exchange solid phase: Topics by Science.gov

Sample records for exchange solid phase

Preparation of Ion Exchange Films for Solid-Phase Spectrophotometry and Solid-Phase Fluorometry

NASA Technical Reports Server (NTRS)

Hill, Carol M.; Street, Kenneth W.; Tanner, Stephen P.; Philipp, Warren H.

2000-01-01

Atomic spectroscopy has dominated the field of trace inorganic analysis because of its high sensitivity and selectivity. The advantages gained by the atomic spectroscopies come with the disadvantage of expensive and often complicated instrumentation. Solid-phase spectroscopy, in which the analyte is preconcentrated on a solid medium followed by conventional spectrophotometry or fluorometry, requires less expensive instrumentation and has considerable sensitivity and selectivity. The sensitivity gains come from preconcentration and the use of chromophore (or fluorophore) developers and the selectivity is achieved by use of ion exchange conditions that favor the analyte in combination with speciative chromophores. Little work has been done to optimize the ion exchange medium (IEM) associated with these techniques. In this report we present a method for making ion exchange polymer films, which considerably simplify the solid-phase spectroscopic techniques. The polymer consists of formaldehyde-crosslinked polyvinyl alcohol with polyacrylic acid entrapped therein. The films are a carboxylate weak cation exchanger in the calcium form. They are mechanically sturdy and optically transparent in the ultraviolet and visible portion of the spectrum, which makes them suitable for spectrophotometry and fluorometry.
FOURTH ANNUAL REPORT ON DISTRIBUTION STUDIES BETWEEN MELTS AND SOLID PHASES USING RADIOACTIVE TRACERS

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

Ward, R.; Orr, W.C.; Katz, L.

Cerium(III) ion in a barium chloride flux does not readily exchangs with any of the ions in solid BaZrO/sub 3/ or BaTiO/sub 3/. It reacts to form new solid phases, which are identified, and does not enter the original crystal lattices at an appreciable rate. The strontium was found to exchange at a measurable rate with barium in BaTiO/sub 3/ and with the corresponding ions in alkaline-earth zirconates. Results of a series of equilibrium and rate measurements were interpreted to ahow that the exchange produces an additional solid phase, SrTiO/sub 3/, rather than the mixed phase, or solid solution, thatmore » ndght have been expected. The significance of this observation is discussed. The self-exchange of yttnium ions between a solid compound of yttrium and an alkali chloride flux in which yttrium chloride is dissolved appears in the systems studied to depend primaaily on the solubility of the solid. Exchange is rapid and complete in the case of yttrium oxychlonide, which is soluble to the extent of 0.6%, but is limited to the surface of yttrium chromium oxide, which has no measurable solubility in the flux. The introduction of yttrium ion vacancies in the lattice of yttrium chromium oxide has no detectable effect in promoting exchange. (For preceding period see NYO-3279.) (auth)« less
Solid phase monofunctionalization of gold nanoparticles using ionic exchange resin as polymer support.

PubMed

Zou, Jianhua; Dai, Qiu; Wang, Jinhai; Liu, Xiong; Huo, Qun

2007-07-01

A solid phase modification method using anionic exchange resin as polymer support was developed for the synthesis of monofunctional gold nanoparticles. Based on a "catch and release" mechanism to control the number of functional groups attached to the nanoparticle surface, bifunctional thiol ligands with a carboxylic acid end group were first immobilized at a controlled density on anionic exchange resin through electrostatic interactions. Gold nanoparticles were then immobilized to the anionic exchange resin by a one-to-one place exchange reaction between resin-bound thiol ligands and butanethiol-protected gold nanoparticles in solution. After cleaving off from the resin under mild conditions, gold nanoparticles with a single carboxyl group attached to the surface were obtained as the major product. Experimental conditions such as the solvents used for ligand loading and solid phase place exchange reaction, and the loading density of the ligands, were found to play a critical role towards the successful synthesis of monofunctional nanoparticles. Overall, the noncovalent bond-based ligand immobilization technique reported here greatly simplified the process of solid phase monofunctionalization of nanoparticles compared to a previously reported covalent bond-based ligand immobilization technique.
Two-dimensional solid-phase extraction strategy for the selective enrichment of aminoglycosides in milk.

PubMed

Shen, Aijin; Wei, Jie; Yan, Jingyu; Jin, Gaowa; Ding, Junjie; Yang, Bingcheng; Guo, Zhimou; Zhang, Feifang; Liang, Xinmiao

2017-03-01

An orthogonal two-dimensional solid-phase extraction strategy was established for the selective enrichment of three aminoglycosides including spectinomycin, streptomycin, and dihydrostreptomycin in milk. A reversed-phase liquid chromatography material (C 18 ) and a weak cation-exchange material (TGA) were integrated in a single solid-phase extraction cartridge. The feasibility of two-dimensional clean-up procedure that experienced two-step adsorption, two-step rinsing, and two-step elution was systematically investigated. Based on the orthogonality of reversed-phase and weak cation-exchange procedures, the two-dimensional solid-phase extraction strategy could minimize the interference from the hydrophobic matrix existing in traditional reversed-phase solid-phase extraction. In addition, high ionic strength in the extracts could be effectively removed before the second dimension of weak cation-exchange solid-phase extraction. Combined with liquid chromatography and tandem mass spectrometry, the optimized procedure was validated according to the European Union Commission directive 2002/657/EC. A good performance was achieved in terms of linearity, recovery, precision, decision limit, and detection capability in milk. Finally, the optimized two-dimensional clean-up procedure incorporated with liquid chromatography and tandem mass spectrometry was successfully applied to the rapid monitoring of aminoglycoside residues in milk. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Phase diagram of two-dimensional hard ellipses.

PubMed

Bautista-Carbajal, Gustavo; Odriozola, Gerardo

2014-05-28

We report the phase diagram of two-dimensional hard ellipses as obtained from replica exchange Monte Carlo simulations. The replica exchange is implemented by expanding the isobaric ensemble in pressure. The phase diagram shows four regions: isotropic, nematic, plastic, and solid (letting aside the hexatic phase at the isotropic-plastic two-step transition [E. P. Bernard and W. Krauth, Phys. Rev. Lett. 107, 155704 (2011)]). At low anisotropies, the isotropic fluid turns into a plastic phase which in turn yields a solid for increasing pressure (area fraction). Intermediate anisotropies lead to a single first order transition (isotropic-solid). Finally, large anisotropies yield an isotropic-nematic transition at low pressures and a high-pressure nematic-solid transition. We obtain continuous isotropic-nematic transitions. For the transitions involving quasi-long-range positional ordering, i.e., isotropic-plastic, isotropic-solid, and nematic-solid, we observe bimodal probability density functions. This supports first order transition scenarios.
A new route of oxygen isotope exchange in the solid phase: demonstration in CuSO4.5H2O.

PubMed

Danon, Albert; Saig, Avraham; Finkelstein, Yacov; Koresh, Jacob E

2005-11-10

Temperature-programmed desorption mass spectrometry (TPD-MS) measurements on [(18)O]water-enriched copper sulfate pentahydrate (CuSO(4).5H(2)(18)O) reveal an unambiguous occurrence of efficient oxygen isotope exchange between the water of crystallization and the sulfate in its CuSO(4) solid phase. To the best of our knowledge, the occurrence of such an exchange was never observed in a solid phase. The exchange process was observed during the stepwise dehydration (50-300 degrees C) of the compound. Specifically, the exchange promptly occurs somewhere between 160 and 250 degrees C; however, the exact temperature could not be resolved conclusively. It is shown that only the fifth, sulfate-associated, anionic H(2)O molecule participates in the exchange process and that the exchange seems to occur in a preferable fashion with, at the most, one oxygen atom in SO(4). Such an exchange, occurring below 250 degrees C, questions the common conviction of unfeasible oxygen exchange under geothermic conditions. This new oxygen exchange phenomenon is not exclusive to copper sulfate but is unambiguously observed also in other sulfate- and nitrate-containing minerals.
Boron-Based Hydrogen Storage: Ternary Borides and Beyond

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

Vajo, John J.

DOE continues to seek reversible solid-state hydrogen materials with hydrogen densities of ≥11 wt% and ≥80 g/L that can deliver hydrogen and be recharged at moderate temperatures (≤100 °C) and pressures (≤100 bar) enabling incorporation into hydrogen storage systems suitable for transportation applications. Boron-based hydrogen storage materials have the potential to meet the density requirements given boron’s low atomic weight, high chemical valance, and versatile chemistry. However, the rates of hydrogen exchange in boron-based compounds are thus far much too slow for practical applications. Although contributing to the high hydrogen densities, the high valance of boron also leads to slowmore » rates of hydrogen exchange due to extensive boron-boron atom rearrangements during hydrogen cycling. This rearrangement often leads to multiple solid phases occurring over hydrogen release and recharge cycles. These phases must nucleate and react with each other across solid-solid phase boundaries leading to energy barriers that slow the rates of hydrogen exchange. This project sought to overcome the slow rates of hydrogen exchange in boron-based hydrogen storage materials by minimizing the number of solid phases and the boron atom rearrangement over a hydrogen release and recharge cycle. Two novel approaches were explored: 1) developing matched pairs of ternary borides and mixed-metal borohydrides that could exchange hydrogen with only one hydrogenated phase (the mixed-metal borohydride) and only one dehydrogenated phase (the ternary boride); and 2) developing boranes that could release hydrogen by being lithiated using lithium hydride with no boron-boron atom rearrangement.« less
Modeling multicomponent ion exchange equilibrium utilizing hydrous crystalline silicotitanates by a multiple interactive ion exchange site model

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

Zheng, Z.; Anthony, R.G.; Miller, J.E.

