter experimental phenomenon was explained with the hypothesis that the adsorption of AFP to ice surfaces introduces a less hydrophilic water-AFP-ice interfacial region, which repels the ionic/hydrophilic solutes. Thus, this interfacial region formed an intermediate chemical potential layer between the water phase and the ice phase, which prevented the transfer of water from the ice phase to the water phase. We have also attempted to understand the significance of the observed melting phenomena to the survival of organisms that express AFPs over cold winters.

Mechanical improvement of metal reinforcement rings for a finite ring-shaped superconducting bulk

NASA Astrophysics Data System (ADS)

Huang, Chen-Guang; Zhou, You-He

2018-03-01

As a key technique, reinforcement of type-II superconducting bulks with metal rings can efficiently improve their mechanical properties to enhance the maximum trapped field. In this paper, we study the magnetostrictive and fracture behaviors of a finite superconducting ring bulk reinforced by three typical reinforcing structures composed of metal rings during the magnetizing process by means of the minimization of magnetic energy and the finite element method. After a field-dependent critical current density is adopted, the magnetostriction, pinning-induced stress, and crack tip stress intensity factor are calculated considering the demagnetization effects. The results show that the mechanical properties of the ring bulk are strongly dependent on the reinforcing structure and the material and geometrical parameters of the metal rings. Introducing the metal ring can significantly reduce the hoop stress, and the reduction effect by internal reinforcement is much improved relative to external reinforcement. By comparison, bilateral reinforcement seems to be the best candidate structure. Only when the metal rings have particular Young's modulus and radial thickness will they contribute to improve the mechanical properties the most. In addition, if an edge crack is pre-existing in the ring bulk, the presence of metal rings can effectively avoid crack propagation since it reduces the crack tip stress intensity factor by nearly one order of magnitude.

"Peak tracking chip" for label-free optical detection of bio-molecular interaction and bulk sensing.

PubMed

Bougot-Robin, Kristelle; Li, Shunbo; Zhang, Yinghua; Hsing, I-Ming; Benisty, Henri; Wen, Weijia

2012-10-21

A novel imaging method for bulk refractive index sensing or label-free bio-molecular interaction sensing is presented. This method is based on specially designed "Peak tracking chip" (PTC) involving "tracks" of adjacent resonant waveguide gratings (RWG) "micropads" with slowly evolving resonance position. Using a simple camera the spatial information robustly retrieves the diffraction efficiency, which in turn transduces either the refractive index of the liquids on the tracks or the effective thickness of an immobilized biological layer. Our intrinsically multiplex chip combines tunability and versatility advantages of dielectric guided wave biochips without the need of costly hyperspectral instrumentation. The current success of surface plasmon imaging techniques suggests that our chip proposal could leverage an untapped potential to routinely extend such techniques in a convenient and sturdy optical configuration toward, for instance for large analytes detection. PTC design and fabrication are discussed with challenging process to control micropads properties by varying their period (step of 2 nm) or their duty cycle through the groove width (steps of 4 nm). Through monochromatic imaging of our PTC, we present experimental demonstration of bulk index sensing on the range [1.33-1.47] and of surface biomolecule detection of molecular weight 30 kDa in aqueous solution using different surface densities. A sensitivity of the order of 10(-5) RIU for bulk detection and a sensitivity of the order of ∼10 pg mm(-2) for label-free surface detection are expected, therefore opening a large range of application of our chip based imaging technique. Exploiting and chip design, we expect as well our chip to open new direction for multispectral studies through imaging.

Temperature Dependent Electrical Properties of PZT Wafer

NASA Astrophysics Data System (ADS)

Basu, T.; Sen, S.; Seal, A.; Sen, A.

2016-04-01

The electrical and electromechanical properties of lead zirconate titanate (PZT) wafers were investigated and compared with PZT bulk. PZT wafers were prepared by tape casting technique. The transition temperature of both the PZT forms remained the same. The transition from an asymmetric to a symmetric shape was observed for PZT wafers at higher temperature. The piezoelectric coefficient (d 33) values obtained were 560 pc/N and 234 pc/N, and the electromechanical coupling coefficient (k p) values were 0.68 and 0.49 for bulk and wafer, respectively. The reduction in polarization after fatigue was only ~3% in case of PZT bulk and ~7% for PZT wafer.