1997-06-01

An equilibrium multicomponent ion exchange model is presented for the ion exchange of group I metals by TAM-5, a hydrous crystalline silicotitanate. On the basis of the data from ion exchange and structure studies, the solid phase is represented as Na{sub 3}X instead of the usual form of NaX. By using this solid phase representation, the solid can be considered as an ideal phase. A set of model ion exchange reactions is proposed for ion exchange between H{sup +}, Na{sup +}, K{sup +}, Rb{sup +}, and Cs{sup +}. The equilibrium constants for these reactions were estimated from experiments with simplemore » ion exchange systems. Bromley`s model for activity coefficients of electrolytic solutions was used to account for liquid phase nonideality. Bromley`s model parameters for CsOH at high ionic strength and for NO{sub 2}{sup {minus}} and Al(OH){sub 4}{sup {minus}} were estimated in order to apply the model for complex waste simulants. The equilibrium compositions and distribution coefficients of counterions were calculated for complex simulants typical of DOE wastes by solving the equilibrium equations for the model reactions and material balance equations. The predictions match the experimental results within 10% for all of these solutions.« less
A porous flow approach to model thermal non-equilibrium applicable to melt migration

NASA Astrophysics Data System (ADS)

Schmeling, Harro; Marquart, Gabriele; Grebe, Michael

2018-01-01

We develop an approach for heat exchange between a fluid and a solid phase of a porous medium where the temperatures of the fluid and matrix are not in thermal equilibrium. The formulation considers moving of the fluid within a resting or deforming porous matrix in an Eulerian coordinate system. The approach can be applied, for example, to partially molten systems or to brine transport in porous rocks. We start from an existing theory for heat exchange where the energy conservation equations for the fluid and the solid phases are separated and coupled by a heat exchange term. This term is extended to account for the full history of heat exchange. It depends on the microscopic geometry of the fluid phase. For the case of solid containing hot, fluid-filled channels, we derive an expression based on a time-dependent Fourier approach for periodic half-waves. On the macroscopic scale, the temporal evolution of the heat exchange leads to a convolution integral along the flow path of the solid, which simplifies considerably in case of a resting matrix. The evolution of the temperature in both phases with time is derived by inserting the heat exchange term into the energy equations. We explore the effects of thermal non-equilibrium between fluid and solid by considering simple cases with sudden temperature differences between fluid and solid as initial or boundary conditions, and by varying the fluid velocity with respect to the resting porous solid. Our results agree well with an analytical solution for non-moving fluid and solid. The temperature difference between solid and fluid depends on the Peclet number based on the Darcy velocity. For Peclet numbers larger than 1, the temperature difference after one diffusion time reaches 5 per cent of \\tilde{T} or more (\\tilde{T} is a scaling temperature, e.g. the initial temperature difference). Thus, our results imply that thermal non-equilibrium can play an important role for melt migration through partially molten systems where melt focuses into melt channels near the transition to melt ascent by dykes. Our method is based on solving the convolution integration for the heat exchange over the full flow history, which is numerically expensive. We tested to replace the heat exchange term by an instantaneous, approximate term. We found considerable errors on the short timescale, but a good agreement on the long timescale if appropriate parameters for the approximate terms are used. We derived these parameters which may be implemented in fully dynamical two-phase flow formulations of melt migration in the Earth.
WKB calculation of multiple spin exchange in monolayer solid 3He

NASA Astrophysics Data System (ADS)

Ashizawa, Hisayuki; Hirashima, D. S.

2000-10-01

An insight is given into the multiple spin exchange in the registered 3×3 phase of solid 3He adsorbed on graphite with a WKB calculation taking account of the corrugation of the substrate potential. The corrugation is essential for this phase to be realized, and is found to suppress the exchange processes of many (>=4) particles to make only the two- and the three-spin exchanges relevant. When the magnitude of the corrugation is modest, the exchange can be ferromagnetic, in agreement with the experiment by Ikegami et al. [Phys. Rev. Lett. 81, 2478 (1998)]. Validity and limitation of the WKB approximation are also discussed.
Perspectives of advanced thermal management in solar thermochemical syngas production using a counter-flow solid-solid heat exchanger

NASA Astrophysics Data System (ADS)

Falter, Christoph; Sizmann, Andreas; Pitz-Paal, Robert

2017-06-01

A modular reactor model is presented for the description of solar thermochemical syngas production involving counter-flow heat exchangers that recuperate heat from the solid phase. The development of the model is described including heat diffusion within the reactive material as it travels through the heat exchanger, which was previously identified to be a possibly limiting factor in heat exchanger design. Heat transfer within the reactive medium is described by conduction and radiation, where the former is modeled with the three-resistor model and the latter with the Rosseland diffusion approximation. The applicability of the model is shown by the analysis of heat exchanger efficiency for different material thicknesses and porosities in a system with 8 chambers and oxidation and reduction temperatures of 1000 K and 1800 K, respectively. Heat exchanger efficiency is found to rise strongly for a reduction of material thickness, as the element mass is reduced and a larger part of the elements takes part in the heat exchange process. An increase of porosity enhances radiation heat exchange but deteriorates conduction. The overall heat exchange in the material is improved for high temperatures in the heat exchanger, as radiation dominates the energy transfer. The model is shown to be a valuable tool for the development and analysis of solar thermochemical reactor concepts involving heat exchange from the solid phase.
Solid-phase extraction sorbent consisting of alkyltrimethylammonium surfactants immobilized onto strong cation-exchange polystyrene resin.

PubMed

Reid, Kendra R; Kennedy, Lonnie J; Crick, Eric W; Conte, Eric D

2002-10-25

Presented is a solid-phase extraction sorbent material composed of cationic alkyltrimethylammonium surfactants attached to a strong cation-exchange resin via ion-exchange. The original hydrophilic cation-exchange resin is made hydrophobic by covering the surface with alkyl chains from the hydrophobic portion of the surfactant. The sorbent material now has a better ability to extract hydrophobic molecules from aqueous samples. The entire stationary phase (alkyltrimethylammonium surfactant) is removed along with the analyte during the elution step. The elution step requires a mild elution solvent consisting of 0.25 M Mg2+ in a 50% 2-propanol solution. The main advantage of using a removable stationary phase is that traditionally utilized toxic elution solvents such as methylene chloride, which are necessary to efficiently release strongly hydrophobic species from SPE stationary phases, may now be avoided. Also, the final extract is directly compatible with reversed-phase liquid chromatography. The performance of this procedure is presented using pyrene as a test molecule.
Numerical investigation of influence on heat transfer characteristics to pneumatically conveyed dense phase flow by selecting models and boundary conditions

NASA Astrophysics Data System (ADS)

Zheng, Y.; Liu, Q.; Li, Y.

2012-03-01

Solids moving with a gas stream in a pipeline can be found in many industrial processes, such as power generation, chemical, pharmaceutical, food and commodity transfer processes. A mass flow rate of the solids is important characteristic that is often required to be measured (and controlled) to achieve efficient utilization of energy and raw materials in pneumatic conveying systems. The methods of measuring the mass flow rate of solids in a pneumatic pipeline can be divided into direct and indirect (inferential) measurements. A thermal solids' mass flow-meter, in principle, should ideally provide a direct measurement of solids flow rate, regardless of inhomogeneities in solids' distribution and environmental impacts. One key issue in developing a thermal solids' mass flow-meter is to characterize the heat transfer between the hot pipe wall and the gas-solids dense phase flow. The Eulerian continuum modeling with gas-solid two phases is the most common method for pneumatic transport. To model a gas-solid dense phase flow passing through a heated region, the gas phase is described as a continuous phase and the particles as the second phase. This study aims to describe the heat transfer characteristics between the hot wall and the gas-solids dense phase flow in pneumatic pipelines by modeling a turbulence gas-solid plug passing through the heated region which involves several actual and crucial issues: selections of interphase exchange coefficient, near-wall region functions and different wall surface temperatures. A sensitivity analysis was discussed to identify the influence on the heat transfer characteristics by selecting different interphase exchange coefficient models and different boundary conditions. Simulation results suggest that sensitivity analysis in the choice of models is very significant. The simulation results appear to show that a combination of choosing the Syamlal-O'Brien interphase exchange coefficient model and the standard k-ɛ model along with the standard wall function model might be the best approach, by which, the simulation data seems to be closest to the experimental results.
Three-phase flow? Consider helical-coil heat exchangers

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

Haraburda, S.S.

1995-07-01

In recent years, chemical process plants are increasingly encountering processes that require heat exchange in three-phase fluids. A typical application, for example, is heating liquids containing solid catalyst particles and non-condensable gases. Heat exchangers designed for three-phase flow generally have tubes with large diameters (typically greater than two inches), because solids can build-up inside the tube and lead to plugging. At the same time, in order to keep heat-transfer coefficients high, the velocity of the process fluid within the tube should also be high. As a result, heat exchangers for three-phase flow may require less than five tubes -- eachmore » having a required linear length that could exceed several hundred feet. Given these limitations, it is obvious that a basic shell-and-tube heat exchanger is not the most practical solution for this purpose. An alternative for three-phase flow is a helical-coil heat exchanger. The helical-coil units offer a number of advantages, including perpendicular, counter-current flow and flexible overall dimensions for the exchanger itself. The paper presents equations for: calculating the tube-side heat-transfer coefficient; calculating the shell-side heat-transfer coefficient; calculating the heat-exchanger size; calculating the tube-side pressure drop; and calculating shell-side pressure-drop.« less
Quantification of VX Nerve Agent in Various Food Matrices by Solid-Phase Extraction Ultra-Performance Liquid ChromatographyTime-of-Flight Mass Spectrometry

DTIC Science & Technology

2016-04-01

QUANTIFICATION OF VX NERVE AGENT IN VARIOUS FOOD MATRICES BY SOLID-PHASE EXTRACTION ULTRA-PERFORMANCE...TITLE AND SUBTITLE Quantification of VX Nerve Agent in Various Food Matrices by Solid-Phase Extraction Ultra-Performance Liquid Chromatography... food matrices. The mixed-mode cation exchange (MCX) sorbent and Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) methods were used for
Issues associated with Galilean invariance on a moving solid boundary in the lattice Boltzmann method