Improvement of flow and bulk density of pharmaceutical powders using surface modification.

PubMed

Jallo, Laila J; Ghoroi, Chinmay; Gurumurthy, Lakxmi; Patel, Utsav; Davé, Rajesh N

2012-02-28

Improvement in flow and bulk density, the two most important properties that determine the ease with which pharmaceutical powders can be handled, stored and processed, is done through surface modification. A limited design of experiment was conducted to establish a standardized dry coating procedure that limits the extent of powder attrition, while providing the most consistent improvement in angle of repose (AOR). The magnetically assisted impaction coating (MAIC) was considered as a model dry-coater for pharmaceutical powders; ibuprofen, acetaminophen, and ascorbic acid. Dry coated drug powders were characterized by AOR, particle size as a function of dispersion pressure, particle size distribution, conditioned bulk density (CBD), Carr index (CI), flow function coefficient (FFC), cohesion coefficient using different instruments, including a shear cell in the Freeman FT4 powder rheometer, and Hansen flowability index. Substantial improvement was observed in all the measured properties after dry coating relative to the uncoated powders, such that each powder moved from a poorer to a better flow classification and showed improved dispersion. The material intrinsic property such as cohesion, plotted as a function of particle size, gave a trend similar to those of bulk flow properties, AOR and CI. Property improvement is also illustrated in a phase map of inverse cohesion (or FFC) as a function of bulk density, which also indicated a significant positive shift due to dry coating. It is hoped that such phase maps are useful in manufacturing decisions regarding the need for dry coating, which will allow moving from wet granulation to roller compaction or to direct compression based formulations. Copyright © 2011 Elsevier B.V. All rights reserved.

The applicability of physical optics in the millimetre and sub-millimetre spectral region. Part II: Application to a three-component model of ice cloud and its evaluation against the bulk single-scattering properties of various other aggregate models

NASA Astrophysics Data System (ADS)

Baran, Anthony J.; Ishimoto, Hiroshi; Sourdeval, Odran; Hesse, Evelyn; Harlow, Chawn

2018-02-01

The bulk single-scattering properties of various randomly oriented aggregate ice crystal models are compared and contrasted at a number of frequencies between 89 and 874 GHz. The model ice particles consist of the ten-branched plate aggregate, five-branched plate aggregate, eight-branched hexagonal aggregate, Voronoi ice aggregate, six-branched hollow bullet rosette, hexagonal column of aspect ratio unity, and the ten-branched hexagonal aggregate. The bulk single-scattering properties of the latter two ice particle models have been calculated using the light scattering methods described in Part I, which represent the two most extreme members of an ensemble model of cirrus ice crystals. In Part I, it was shown that the method of physical optics could be combined with the T-matrix at a size parameter of about 18 to compute the bulk integral ice optical properties and the phase function in the microwave to sufficient accuracy to be of practical value. Here, the bulk single-scattering properties predicted by the two ensemble model members and the Voronoi model are shown to generally bound those of all other models at frequencies between 89 and 874 GHz, thus representing a three-component model of ice cloud that can be generally applied to the microwave, rather than using many differing ice particle models. Moreover, the Voronoi model and hollow bullet rosette scatter similarly to each other in the microwave. Furthermore, from the various comparisons, the importance of assumed shapes of the particle size distribution as well as cm-sized ice aggregates is demonstrated.

Sensitivity of simulated snow cloud properties to mass-diameter parameterizations.

NASA Astrophysics Data System (ADS)

Duffy, G.; Nesbitt, S. W.; McFarquhar, G. M.