NASA Astrophysics Data System (ADS)

Peng, Cheng; Geneva, Nicholas; Guo, Zhaoli; Wang, Lian-Ping

2017-01-01

In lattice Boltzmann simulations involving moving solid boundaries, the momentum exchange between the solid and fluid phases was recently found to be not fully consistent with the principle of local Galilean invariance (GI) when the bounce-back schemes (BBS) and the momentum exchange method (MEM) are used. In the past, this inconsistency was resolved by introducing modified MEM schemes so that the overall moving-boundary algorithm could be more consistent with GI. However, in this paper we argue that the true origin of this violation of Galilean invariance (VGI) in the presence of a moving solid-fluid interface is due to the BBS itself, as the VGI error not only exists in the hydrodynamic force acting on the solid phase, but also in the boundary force exerted on the fluid phase, according to Newton's Third Law. The latter, however, has so far gone unnoticed in previously proposed modified MEM schemes. Based on this argument, we conclude that the previous modifications to the momentum exchange method are incomplete solutions to the VGI error in the lattice Boltzmann method (LBM). An implicit remedy to the VGI error in the LBM and its limitation is then revealed. To address the VGI error for a case when this implicit remedy does not exist, a bounce-back scheme based on coordinate transformation is proposed. Numerical tests in both laminar and turbulent flows show that the proposed scheme can effectively eliminate the errors associated with the usual bounce-back implementations on a no-slip solid boundary, and it can maintain an accurate momentum exchange calculation with minimal computational overhead.
Modeling of sorption processes on solid-phase ion-exchangers

NASA Astrophysics Data System (ADS)

Dorofeeva, Ludmila; Kuan, Nguyen Anh

2018-03-01

Research of alkaline elements separation on solid-phase ion-exchangers is carried out to define the selectivity coefficients and height of an equivalent theoretical stage for both continuous and stepwise filling of column by ionite. On inorganic selective sorbents the increase in isotope enrichment factor up to 0.0127 is received. Also, parametrical models that are adequately describing dependence of the pressure difference and the magnitude expansion in the ion-exchange layer from the flow rate and temperature have been obtained. The concentration rate value under the optimum realization conditions of process and depending on type of a selective material changes in a range 1.021÷1.092. Calculated results show agreement with experimental data.
Improved Heat-of-Fusion Energy Storage

NASA Technical Reports Server (NTRS)

Chen, K. H.; Manvi, R.

1982-01-01

Alkali metal/alkali-halide mixtures proposed for preventing solid buildup during energy recovery. When mixture melts (by absorption of heat of fusion), it forms two immiscible liquids. Salt-rich phase is heavier and has higher melting/recrysallization temperature; so during energy recovery salt crystallizes in this phase first. Since heat exchanger for energy recovery is in lighter metal-rich phase, solids do not form and there is no reduction of heat-recovery efficiency.
Atom exchange between aqueous Fe(II) and structural Fe in clay minerals.

PubMed

Neumann, Anke; Wu, Lingling; Li, Weiqiang; Beard, Brian L; Johnson, Clark M; Rosso, Kevin M; Frierdich, Andrew J; Scherer, Michelle M

2015-03-03

Due to their stability toward reductive dissolution, Fe-bearing clay minerals are viewed as a renewable source of Fe redox activity in diverse environments. Recent findings of interfacial electron transfer between aqueous Fe(II) and structural Fe in clay minerals and electron conduction in octahedral sheets of nontronite, however, raise the question whether Fe interaction with clay minerals is more dynamic than previously thought. Here, we use an enriched isotope tracer approach to simultaneously trace Fe atom movement from the aqueous phase to the solid ((57)Fe) and from the solid into the aqueous phase ((56)Fe). Over 6 months, we observed a significant decrease in aqueous (57)Fe isotope fraction, with a fast initial decrease which slowed after 3 days and stabilized after about 50 days. For the aqueous (56)Fe isotope fraction, we observed a similar but opposite trend, indicating that Fe atom movement had occurred in both directions: from the aqueous phase into the solid and from the solid into aqueous phase. We calculated that 5-20% of structural Fe in clay minerals NAu-1, NAu-2, and SWa-1 exchanged with aqueous Fe(II), which significantly exceeds the Fe atom layer exposed directly to solution. Calculations based on electron-hopping rates in nontronite suggest that the bulk conduction mechanism previously demonstrated for hematite1 and suggested as an explanation for the significant Fe atom exchange observed in goethite2 may be a plausible mechanism for Fe atom exchange in Fe-bearing clay minerals. Our finding of 5-20% Fe atom exchange in clay minerals indicates that we need to rethink how Fe mobility affects the macroscopic properties of Fe-bearing phyllosilicates and its role in Fe biogeochemical cycling, as well as its use in a variety of engineered applications, such as landfill liners and nuclear repositories.
Modelling the diffusive transport and remobilisation of 137Cs in sediments: The effects of sorption kinetics and reversibility

NASA Astrophysics Data System (ADS)

Smith, J. T.; Comans, R. N. J.

1996-03-01

In determining the mobility of ions in sediments it is important to take account of the solid phase sorption and speciation. Measurements were made of activity depth profiles of 137Cs from fallout from Nuclear Weapons Testing and from the Chernobyl accident in two lake sediments. The fraction of 137Cs in the aqueous, exchangeably sorbed and "fixed" phases was determined at each depth interval. A model was developed to simulate the transport of 137Cs in these sediments, taking account of changes in sorption properties as the concentration of the competing ammonium ion changes with depth, as well as transfers of activity to less-exchangeable sites on the solids. The model simulations give reasonable agreement with experimental data, and the fitted rate constant for slow transfers to less-exchangeable sites ( T1/2 = 50-125 d) is in agreement with independent measurements. The modelling gave evidence for a reverse reaction from less-exchangeable to exchangeable sites with a half-life of order 10 y. Model results were compared with those generated by a physical mixing model and the standard molecular diffusion model assuming equilibrium sorption to the solid phase. Estimates were made of the remobilisation of Chernobyl 137Cs from these sediments to the water column: predicted rates vary from around 3% of the inventory per year 2 years after the fallout event to 0.04% per year 30 years after the fallout.

Solid-Phase Spectrophotometric Analysis of 1-Naphthol Using Silica Functionalized with m-Diazophenylarsonic Acid

NASA Astrophysics Data System (ADS)

Zaitseva, Nataliya; Alekseev, Sergei; Zaitsev, Vladimir; Raks, Viktoria

2016-03-01

The m-aminophenylarsonic acid (m-APAA) was immobilized onto the silica gel surface with covalently grafted quaternary ammonium groups via ion exchange. The diazotization of ion-bonded m-APAA resulted in a new solid-phase spectrophotometric reagent for detection of 1-naphtol in environmental water samples. The procedure of solid-phase spectrophotometric analysis is characterized by 20 μg L-1 limit of detection (LOD) of 1-naphtol, up to 2000 concentration factor, and insensitivity to the presence of natural water components as well as to 30-fold excess of phenol, resorcinol, and catechol.
Solid phase pegylation of hemoglobin.

PubMed

Suo, Xiaoyan; Zheng, Chunyang; Yu, Pengzhan; Lu, Xiuling; Ma, Guanghui; Su, Zhiguo

2009-01-01

A solid phase conjugation process was developed for attachment of polyethylene glycol to hemoglobin molecule. Bovine hemoglobin was loaded onto an ion exchange chromatography column and adsorbed by the solid medium. Succinimidyl carbonate mPEG was introduced in the mobile phase after the adsorption. Pegylation took place between the hemoglobin on the solid phase, and the pegylation reagent in the liquid phase. A further elution was carried out to separate the pegylated and the unpegylated protein. Analysis by HPSEC, SDS-PAGE, and MALLS demonstrated that the fractions eluted from the solid phase contained well-defined components. Pegylated hemoglobin with one PEG chain was obtained with the yield of 75%, in comparison to the yield of 30% in the liquid phase pegylation. The P(50) values of the mono-pegylated hemoglobin, prepared with SC-mPEG 5 kDa, 10 kDa and 20 kDa, were 19.97, 20.23 and 20.54 mmHg, which were much closer to the value of red blood cells than that of pegylated hemoglobin prepared with the conventional method.
Geochemical modeling of reactions and partitioning of trace metals and radionuclides during titration of contaminated acidic sediments.

PubMed

Zhang, Fan; Luo, Wensui; Parker, Jack C; Spalding, Brian P; Brooks, Scott C; Watson, David B; Jardine, Philip M; Gu, Baohua

2008-11-01

Many geochemical reactions that control aqueous metal concentrations are directly affected by solution pH. However, changes in solution pH are strongly buffered by various aqueous phase and solid phase precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior of the soil-solution system is thus critical to predict metal transport under variable pH conditions. This studywas undertaken to develop a practical generic geochemical modeling approach to predict aqueous and solid phase concentrations of metals and anions during conditions of acid or base additions. The method of Spalding and Spalding was utilized to model soil buffer capacity and pH-dependent cation exchange capacity by treating aquifer solids as a polyprotic acid. To simulate the dynamic and pH-dependent anion exchange capacity, the aquifer solids were simultaneously treated as a polyprotic base controlled by mineral precipitation/ dissolution reactions. An equilibrium reaction model that describes aqueous complexation, precipitation, sorption and soil buffering with pH-dependent ion exchange was developed using HydroGeoChem v5.0 (HGC5). Comparison of model results with experimental titration data of pH, Al, Ca, Mg, Sr, Mn, Ni, Co, and SO4(2-) for contaminated sediments indicated close agreement suggesting that the model could potentially be used to predictthe acid-base behavior of the sediment-solution system under variable pH conditions.
Heat exchange studies on coconut oil cells as thermal energy storage for room thermal conditioning

NASA Astrophysics Data System (ADS)

Sutjahja, I. M.; Putri, Widya A.; Fahmi, Z.; Wonorahardjo, S.; Kurnia, D.

2017-07-01

As reported by many thermal environment experts, room air conditioning might be controlled by thermal mass system. In this paper we discuss the performance of coconut oil cells as room thermal energy storage. The heat exchange mechanism of coconut oil (CO) which is one of potential organic Phase Change Material (PCM) is studied based on the results of temperature measurements in the perimeter and core parts of cells. We found that the heat exchange performance, i.e. heat absorption and heat release processes of CO cells are dominated by heat conduction in the sensible solid from the higher temperature perimeter part to the lower temperature core part and heat convection during the solid-liquid phase transition and sensible liquid phase. The capability of heat absorption as measured by the reduction of air temperature is not influenced by CO cell size. Besides that, the application of CO as the thermal mass has to be accompanied by air circulation to get the cool sensation of the room’s occupants.
Novel Anaerobic Wastewater Treatment System for Energy Generation at Forward Operating Bases

DTIC Science & Technology

2016-08-01

AnMBR) technology with clinoptilolite ion exchange and GreenBox™ ammonia electrolysis. The system generates both methane and hydrogen fuels...experimental setup. ................................................ 21 Figure 10. Methane phase semi batch experimental setup, a total of three reactors were...set up for PS + solid, Bioc and ADS methane phase reactors. .................... 21 Figure 11. Dried PS solid for the control, Bioc blend for the
[Study on solid phase extraction spectrophotometric determination of zinc with 2-(2-quinolylazo)-5-dimthylaminophenol].

PubMed

Zhou, Shi-ping; Duan, Chang-qun; Liu, Hong-cheng; Hu, Qiu-fen

2005-10-01

A highly sensitive, selective and rapid method for the determination of zinc based on the rapid reaction of zinc(II) with 2-(2-quinolylazo)-5-dimthylaminophenol (QADMAP) and the solid phase extraction of zinc ion with anion exchange resin cartridge was developed. In the presence of pH 8.5 buffer solution and Triton X-100 medium, QADMAP can react with zinc(II) to form a stable 2 :1 complex (QADMAP:Zn(II)). The molar absorptivity is 1.22 x 10(5)L x moL(-1) x cm(-1) at 590 nm. Beer's law is obeyed in the range of 0-1.0 microg x mL(-1). The zinc ions in the samples can be enriched and separated by solid phase extraction with anion exchange resincartridge. Testing results show that recovery for zinc(II) was from 95% to 104%, and RSD was below 3%. This method was applied to the determination of zinc in water and food with good results.
Measurement of backbone hydrogen-deuterium exchange in the type III secretion system needle protein PrgI by solid-state NMR

NASA Astrophysics Data System (ADS)

Chevelkov, Veniamin; Giller, Karin; Becker, Stefan; Lange, Adam

2017-10-01

In this report we present site-specific measurements of amide hydrogen-deuterium exchange rates in a protein in the solid state phase by MAS NMR. Employing perdeuteration, proton detection and a high external magnetic field we could adopt the highly efficient Relax-EXSY protocol previously developed for liquid state NMR. According to this method, we measured the contribution of hydrogen exchange on apparent 15N longitudinal relaxation rates in samples with differing D2O buffer content. Differences in the apparent T1 times allowed us to derive exchange rates for multiple residues in the type III secretion system needle protein.
Habitable Planets with Dynamic System of Global Air-Liquid-Solid Planet and Life

NASA Astrophysics Data System (ADS)

Miura, Y.; Kato, T.

2017-11-01

Habitable zone is dynamic three phase states (air-liquid-solid), which will be obtained in water-planet with volatile exchanges. Water and carbon-bearing grains at older extraterrestrial stones suggest that there are no global ocean water system.
Self-healing liquid/solid state battery

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

Burke, Paul J.; Chung, Brice H.V.; Phadke, Satyajit R.

A battery system that exchanges energy with an external device is provided. The battery system includes a positive electrode having a first metal or alloy, a negative electrode having a second metal or alloy, and an electrolyte including a salt of the second metal or alloy. The positive electrode, the negative electrode, and the electrolyte are in a liquid phase at an operating temperature during at least one portion of operation. The positive electrode is entirely in a liquid phase in one charged state and includes a solid phase in another charged state. The solid phase of the positive electrodemore » includes a solid intermetallic formed by the first and the second metals or alloys. Methods of storing electrical energy from an external circuit using such a battery system are also provided.« less
Ion exchange of Group I metals by hydrous crystalline silicotitanates

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

Zheng, Z.; Philip, C.V.; Anthony, R.G.

1996-11-01

A new hydrous crystalline silicotitanate, labeled TAM-5 or CST, was developed for removing radioactive Cs{sup +} from aqueous nuclear waste. This material is stable to radiation, highly selective for cesium relative to sodium, potassium, rubidium, and protons, and performs well in acidic, neutral, and basic solutions. Various experiments were conducted to determine the ion exchange properties of TAM-5. Two kinds of ion exchange sites exist in the solid, and cation exchange in one site affects the ion exchange properties of the other site. These two types of sites have different thermal effects: with increasing temperature the pH of one increasesmore » and the pH of the other one decreases. The total ion exchange capacity is 4.6 mequiv/g, but the cesium ion exchange capacity was less, which shows that not all of the ion exchange sites are available for cesium exchange. Step changes were observed in the ion exchange isotherms. The solid phase behaved ideally prior to the step changes. The apparent capacities within the ideal solid region were 0.57 mequiv/g for Cs{sup +}, 1.18 mequiv/g for Rb{sup +}, and 1.2 mequiv/g for K{sup +}. Both direct competition by rubidium and protons and indirect competition by protons and potassium were observed. The rational selectivities, which were measured from binary ion exchange data, can be used in different solutions including the multicomponent ion exchange systems, because they are constant for an ideal solid. Binary ion exchange isotherms were also developed using the rational selectivity as the parameter for the isotherms of cesium, rubidinium, and potassium.« less
Solid Phase Luminescence of Several Rare Earth Ions on Ion-Exchange Films

NASA Technical Reports Server (NTRS)

Tanner, Stephen P.; Street, Kenneth W., Jr.

1999-01-01

The development and characterization of a novel ion-exchange film for solid-phase fluorometry and phosphorimetry is reported. This new cation-exchange material is suitable for spectroscopic applications in the ultraviolet and visible regions. It is advantageous because it, as a single entity, is easily recovered from solution and mounted in the spectrofluorometers. After preconcentration on the film, the luminescence intensity of lanthanide ions is several orders of magnitude greater than that of the corresponding solution, depending on the volume of solution and the amount of film. This procedure allows emission spectral measurements and determination of lanthanide ions at solution concentrations of < 5 (micro)g/L. The film may be stored for subsequent reuse or as a permanent record of the analysis. The major drawback to the use of the film is slow uptake of analyte due to diffusion limitations.
Geochemical Modeling of Reactions and Partitioning of Trace Metals and Radionuclides during Titration of Contaminated Acidic Sediments

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

Zhang, Fan; Parker, Jack C.; Luo, Wensui

2008-01-01

Many geochemical reactions that control aqueous metal concentrations are directly affected by solution pH. However, changes in solution pH are strongly buffered by various aqueous phase and solid phase precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior of the soil-solution system is thus critical to predict metal transport under variable pH conditions. This study was undertaken to develop a practical generic geochemical modeling approach to predict aqueous and solid phase concentrations of metals and anions during conditions of acid or base additions. The method of Spalding and Spalding was utilized to model soil buffer capacity and pH-dependent cationmore » exchange capacity by treating aquifer solids as a polyprotic acid. To simulate the dynamic and pH-dependent anion exchange capacity, the aquifer solids were simultaneously treated as a polyprotic base controlled by mineral precipitation/dissolution reactions. An equilibrium reaction model that describes aqueous complexation, precipitation, sorption and soil buffering with pH-dependent ion exchange was developed using HydroGeoChem v5.0 (HGC5). Comparison of model results with experimental titration data of pH, Al, Ca, Mg, Sr, Mn, Ni, Co, and SO{sub 4}{sup 2-} for contaminated sediments indicated close agreement, suggesting that the model could potentially be used to predict the acid-base behavior of the sediment-solution system under variable pH conditions.« less
A Quantitative Tunneling/Desorption Model for the Exchange Current at the Porous Electrode/Beta - Alumina/Alkali Metal Gas Three Phase Zone at 700-1300K

NASA Technical Reports Server (NTRS)

Williams, R. M.; Ryan, M. A.; Saipetch, C.; LeDuc, H. G.

1996-01-01

The exchange current observed at porous metal electrodes on sodium or potassium beta -alumina solid electrolytes in alkali metal vapor is quantitatively modeled with a multi-step process with good agreement with experimental results.
Solid Electrolytes and Photoelectrolysis

DTIC Science & Technology

1974-12-31

some DC and low-frequency AC measurements are made with molten NaNO, on both sides of the specimen. These molten - salt measurements have been in...transport properties. 1. Im3 phase. A metastable cubic phase of NaSbO, was obtained from high-pressure KSbO, by ion exchange in molten NaNO...sieves. As these latter structures are stabilized by water, they are unsuitable for solid electrolytes that are to be in contact with molten
Isotopic Exchange in Porous and Dense Magnesium Borohydride.