2015-12-01

Mass to diameter (m-D) relationships are used in model parameterization schemes to represent ice cloud microphysics and in retrievals of bulk cloud properties from remote sensing instruments. One of the most common relationships, used in the current Global Precipitation Measurement retrieval algorithm for example, assigns the density of snow as a constant tenth of the density of ice (0.1g/m^3). This assumption stands in contrast to the results of derived m-D relationships of snow particles, which imply decreasing particle densities at larger sizes and result in particle masses orders of magnitude below the constant density relationship. In this study, forward simulations of bulk cloud properties (e.g., total water content, radar reflectivity and precipitation rate) derived from measured size distributions using several historical m-D relationships are presented. This expands upon previous studies that mainly focused on smaller ice particles because of the examination of precipitation-sized particles here. In situ and remote sensing data from the GPM Cold season Experiment (GCPEx) and Canadian CloudSAT/Calypso Validation Program (C3VP), both synoptic snowstorm field experiments in southern Ontario, Canada, are used to evaluate the forward simulations against total water content measured by the Nevzorov and Cloud Spectrometer and Impactor (CSI) probe, radar reflectivity measured by a C band ground based radar and a nadir pointing Ku/Ka dual frequency airborne radar, and precipitation rate measured by a 2D video disdrometer. There are differences between the bulk cloud properties derived using varying m-D relations, with constant density assumptions producing results differing substantially from the bulk measured quantities. The variability in bulk cloud properties derived using different m-D relations is compared against the natural variability in those parameters seen in the GCPEx and C3VP field experiments.

Single- and dual-bead microrheology of semiflexiblefd virus solutions

NASA Astrophysics Data System (ADS)

Addas, Karim M.

Semiflexible polymers are of great biological importance in determining the mechanical properties of cells. Techniques collectively known as microrheology have recently been developed to measure the viscoelastic properties of solutions of sub-microliter volumes. We employ one such technique, which uses single or dual focused laser beams, to trap one or a pair of micron-sized silica beads, and interferometric photodiode detection to measure passively the position fluctuations of the trapped beads with nanometer resolution and high bandwidth of detection. One- and two-bead, frequency-dependent complex shear moduli can be extracted from the position fluctuations via the fluctuation-dissipation theorem. The two-bead method is used to extract the bulk viscoelastic properties of the solution. Using particle tracking microrheology, we report measurements of shear moduli of solutions of fd viruses, which are filamentous, semiflexible, and monodisperse bacteriophages each 0.9 mum long, 7 nm in diameter, and having a persistence length of 2.2 mum. Recent theoretical treatments of semiflexible polymer dynamics provide some quantitative predictions of the rheological properties of such a model system, although the exact limit of short semiflexible rods has not been treated yet. The fd samples measured span the dilute, semi-dilute and concentrated regimes. In the dilute regime the shear modulus is dominated by (rigid rod) rotational relaxation, whereas the high-frequency regime reflects single-semi flexible filament dynamics consistent with the theoretical prediction. Due to the short length of fd viruses used in this study, the intermediate regime does not exhibit a well developed plateau which is expected to occur for long filaments. A dynamic scaling analysis of the shear modulus gives rise to a concentration scaling of c1.36 (r = 0.99) in the transition regime and a frequency scaling of f0.63 (r = 0.98) at high frequencies. One- and two-bead microrheology results agree for this well-defined system of monodisperse virus solutions. The results are also compared with an active microrheology method. In the active method, an oscillatory magnetic force is applied to single micron-sized magnetic beads and the complex shear modulus is derived from the response of the bead. Measurements are also shown for a rotating disk macrorheology technique. The results from the three methods agree within experimental errors.

Combined IR-Raman vs vibrational sum-frequency heterospectral correlation spectroscopy

NASA Astrophysics Data System (ADS)

Roy, Sandra; Beutier, Clémentine; Hore, Dennis K.

2018-06-01

Vibrational sum-frequency generation spectroscopy is a valuable probe of surface structure, particularly when the same molecules are present in one of the adjacent bulk solid or solution phases. As a result of the non-centrosymmetric requirement of SFG, the signal generated is a marker of the extent to which the molecules are ordered in an arrangement that breaks the up-down symmetry at the surface. In cases where the accompanying changes in the bulk are of interest in understanding and interpreting the surface structure, simultaneous analysis of the bulk IR absorption or bulk Raman scattering is helpful, and may be used in heterospectral surface-bulk two-dimensional correlation. We demonstrate that, in such cases, generating a new type of bulk spectrum that combines the IR and Raman amplitudes is a better candidate than the individual IR and Raman spectra for the purpose of correlation with the SFG signal.