PubMed

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

2015-09-01

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

PubMed

Pesavento, Maria; Sturini, Michela; D'Agostino, Girolamo; Biesuz, Raffaela

2010-02-19

The efficiency of the metal ion recovery by solid phase extraction (SPE) in complexing resins columns is predicted by a simple model based on two parameters reflecting the sorption equilibria and kinetics of the metal ion on the considered resin. The parameter related to the adsorption equilibria was evaluated by the Gibbs-Donnan model, and that related to the kinetics by assuming that the ion exchange is the adsorption rate determining step. The predicted parameters make it possible to evaluate the breakthrough volume of the considered metal ion, Cu(II), from different kinds of complexing resins, and at different conditions, such as acidity and ionic composition. Copyright 2009. Published by Elsevier B.V.
Development of a Direct Contact Heat Exchanger, Phase 1 Study Report

NASA Technical Reports Server (NTRS)

Manvi, R.

1978-01-01

Electric power generation from geothermal brine requires, first, bringing the hot brine to the surface and then converting the heat to electric power. Binary conversion schemes were proposed, with the heat transfer between the brine and the working organic fluid taking place in a conventional tube and shell heat exchanger. If the brine is heavily laden with dissolved solids, however, solids buildup on the heat exchanger surfaces leads to a considerable degree of fouling and an accompanying drop in performance is experienced. A possible solution to this problem is the use of a direct contact exchanger with the secondary fluid power cycle. The proposed concept involves the formation of fluid sheets and bells as heat angles. Results of a study concerning the fluid mechanics of such surfaces are given.
Double-disk solid-phase extraction--Simultaneous cleanup and trace enrichment of herbicides and metabolites from environmental samples

USGS Publications Warehouse

Ferrar, Imma; Barceló, Damià; Thurman, E.M.

1999-01-01

Phenylurea and triazine herbicides, including some metabolites, were isolated from water and soil extracts by solid-phase extraction using a layered system of two extraction disks, a method called double-disk solid-phase extraction. The first disk consisted of strong anion exchange (SAX) of 10-μm styrene divinylbenzene (SDB) particles embedded in Teflon, and the second disk was a C18 disk of 10-μm particles also embedded in Teflon. A volume of 500 mL of water or aqueous soil extract is passed through the layered system with the SAX disk first. The purpose of the SAX disk is to remove the humic and fulvic acids from the water or aqueous soil extract by ion exchange through their carboxyl groups. Even during methanol elution of herbicides, the humic substances remain bound to the SAX disk with >85% retention. Elution with methanol results in more than 90% recovery of the herbicides from the layered extraction disks. Removal of the humic and fulvic acids results in greater sensitivity for diode array detection quantitation (0.05 μg/L for herbicides) by substantially reducing the absorbance of the humic peak on the LC chromatogram. The herbicides adsorb to the SAX disk either through hydrogen bonding to the anion-exchange sites or by hydrophobic interaction with the SDB surface of the anion-exchange disk. The method was tested for the analysis of natural water samples from the Mississippi Embayment, a cotton-growing area of the southeastern United States.
Phase diagram of nanoscale alloy particles used for vapor-liquid-solid growth of semiconductor nanowires.

PubMed

Sutter, Eli; Sutter, Peter

2008-02-01

We use transmission electron microscopy observations to establish the parts of the phase diagram of nanometer sized Au-Ge alloy drops at the tips of Ge nanowires (NWs) that determine their temperature-dependent equilibrium composition and, hence, their exchange of semiconductor material with the NWs. We find that the phase diagram of the nanoscale drop deviates significantly from that of the bulk alloy, which explains discrepancies between actual growth results and predictions on the basis of the bulk-phase equilibria. Our findings provide the basis for tailoring vapor-liquid-solid growth to achieve complex one-dimensional materials geometries.
Hybrid organic-inorganic inks flatten the energy landscape in colloidal quantum dot solids

NASA Astrophysics Data System (ADS)

Liu, Mengxia; Voznyy, Oleksandr; Sabatini, Randy; García de Arquer, F. Pelayo; Munir, Rahim; Balawi, Ahmed Hesham; Lan, Xinzheng; Fan, Fengjia; Walters, Grant; Kirmani, Ahmad R.; Hoogland, Sjoerd; Laquai, Frédéric; Amassian, Aram; Sargent, Edward H.

2017-02-01

Bandtail states in disordered semiconductor materials result in losses in open-circuit voltage (Voc) and inhibit carrier transport in photovoltaics. For colloidal quantum dot (CQD) films that promise low-cost, large-area, air-stable photovoltaics, bandtails are determined by CQD synthetic polydispersity and inhomogeneous aggregation during the ligand-exchange process. Here we introduce a new method for the synthesis of solution-phase ligand-exchanged CQD inks that enable a flat energy landscape and an advantageously high packing density. In the solid state, these materials exhibit a sharper bandtail and reduced energy funnelling compared with the previous best CQD thin films for photovoltaics. Consequently, we demonstrate solar cells with higher Voc and more efficient charge injection into the electron acceptor, allowing the use of a closer-to-optimum bandgap to absorb more light. These enable the fabrication of CQD solar cells made via a solution-phase ligand exchange, with a certified power conversion efficiency of 11.28%. The devices are stable when stored in air, unencapsulated, for over 1,000 h.

Melting of Simple Solids and the Elementary Excitations of the Communal Entropy

NASA Astrophysics Data System (ADS)

Bongiorno, Angelo

2010-03-01

The melting phase transition of simple solids is addressed through the use of atomistic computer simulations. Three transition metals (Ni, Au, and Pt) and a semiconductor (Si) are considered in this study. Iso-enthalpic molecular dynamics simulations are used to compute caloric curves across the solid-to-liquid phase transition of a periodic crystalline system, to construct the free energy function of the solid and liquid phases, and thus to derive the thermodynamical limit of the melting point, latent heat and entropy of fusion of the material. The computational strategy used in this study yields accurate estimates of melting parameters, it consents to determine the superheating and supercooling temperature limits, and it gives access to the atomistic mechanisms mediating the melting process. In particular, it is found that the melting phase transition in simple solids is driven by exchange steps involving a few atoms and preserving the crystalline structure. These self-diffusion phenomena correspond to the elementary excitations of the communal entropy and, as their rate depends on the local material cohesivity, they mediate both the homogeneous and non-homogeneous melting process in simple solids.
Resolving Confined 7Li Dynamics of Uranyl Peroxide Capsule U 24

DOE PAGES

Xie, Jing; Neal, Harrison A.; Szymanowski, Jennifer; ...

2018-04-18

Here, we obtained a kerosene-soluble form of the lithium salt [UO 2(O 2)(OH) 2] 24 phase (Li-U 24), by adding cetyltrimethylammonium bromide surfactant to aqueous Li-U 24. Interestingly, its variable-temperature solution 7Li NMR spectroscopy resolves two narrowly spaced resonances down to –10 °C, which shift upfield with increasing temperature, and finally coalesce at temperatures > 85 °C. Comparison with solid-state NMR demonstrates that the Li dynamics in the Li-U 24-CTA phase involves only exchange between different local encapsulated environments. This behavior is distinct from the rapid Li exchange dynamics observed between encapsulated and external Li environments for Li-U 24 inmore » both the aqueous and the solid-state phases. Density functional theory calculations suggest that the two experimental 7Li NMR chemical shifts are due to Li cations coordinated within the square and hexagonal faces of the U 24 cage, and they can undergo exchange within the confined environment, as the solution is heated. Very different than U 24 in aqueous media, there is no evidence that the Li cations exit the cage, and therefore, this represents a truly confined space.« less
Resolving Confined 7Li Dynamics of Uranyl Peroxide Capsule U 24

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

Xie, Jing; Neal, Harrison A.; Szymanowski, Jennifer

Here, we obtained a kerosene-soluble form of the lithium salt [UO 2(O 2)(OH) 2] 24 phase (Li-U 24), by adding cetyltrimethylammonium bromide surfactant to aqueous Li-U 24. Interestingly, its variable-temperature solution 7Li NMR spectroscopy resolves two narrowly spaced resonances down to –10 °C, which shift upfield with increasing temperature, and finally coalesce at temperatures > 85 °C. Comparison with solid-state NMR demonstrates that the Li dynamics in the Li-U 24-CTA phase involves only exchange between different local encapsulated environments. This behavior is distinct from the rapid Li exchange dynamics observed between encapsulated and external Li environments for Li-U 24 inmore » both the aqueous and the solid-state phases. Density functional theory calculations suggest that the two experimental 7Li NMR chemical shifts are due to Li cations coordinated within the square and hexagonal faces of the U 24 cage, and they can undergo exchange within the confined environment, as the solution is heated. Very different than U 24 in aqueous media, there is no evidence that the Li cations exit the cage, and therefore, this represents a truly confined space.« less
End-Member Formulation of Solid Solutions and Reactive Transport

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

Lichtner, Peter C.

2015-09-01

A model for incorporating solid solutions into reactive transport equations is presented based on an end-member representation. Reactive transport equations are solved directly for the composition and bulk concentration of the solid solution. Reactions of a solid solution with an aqueous solution are formulated in terms of an overall stoichiometric reaction corresponding to a time-varying composition and exchange reactions, equivalent to reaction end-members. Reaction rates are treated kinetically using a transition state rate law for the overall reaction and a pseudo-kinetic rate law for exchange reactions. The composition of the solid solution at the onset of precipitation is assumed tomore » correspond to the least soluble composition, equivalent to the composition at equilibrium. The stoichiometric saturation determines if the solid solution is super-saturated with respect to the aqueous solution. The method is implemented for a simple prototype batch reactor using Mathematica for a binary solid solution. Finally, the sensitivity of the results on the kinetic rate constant for a binary solid solution is investigated for reaction of an initially stoichiometric solid phase with an undersaturated aqueous solution.« less
A fluorescent-photochrome method for the quantitative characterization of solid phase antibody orientation.

PubMed

Ahluwalia, Arti; De Rossi, Danilo; Giusto, Giuseppe; Chen, Oren; Papper, Vladislav; Likhtenshtein, Gertz I

2002-06-15

A fluorescent-photochrome method of quantifying the orientation and surface density of solid phase antibodies is described. The method is based on measurements of quenching and rates of cis-trans photoisomerization and photodestruction of a stilbene-labeled hapten by a quencher in solution. These experimental parameters enable a quantitative description of the order of binding sites of antibodies immobilized on a surface and can be used to characterize the microviscosity and steric hindrance in the vicinity of the binding site. Furthermore, a theoretical method for the determination of the depth of immersion of the fluorescent label in a two-phase system was developed. The model exploits the concept of dynamic interactions and is based on the empirical dependence of parameters of static exchange interactions on distances between exchangeable centers. In the present work, anti-dinitrophenyl (DNP) antibodies and stilbene-labeled DNP were used to investigate three different protein immobilization methods: physical adsorption, covalent binding, and the Langmuir-Blodgett technique. Copyright 2002 Elsevier Science (USA).
Measurement of thyroxine and its glucuronide in municipal wastewater and solids using weak anion exchange solid phase extraction and ultrahigh performance liquid chromatography-tandem mass spectrometry.

PubMed

Brown, Alistair K; Wong, Charles S

2017-11-24

A solids extraction method, using sonication in combination with weak anion exchange solid phase extraction, was created to extract thyroxine (T4) and thyroxine-O-β-d-glucuronide (T4-Glc) simultaneously from wastewaters and sludges, and to quantify these compounds via reversed-phase ultra-high performance liquid chromatography-tandem mass spectrometry. The method limits of quantification were all in the low ng/g (dry weight solids) range for both T4 and T4-Glc: 2.13 and 2.63ng/g respectively in primary wastewater, 4.3 and 28.3ng/g for primary suspended solids, for 1.1 and 3.7ng/g for return activated sludge. Precision for measurements of T4 and T4-Glc were 2.6 and 6.5% (intraday) and 9.6 and 5.7% (interday) respectively, while linearity was 0.9967 and 0.9943 respectively. Overall recoveries for T4 and T4-Glc in primary suspended solids were 94% and 95%, and 86 and 101% in primary wastewater, respectively. Extraction efficiency tests using primary sludge determined that one methanol aliquot was sufficient during the extraction process as opposed to 2 or 3 aliquots. Mass loadings at the North Main Wastewater Treatment Plant in Winnipeg, Canada showed 316%, 714%, and 714% greater T4-Glc than T4 associated with the suspended solids of the primary, secondary, and final effluent respectively, yet 765% more T4 than T4-Glc associated with the solids of the mixed liquor. Moreover, 26% of T4 and 49% of T4-Glc were associated with the suspended solids during the treatment process. This method demonstrates the need to assess accurately both metabolite conjugates of contaminants of emerging concern, as well as the sorbed levels of particle-reactive analytes such as T4 in the aquatic environment. Copyright © 2017 Elsevier B.V. All rights reserved.
Stability of the solid electrolyte Li{sub 3}OBr to common battery solvents

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

Schroeder, D.J.; Hubaud, A.A.; Vaughey, J.T., E-mail: vaughey@anl.gov

2014-01-01

Graphical abstract: The stability of the anti-perovskite phase Li{sub 3}OBr has been assessed in a variety of battery solvents. - Highlights: • Lithium stable solid electrolyte Li{sub 3}OBr unstable to polar organic solvents. • Solvation with no dissolution destroys long-range structure. • Ion exchange with protons observed. - Abstract: Recently a new class of solid lithium ion conductors was reported based on the anti-perovskite structure, notably Li{sub 3}OCl and Li{sub 3}OBr. For many beyond lithium-ion battery uses, the solid electrolyte is envisioned to be in direct contact with liquid electrolytes and lithium metal. In this study we evaluated the stabilitymore » of the Li{sub 3}OBr phase against common battery solvents electrolytes, including diethylcarbonate (DEC) and dimethylcarbonate (DMC), as well as a LiPF{sub 6} containing commercial electrolyte. In contact with battery-grade organic solvents, Li{sub 3}OBr was typically found to be insoluble but lost its crystallinity and reacted with available protons and in some cases with the solvent. A low temperature heat treatment was able to restore crystallinity of the samples; however evidence of proton ion exchange was conserved.« less
Thermal power transfer system using applied potential difference to sustain operating pressure difference

NASA Technical Reports Server (NTRS)

Bhandari, Pradeep (Inventor); Fujita, Toshio (Inventor)

1991-01-01

A thermal power transfer system using a phase change liquid gas fluid in a closed loop configuration has a heat exchanger member connected to a gas conduit for inputting thermal energy into the fluid. The pressure in the gas conduit is higher than a liquid conduit that is connected to a heat exchanger member for outputting thermal energy. A solid electrolyte member acts as a barrier between the gas conduit and the liquid conduit adjacent to a solid electrolyte member. The solid electrolyte member has the capacity of transmitting ions of a fluid through the electrolyte member. The ions can be recombined with electrons with the assistance of a porous electrode. An electrical field is applied across the solid electrolyte member to force the ions of the fluid from a lower pressure liquid conduit to the higher pressure gas conduit.
Hybrid organic-inorganic inks flatten the energy landscape in colloidal quantum dot solids.

PubMed

Liu, Mengxia; Voznyy, Oleksandr; Sabatini, Randy; García de Arquer, F Pelayo; Munir, Rahim; Balawi, Ahmed Hesham; Lan, Xinzheng; Fan, Fengjia; Walters, Grant; Kirmani, Ahmad R; Hoogland, Sjoerd; Laquai, Frédéric; Amassian, Aram; Sargent, Edward H

2017-02-01

Bandtail states in disordered semiconductor materials result in losses in open-circuit voltage (V oc ) and inhibit carrier transport in photovoltaics. For colloidal quantum dot (CQD) films that promise low-cost, large-area, air-stable photovoltaics, bandtails are determined by CQD synthetic polydispersity and inhomogeneous aggregation during the ligand-exchange process. Here we introduce a new method for the synthesis of solution-phase ligand-exchanged CQD inks that enable a flat energy landscape and an advantageously high packing density. In the solid state, these materials exhibit a sharper bandtail and reduced energy funnelling compared with the previous best CQD thin films for photovoltaics. Consequently, we demonstrate solar cells with higher V oc and more efficient charge injection into the electron acceptor, allowing the use of a closer-to-optimum bandgap to absorb more light. These enable the fabrication of CQD solar cells made via a solution-phase ligand exchange, with a certified power conversion efficiency of 11.28%. The devices are stable when stored in air, unencapsulated, for over 1,000 h.
Dye-doped nanostructure polypyrrole film for electrochemically switching solid-phase microextraction of Ni(II) and ICP-OES analysis of waste water.

PubMed

Shamaeli, Ehsan; Alizadeh, Naader

2012-01-01

A nanostructure fiber based on conducting polypyrrole synthesized by an electrochemical method has been developed, and used for electrochemically switching solid-phase microextraction (ES-SPME). The ES-SPME was prepared by the doping of eriochrome blue in polypyrrole (PPy-ECB) and used for selectively extracting the Ni(II) cation in the presence of some transition and heavy metal ions. The cation-exchange behavior of electrochemically prepared polypyrrole on stainless-steel with and without eriochrome blue (ECB) dye was characterized using ICP-OES analysis. The effects of the scan rate for electrochemical synthesis, uptake and the release potential on the extraction behavior of the PPy-ECB conductive fiber were studied. Uptake and release time profiles show that the process of electrically switched cation exchange could be completed within 250 s. The results of the present study point concerning the possibility of developing a selective extraction process for Ni(II) from waste water was explored using such a nanostructured PPy-ECB film through an electrically switched cation exchange. 2012 © The Japan Society for Analytical Chemistry
An Isotopic Exchange Kinetic Model to Assess the Speciation of Metal Available Pool in Soil: The Case of Nickel.

PubMed

Zelano, I O; Sivry, Y; Quantin, C; Gélabert, A; Maury, A; Phalyvong, K; Benedetti, M F

2016-12-06

In this study an innovative approach is proposed to predict the relative contribution of each mineral phase to the total metal availability in soils, which, in other words, could be called the available metal fractionation. Through the use of isotopic exchange kinetics (IEK) performed on typical Ni bearing phases (i.e., two types of serpentines, chlorite, smectite, goethite, and hematite) the isotopic exchange and metal-solid interaction processes are connected, considering both the thermodynamic and kinetic aspects. Results of Ni IEK experiments on mineral phases are fitted with a pseudo-first order kinetic model. For each Ni bearing phase, this allows to (i) determine the number and size of exchangeable pools (E Ni(i) ), (ii) assess their corresponding kinetic constants (k (i) ), and (iii) discuss the mechanism of Ni isotopic exchange at mineral surfaces. It is shown that all the phases investigated, with the only exception of hematite, present at least two distinct reactive pools with significantly different k (i) values. Results suggest also that metal involved in outer-sphere complexes would display isotopic exchange between 100 and 1000 times faster than metal involved in inner-sphere complexes, and that the presence of high and low affinity sites may influence the rate of isotopic exchange up to 1 order of magnitude. Moreover, the method developed represents a tool to predict and estimate Ni mobility and availability in natural soil samples on the basis of soil mineral composition, providing information barely obtained with other techniques.
A review on solid phase extraction of actinides and lanthanides with amide based extractants.

PubMed

Ansari, Seraj A; Mohapatra, Prasanta K

2017-05-26

Solid phase extraction is gaining attention from separation scientists due to its high chromatographic utility. Though both grafted and impregnated forms of solid phase extraction resins are popular, the later is easy to make by impregnating a given organic extractant on to an inert solid support. Solid phase extraction on an impregnated support, also known as extraction chromatography, combines the advantages of liquid-liquid extraction and the ion exchange chromatography methods. On the flip side, the impregnated extraction chromatographic resins are less stable against leaching out of the organic extractant from the pores of the support material. Grafted resins, on the other hand, have a higher stability, which allows their prolong use. The goal of this article is a brief literature review on reported actinide and lanthanide separation methods based on solid phase extractants of both the types, i.e., (i) ligand impregnation on the solid support or (ii) ligand functionalized polymers (chemically bonded resins). Though the literature survey reveals an enormous volume of studies on the extraction chromatographic separation of actinides and lanthanides using several extractants, the focus of the present article is limited to the work carried out with amide based ligands, viz. monoamides, diamides and diglycolamides. The emphasis will be on reported applied experimental results rather than on data pertaining fundamental metal complexation. Copyright © 2017 Elsevier B.V. All rights reserved.
Automated solid-phase extraction of phenolic acids using layered double hydroxide-alumina-polymer disks.