Tetradymites as thermoelectrics and topological insulators

NASA Astrophysics Data System (ADS)

Heremans, Joseph P.; Cava, Robert J.; Samarth, Nitin

2017-10-01

Tetradymites are M2X3 compounds — in which M is a group V metal, usually Bi or Sb, and X is a group VI anion, Te, Se or S — that crystallize in a rhombohedral structure. Bi2Se3, Bi2Te3 and Sb2Te3 are archetypical tetradymites. Other mixtures of M and X elements produce common variants, such as Bi2Te2Se. Because tetradymites are based on heavy p-block elements, strong spin-orbit coupling greatly influences their electronic properties, both on the surface and in the bulk. Their surface electronic states are a cornerstone of frontier work on topological insulators. The bulk energy bands are characterized by small energy gaps, high group velocities, small effective masses and band inversion near the centre of the Brillouin zone. These properties are favourable for high-efficiency thermoelectric materials but make it difficult to obtain an electrically insulating bulk, which is a requirement of topological insulators. This Review outlines recent progress made in bulk and thin-film tetradymite materials for the optimization of their properties both as thermoelectrics and as topological insulators.

Bulk properties of the medium produced in relativistic heavy-ion collisions from the beam energy scan program

NASA Astrophysics Data System (ADS)

Adamczyk, L.; Adkins, J. K.; Agakishiev, G.; Aggarwal, M. M.; Ahammed, Z.; Ajitanand, N. N.; Alekseev, I.; Anderson, D. M.; Aoyama, R.; Aparin, A.; Arkhipkin, D.; Aschenauer, E. C.; Ashraf, M. U.; Attri, A.; Averichev, G. S.; Bai, X.; Bairathi, V.; Behera, A.; Bellwied, R.; Bhasin, A.; Bhati, A. K.; Bhattarai, P.; Bielcik, J.; Bielcikova, J.; Bland, L. C.; Bordyuzhin, I. G.; Bouchet, J.; Brandenburg, J. D.; Brandin, A. V.; Brown, D.; Bunzarov, I.; Butterworth, J.; Caines, H.; Calderón de la Barca Sánchez, M.; Campbell, J. M.; Cebra, D.; Chakaberia, I.; Chaloupka, P.; Chang, Z.; Chankova-Bunzarova, N.; Chatterjee, A.; Chattopadhyay, S.; Chen, X.; Chen, J. H.; Chen, X.; Cheng, J.; Cherney, M.; Christie, W.; Contin, G.; Crawford, H. J.; Das, S.; De Silva, L. C.; Debbe, R. R.; Dedovich, T. G.; Deng, J.; Derevschikov, A. A.; Didenko, L.; Dilks, C.; Dong, X.; Drachenberg, J. L.; Draper, J. E.; Dunkelberger, L. E.; Dunlop, J. C.; Efimov, L. G.; Elsey, N.; Engelage, J.; Eppley, G.; Esha, R.; Esumi, S.; Evdokimov, O.; Ewigleben, J.; Eyser, O.; Fatemi, R.; Fazio, S.; Federic, P.; Federicova, P.; Fedorisin, J.; Feng, Z.; Filip, P.; Finch, E.; Fisyak, Y.; Flores, C. E.; Fulek, L.; Gagliardi, C. A.; Garand, D.; Geurts, F.; Gibson, A.; Girard, M.; Grosnick, D.; Gunarathne, D. S.; Guo, Y.; Gupta, A.; Gupta, S.; Guryn, W.; Hamad, A. I.; Hamed, A.; Harlenderova, A.; Harris, J. W.; He, L.; Heppelmann, S.; Heppelmann, S.; Hirsch, A.; Hoffmann, G. W.; Horvat, S.; Huang, T.; Huang, B.; Huang, X.; Huang, H. Z.; Humanic, T. J.; Huo, P.; Igo, G.; Jacobs, W. W.; Jentsch, A.; Jia, J.; Jiang, K.; Jowzaee, S.; Judd, E. G.; Kabana, S.; Kalinkin, D.; Kang, K.; Kauder, K.; Ke, H. W.; Keane, D.; Kechechyan, A.; Khan, Z.; Kikoła, D. P.; Kisel, I.; Kisiel, A.; Kochenda, L.; Kocmanek, M.; Kollegger, T.; Kosarzewski, L. K.; Kraishan, A. F.; Kravtsov, P.; Krueger, K.; Kulathunga, N.; Kumar, L.; Kvapil, J.; Kwasizur, J. H.; Lacey, R.; Landgraf, J. M.; Landry, K. D.; Lauret, J.; Lebedev, A.; Lednicky, R.; Lee, J. H.; Li, X.; Li, C.; Li, W.; Li, Y.; Lidrych, J.; Lin, T.; Lisa, M. A.; Liu, H.; Liu, P.; Liu, Y.; Liu, F.; Ljubicic, T.; Llope, W. J.; Lomnitz, M.; Longacre, R. S.; Luo, S.; Luo, X.; Ma, G. L.; Ma, L.; Ma, Y. G.; Ma, R.; Magdy, N.; Majka, R.; Mallick, D.; Margetis, S.; Markert, C.; Matis, H. S.; Meehan, K.; Mei, J. C.; Miller, Z. W.; Minaev, N. G.; Mioduszewski, S.; Mishra, D.; Mizuno, S.; Mohanty, B.; Mondal, M. M.; Morozov, D. A.; Mustafa, M. K.; Nasim, Md.; Nayak, T. K.; Nelson, J. M.; Nie, M.; Nigmatkulov, G.; Niida, T.; Nogach, L. V.; Nonaka, T.; Nurushev, S. B.; Odyniec, G.; Ogawa, A.; Oh, K.; Okorokov, V. A.; Olvitt, D.; Page, B. S.; Pak, R.; Pandit, Y.; Panebratsev, Y.; Pawlik, B.; Pei, H.; Perkins, C.; Pile, P.; Pluta, J.; Poniatowska, K.; Porter, J.; Posik, M.; Poskanzer, A. M.; Pruthi, N. K.; Przybycien, M.; Putschke, J.; Qiu, H.; Quintero, A.; Ramachandran, S.; Ray, R. L.; Reed, R.; Rehbein, M. J.; Ritter, H. G.; Roberts, J. B.; Rogachevskiy, O. V.; Romero, J. L.; Roth, J. D.; Ruan, L.; Rusnak, J.; Rusnakova, O.; Sahoo, N. R.; Sahu, P. K.; Salur, S.; Sandweiss, J.; Saur, M.; Schambach, J.; Schmah, A. M.; Schmidke, W. B.; Schmitz, N.; Schweid, B. R.; Seger, J.; Sergeeva, M.; Seyboth, P.; Shah, N.; Shahaliev, E.; Shanmuganathan, P. V.; Shao, M.; Sharma, A.; Sharma, M. K.; Shen, W. Q.; Shi, Z.; Shi, S. S.; Shou, Q. Y.; Sichtermann, E. P.; Sikora, R.; Simko, M.; Singha, S.; Skoby, M. J.; Smirnov, N.; Smirnov, D.; Solyst, W.; Song, L.; Sorensen, P.; Spinka, H. M.; Srivastava, B.; Stanislaus, T. D. S.; Strikhanov, M.; Stringfellow, B.; Sugiura, T.; Sumbera, M.; Summa, B.; Sun, Y.; Sun, X. M.; Sun, X.; Surrow, B.; Svirida, D. N.; Tang, A. H.; Tang, Z.; Taranenko, A.; Tarnowsky, T.; Tawfik, A.; Thäder, J.; Thomas, J. H.; Timmins, A. R.; Tlusty, D.; Todoroki, T.; Tokarev, M.; Trentalange, S.; Tribble, R. E.; Tribedy, P.; Tripathy, S. K.; Trzeciak, B. A.; Tsai, O. D.; Ullrich, T.; Underwood, D. G.; Upsal, I.; Van Buren, G.; van Nieuwenhuizen, G.; Vasiliev, A. N.; Videbæk, F.; Vokal, S.; Voloshin, S. A.; Vossen, A.; Wang, G.; Wang, Y.; Wang, F.; Wang, Y.; Webb, J. C.; Webb, G.; Wen, L.; Westfall, G. D.; Wieman, H.; Wissink, S. W.; Witt, R.; Wu, Y.; Xiao, Z. G.; Xie, W.; Xie, G.; Xu, J.; Xu, N.; Xu, Q. H.; Xu, Y. F.; Xu, Z.; Yang, Y.; Yang, Q.; Yang, C.; Yang, S.; Ye, Z.; Ye, Z.; Yi, L.; Yip, K.; Yoo, I.-K.; Yu, N.; Zbroszczyk, H.; Zha, W.; Zhang, Z.; Zhang, X. P.; Zhang, J. B.; Zhang, S.; Zhang, J.; Zhang, Y.; Zhang, J.; Zhang, S.; Zhao, J.; Zhong, C.; Zhou, L.; Zhou, C.; Zhu, X.; Zhu, Z.; Zyzak, M.; STAR Collaboration

2017-10-01

We present measurements of bulk properties of the matter produced in Au+Au collisions at √{sN N}=7.7 ,11.5 ,19.6 ,27 , and 39 GeV using identified hadrons (π±, K±, p , and p ¯) from the STAR experiment in the Beam Energy Scan (BES) Program at the Relativistic Heavy Ion Collider (RHIC). Midrapidity (|y |<0.1 ) results for multiplicity densities d N /d y , average transverse momenta 〈pT〉 , and particle ratios are presented. The chemical and kinetic freeze-out dynamics at these energies are discussed and presented as a function of collision centrality and energy. These results constitute the systematic measurements of bulk properties of matter formed in heavy-ion collisions over a broad range of energy (or baryon chemical potential) at RHIC.

Degradation of Zr-based bulk metallic glasses used in load-bearing implants: A tribocorrosion appraisal.

PubMed

Zhao, Guo-Hua; Aune, Ragnhild E; Mao, Huahai; Espallargas, Nuria

2016-07-01

Owing to the amorphous structure, Bulk Metallic Glasses (BMGs) have been demonstrating attractive properties for potential biomedical applications. In the present work, the degradation mechanisms of Zr-based BMGs with nominal compositions Zr55Cu30Ni5Al10 and Zr65Cu18Ni7Al10 as potential load-bearing implant material were investigated in a tribocorrosion environment. The composition-dependent micro-mechanical and tribological properties of the two BMGs were evaluated prior to the tribocorrosion tests. The sample Zr65-BMG with a higher Zr content exhibited increased plasticity but relatively reduced wear resistance during the ball-on-disc tests. Both BMGs experienced abrasive wear after the dry wear test under the load of 2N. The cross-sectional subsurface structure of the wear track was examined by Focused Ion Beam (FIB). The electrochemical properties of the BMGs in simulated body fluid were evaluated by means of potentiodynamic polarization and X-ray Photoelectron Spectroscopy (XPS). The spontaneous passivation of Zr-based BMGs in Phosphate Buffer Saline solution was mainly attributed to the highly concentrated zirconium cation (Zr(4+)) in the passive film. The tribocorrosion performance of the BMGs was investigated using a reciprocating tribometer equipped with an electrochemical cell. The more passive nature of the Zr65-BMG had consequently a negative influence on its tribocorrosion resistance, which induced the wear-accelerated corrosion and eventually speeded-up the degradation process. It has been revealed the galvanic coupling was established between the depassivated wear track and the surrounding passive area, which is the main degradation mechanism for the passive Zr65-BMG subjected to the tribocorrosion environment. Copyright © 2015 Elsevier Ltd. All rights reserved.

Physical properties of sidewall cores from Decatur, Illinois

USGS Publications Warehouse

Morrow, Carolyn A.; Kaven, Joern; Moore, Diane E.; Lockner, David A.

2017-10-18

To better assess the reservoir conditions influencing the induced seismicity hazard near a carbon dioxide sequestration demonstration site in Decatur, Ill., core samples from three deep drill holes were tested to determine a suite of physical properties including bulk density, porosity, permeability, Young’s modulus, Poisson’s ratio, and failure strength. Representative samples of the shale cap rock, the sandstone reservoir, and the Precambrian basement were selected for comparison. Physical properties were strongly dependent on lithology. Bulk density was inversely related to porosity, with the cap rock and basement samples being both least porous (