PubMed

Ghani, Milad; Palomino Cabello, Carlos; Saraji, Mohammad; Manuel Estela, Jose; Cerdà, Víctor; Turnes Palomino, Gemma; Maya, Fernando

2018-01-26

The application of layered double hydroxide-Al 2 O 3 -polymer mixed-matrix disks for solid-phase extraction is reported for the first time. Al 2 O 3 is embedded in a polymer matrix followed by an in situ metal-exchange process to obtain a layered double hydroxide-Al 2 O 3 -polymer mixed-matrix disk with excellent flow-through properties. The extraction performance of the prepared disks is evaluated as a proof of concept for the automated extraction using sequential injection analysis of organic acids (p-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid, gallic acid) following an anion-exchange mechanism. After the solid-phase extraction, phenolic acids were quantified by reversed-phase high-performance liquid chromatography with diode-array detection using a core-shell silica-C18 stationary phase and isocratic elution (acetonitrile/0.5% acetic acid in pure water, 5:95, v/v). High sensitivity and reproducibility were obtained with limits of detection in the range of 0.12-0.25 μg/L (sample volume, 4 mL), and relative standard deviations between 2.9 and 3.4% (10 μg/L, n = 6). Enrichment factors of 34-39 were obtained. Layered double hydroxide-Al 2 O 3 -polymer mixed-matrix disks had an average lifetime of 50 extractions. Analyte recoveries ranged from 93 to 96% for grape juice and nonalcoholic beer samples. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Ultrasound-assisted analyte extraction for the determination of sulfate and elemental sulfur in zinc sulfide by different liquid chromatography techniques.

PubMed

Dash, K; Thangavel, S; Krishnamurthy, N V; Rao, S V; Karunasagar, D; Arunachalam, J

2005-04-01

The speciation and determination of sulfate (SO4(2-)) and elemental sulfur (S degree) in zinc sulfide (ZnS) using ion-chromatography (IC) and reversed-phase liquid chromatography (RPLC) respectively is described. Three sample pretreatment approaches were employed with the aim of determining sulfate: (i) conventional water extraction of the analyte; (ii) solid-liquid aqueous extraction with an ultrasonic probe; and (iii) elimination of the zinc sulfide matrix via ion-exchange dissolution (IED). The separation of sulfate was carried out by an anion-exchange column (IonPac AS17), followed by suppressed conductivity detection. Elemental sulfur was extracted ultrasonically from the acid treated sample solution into chloroform and separated on a reversed phase HPLC column equipped with a diode array detector (DAD) at 264 nm. The achievable solid detection limits for sulfate and sulfur were 35 and 10 microg g(-1) respectively.
First-principles investigation of competing magnetic interactions in (Mn ,Fe )Ru2Sn Heusler solid solutions

NASA Astrophysics Data System (ADS)

Decolvenaere, Elizabeth; Gordon, Michael; Seshadri, Ram; Van der Ven, Anton

2017-10-01

Many Heusler compounds possess magnetic properties well suited for applications as spintronic materials. The pseudobinary Mn0.5Fe0.5Ru2Sn , formed as a solid solution of two full Heuslers, has recently been shown to exhibit exchange hardening suggestive of two magnetic phases, despite existing as a single chemical phase. We have performed a first-principles study of the chemical and magnetic degrees of freedom in the Mn1 -xFexRu2Sn pseudobinary to determine the origin of the unique magnetic behavior responsible for exchange hardening within a single phase. We find a transition from antiferromagnetic (AFM) to ferromagnetic (FM) behavior upon replacement of Mn with Fe, consistent with experimental results. The lowest energy orderings in Mn1 -xFexRu2Sn consist of chemically and magnetically uniform (111) planes, with Fe-rich regions preferring FM ordering and Mn-rich regions preferring AFM ordering, independent of the overall composition. Analysis of the electronic structure suggests that the magnetic behavior of this alloy arises from a competition between AFM-favoring Sn-mediated superexchange and FM-favoring RKKY exchange mediated by spin-polarized conduction electrons. Changes in valency upon replacement of Mn with Fe shifts the balance from superexchange-dominated interactions to RKKY-dominated interactions.
A one-dimensional heat transfer model for parallel-plate thermoacoustic heat exchangers.

PubMed

de Jong, J A; Wijnant, Y H; de Boer, A

2014-03-01

A one-dimensional (1D) laminar oscillating flow heat transfer model is derived and applied to parallel-plate thermoacoustic heat exchangers. The model can be used to estimate the heat transfer from the solid wall to the acoustic medium, which is required for the heat input/output of thermoacoustic systems. The model is implementable in existing (quasi-)1D thermoacoustic codes, such as DeltaEC. Examples of generated results show good agreement with literature results. The model allows for arbitrary wave phasing; however, it is shown that the wave phasing does not significantly influence the heat transfer.
Fabrication of a novel hydrophobic/ion-exchange mixed-mode adsorbent for the dispersive solid-phase extraction of chlorophenols from environmental water samples.

PubMed

Gao, Li; Wei, Yinmao

2016-08-01

A novel mixed-mode adsorbent was prepared by functionalizing silica with tris(2-aminoethyl)amine and 3-phenoxybenzaldehyde as the main mixed-mode scaffold due to the presence of the plentiful amino groups and benzene rings in their molecules. The adsorption mechanism was probed with acidic, natural and basic compounds, and the mixed hydrophobic and ion-exchange interactions were found to be responsible for the adsorption of analytes. The suitability of dispersive solid-phase extraction was demonstrated in the determination of chlorophenols in environmental water. Several parameters, including sample pH, desorption solvent, ionic strength, adsorbent dose, and extraction time were optimized. Under the optimal extraction conditions, the proposed dispersive solid-phase extraction coupled with high-performance liquid chromatography showed good linearity range and acceptable limits of detection (0.22∽0.54 ng/mL) for five chlorophenols. Notably, the higher extraction recoveries (88.7∽109.7%) for five chlorophenols were obtained with smaller adsorbent dose (10 mg) and shorter extraction time (15 min) compared with the reported methods. The proposed method might be potentially applied in the determination of trace chlorophenols in real water samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Solid cation exchange phase to remove interfering anthocyanins in the analysis of other bioactive phenols in red wine.

PubMed

da Silva, Letícia Flores; Guerra, Celito Crivellaro; Klein, Diandra; Bergold, Ana Maria

2017-07-15

Bioactive phenols (BPs) are often targets in red wine analysis. However, other compounds interfere in the liquid chromatography methods used for this analysis. Here, purification procedures were tested to eliminate anthocyanin interference during the determination of 19 red-wine BPs. Liquid chromatography, coupled to a diode array detector (HPLC-DAD) and a mass spectrometer (UPLC-MS), was used to compare the direct injection of the samples with solid-phase extractions: reversed-phase (C18) and strong cation-exchange (SCX). The HPLC-DAD method revealed that, out of 13BPs, only six are selectively analyzed with or without C18 treatment, whereas SCX enabled the detection of all BPs. The recovery with SCX was above 86.6% for eight BPs. Moreover, UPLC-MS demonstrated the potential of SCX sample preparation for the determination of 19BPs. The developed procedure may be extended to the analysis of other red wine molecules or to other analytical methods where anthocyanins may interfere. Copyright © 2017 Elsevier Ltd. All rights reserved.
Analytical modeling of localized surface plasmon resonance in heterostructure copper sulfide nanocrystals

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

Caldwell, Andrew H.; Ha, Don-Hyung; Ding, Xiaoyue

2014-10-28

Localized surface plasmon resonance (LSPR) in semiconductor nanocrystals is a relatively new field of investigation that promises greater tunability of plasmonic properties compared to metal nanoparticles. A novel process by which the LSPR in semiconductor nanocrystals can be altered is through heterostructure formation arising from solution-based cation exchange. Herein, we describe the development of an analytical model of LSPR in heterostructure copper sulfide-zinc sulfide nanocrystals synthesized via a cation exchange reaction between copper sulfide (Cu 1.81S) nanocrystals and Zn ions. The cation exchange reaction produces dual-interface, heterostructure nanocrystals in which the geometry of the copper sulfide phase can be tunedmore » from a sphere to a thin disk separating symmetrically-grown sulfide (ZnS) grains. Drude model electronic conduction and Mie-Gans theory are applied to describe how the LSPR wavelength changes during cation exchange, taking into account the morphology evolution and changes to the local permittivity. The results of the modeling indicate that the presence of the ZnS grains has a significant effect on the out-of-plane LSPR mode. By comparing the results of the model to previous studies on solid-solid phase transformations of copper sulfide in these nanocrystals during cation exchange, we show that the carrier concentration is independent of the copper vacancy concentration dictated by its atomic phase. The evolution of the effective carrier concentration calculated from the model suggests that the out-of-plane resonance mode is dominant. The classical model was compared to a simplified quantum mechanical model which suggested that quantum mechanical effects become significant when the characteristic size is less than ~8 nm. Overall, we find that the analytical models are not accurate for these heterostructured semiconductor nanocrystals, indicating the need for new model development for this emerging field.« less
Analytical modeling of localized surface plasmon resonance in heterostructure copper sulfide nanocrystals

NASA Astrophysics Data System (ADS)

Caldwell, Andrew H.; Ha, Don-Hyung; Ding, Xiaoyue; Robinson, Richard D.

2014-10-01

Localized surface plasmon resonance (LSPR) in semiconductor nanocrystals is a relatively new field of investigation that promises greater tunability of plasmonic properties compared to metal nanoparticles. A novel process by which the LSPR in semiconductor nanocrystals can be altered is through heterostructure formation arising from solution-based cation exchange. Herein, we describe the development of an analytical model of LSPR in heterostructure copper sulfide-zinc sulfide nanocrystals synthesized via a cation exchange reaction between copper sulfide (Cu1.81S) nanocrystals and Zn ions. The cation exchange reaction produces dual-interface, heterostructure nanocrystals in which the geometry of the copper sulfide phase can be tuned from a sphere to a thin disk separating symmetrically-grown sulfide (ZnS) grains. Drude model electronic conduction and Mie-Gans theory are applied to describe how the LSPR wavelength changes during cation exchange, taking into account the morphology evolution and changes to the local permittivity. The results of the modeling indicate that the presence of the ZnS grains has a significant effect on the out-of-plane LSPR mode. By comparing the results of the model to previous studies on solid-solid phase transformations of copper sulfide in these nanocrystals during cation exchange, we show that the carrier concentration is independent of the copper vacancy concentration dictated by its atomic phase. The evolution of the effective carrier concentration calculated from the model suggests that the out-of-plane resonance mode is dominant. The classical model was compared to a simplified quantum mechanical model which suggested that quantum mechanical effects become significant when the characteristic size is less than ˜8 nm. Overall, we find that the analytical models are not accurate for these heterostructured semiconductor nanocrystals, indicating the need for new model development for this emerging field.

Clusters and holes: Exchange networks in hematite-ilmenite solid solutions

NASA Astrophysics Data System (ADS)

Fabian, K.; McEnroe, S. A.; Robinson, P.

2009-04-01

Holes and clusters of exchange networks dominate the low-temperature, metastable phase diagram of the system (1 - x)Fe2O3 xF eTiO3 (Ilmx ). By our measurements we have probed and extended the phase diagram of Ishikawa et al. (1985) in the light of magnetic influences of the random exchange links, which originate either by replacing random pairs of Fe2+ and Ti4+ ions in the ordered ilmenite lattice by two Fe3+ions (ordered Ilmx phase), or by randomly replacing two Fe3+ ions in the hematite lattice by a pair of Fe2+ and Ti4+ ions (disordered Ilmx phase). Now a large dataset is available from these measurements, and we propose several new ideas to interpret the sometimes unexpected results. By refining a method of Ishikawa (1967), we analyze the PM' region of the phase diagram in terms of a mean field theory of interacting clusters. This allows to determine cluster sizes and interaction field distribution by inverting hysteresis measurements of Ilm92 and Ilm97. To understand the relation between ordered and disordered phases we design a mean field theory to determine Neel and Curie temperatures of both. An especially interesting finding is that the experimentally observed intersection of PM-PM' crossover with the AF phase boundary close to Ilm97 can be explained by analyzing average exchange interaction strengths.
Allantoin as a solid phase adsorbent for removing endotoxins.

PubMed

Vagenende, Vincent; Ching, Tim-Jang; Chua, Rui-Jing; Gagnon, Pete

2013-10-04

In this study we present a simple and robust method for removing endotoxins from protein solutions by using crystals of the small-molecule compound 2,5-dioxo-4-imidazolidinyl urea (allantoin) as a solid phase adsorbent. Allantoin crystalline powder is added to a protein solution at supersaturated concentrations, endotoxins bind and undissolved allantoin crystals with bound endotoxins are removed by filtration or centrifugation. This method removes an average of 99.98% endotoxin for 20 test proteins. The average protein recovery is ∼80%. Endotoxin binding is largely independent of pH, conductivity, reducing agent and various organic solvents. This is consistent with a hydrogen-bond based binding mechanism. Allantoin does not affect protein activity and stability, and the use of allantoin as a solid phase adsorbent provides better endotoxin removal than anion exchange, polymixin affinity and biological affinity methods for endotoxin clearance. Copyright © 2013 Elsevier B.V. All rights reserved.
Exergy optimization in a steady moving bed heat exchanger.

PubMed

Soria-Verdugo, A; Almendros-Ibáñez, J A; Ruiz-Rivas, U; Santana, D

2009-04-01

This work provides an energy and exergy optimization analysis of a moving bed heat exchanger (MBHE). The exchanger is studied as a cross-flow heat exchanger where one of the phases is a moving granular medium. The optimal MBHE dimensions and the optimal particle diameter are obtained for a range of incoming fluid flow rates. The analyses are carried out over operation data of the exchanger obtained in two ways: a numerical simulation of the steady-state problem and an analytical solution of the simplified equations, neglecting the conduction terms. The numerical simulation considers, for the solid, the convection heat transfer to the fluid and the diffusion term in both directions, and for the fluid only the convection heat transfer to the solid. The results are compared with a well-known analytical solution (neglecting conduction effects) for the temperature distribution in the exchanger. Next, the analytical solution is used to derive an expression for the exergy destruction. The optimal length of the MBHE depends mainly on the flow rate and does not depend on particle diameter unless they become very small (thus increasing sharply the pressure drop). The exergy optimal length is always smaller than the thermal one, although the difference is itself small.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Chezhina, N.V., E-mail: chezhina@nc2490.spb.edu; Korolev, D.A.; Zhuk, N.A.

On the basis of the results of magnetic susceptibility and ESR studies of the Bi{sub 3}Nb{sub 1−x}Fe{sub x}O{sub 7−δ} solid solutions iron atoms in the solid solutions of cubic modification of bismuth niobate were found to exist as Fe(III) monomers and exchange bound Fe(III)-O-Fe(III) dimers with antiferro- and ferromagnetic type of superexchange. The exchange parameters and the distribution of monomers and dimers in the solid solutions were calculated as a function of paramagnetic atom content. - Graphical abstract: The study of the Bi{sub 3}Nb{sub 1−x}Fe{sub x}O{sub 7−δ} solid solutions showed that the introduction of iron atoms into the structure ofmore » Bi{sub 3}NbO{sub 7} stabilizes the cubic structure of bismuth niobate making the phase transition tetragonal ↔ cubic structure irreversible. In the Bi{sub 3}Nb{sub 1−x}Fe{sub x}O{sub 7−δ} solid solutions we observe the formation of dimers with antiferro- and ferromagnetic exchange. Such clusters are partially retained even at the infinite dilution of the solid solution, which testifies for their rigidity. A sufficiently high parameter of ferromagnetic exchange in a dimer (+53 cm{sup −1}) seems to result from iron atoms being located in the vicinity of oxygen vacancy. - Highlights: • The reversible transition cubic – tetragonal modifications in Bi{sub 3}NbO{sub 7} becomes irreversible. • Only cubic modification of Bi{sub 3}Nb{sub 1-x}Fe{sub x}O{sub 7-δ} is stable due to clusters of Fe atoms. • These clusters are sufficiently strong and retained even at the infinite dilution. • The calculations of magnetic susceptibility give the distribution of the clusters and single atoms.« less
Ionic Liquid-Hybrid Molecularly Imprinted Material-Filter Solid-Phase Extraction Coupled with HPLC for Determination of 6-Benzyladenine and 4-Chlorophenoxyacetic Acid in Bean Sprouts.

PubMed

Han, Yehong; Yang, Chunliu; Zhou, Yang; Han, Dandan; Yan, Hongyuan

2017-03-01

A new method involving ionic liquid-hybrid molecularly imprinted material-filter solid-phase extraction coupled to high-performance liquid chromatography (IL-HIM-FSPE-HPLC) was developed for the simultaneous isolation and determination of 6-benzyladenine (6-BA) and 4-chlorophenoxyacetic acid (4-CPA) in bean sprouts. Sample preconcentration was performed using a modified filter, with the new IL-HIM as the adsorbent, which shows double adsorption. The first adsorption involves special recognition of molecular imprinting, and the second involves ion exchange and electrostatic attraction caused by the ionic liquid. This method combines the advantages of ionic liquids, hybrid materials, and molecularly imprinted polymers and was successfully applied to determine 6-BA and 4-CPA in bean sprouts. The adsorption of 6-BA to IL-HIM is based on selective imprinted recognition, whereas the adsorption of 4-CPA is mainly dependent on ion-exchange interactions.
Constitutive Relationships and Models in Continuum Theories of Multiphase Flows. [conferences

NASA Technical Reports Server (NTRS)

Decker, Rand (Editor)

1989-01-01

In April, 1989, a workshop on constitutive relationships and models in continuum theories of multiphase flows was held at NASA's Marshall Space Flight Center. Topics of constitutive relationships for the partial or per phase stresses, including the concept of solid phase pressure are discussed. Models used for the exchange of mass, momentum, and energy between the phases in a multiphase flow are also discussed. The program, abstracts, and texts of the presentations from the workshop are included.
Semiautomated solid-phase extraction manifold with a solvent-level sensor.

PubMed

Orlando, R M; Rath, S; Rohwedder, J J R

2013-11-15

A semiautomated solid-phase extraction manifold for multiple extractions is presented. The manifold utilizes commercial solid-phase syringe cartridges and automatically introduces and elutes all the solvents during the extraction, reducing the typical workload and stress of the analyst. The manifold consists of a peristaltic pump with solenoid valves in a flow circuit that contains transmissive photomicrosensors. The photomicrosensors were used to control the solvent dispenser and the solvent level inside the cartridge. As solvent-level sensors, the photomicrosensors determined the exact time the solvent reached the top frit to avoid sorbent drying and accurately perform the solvent exchange. The repeatability of the manifold to introduce a particular volume of solvent into the cartridges was measured, and the precisions were between 0.05 and 2.89% (RSD). To evaluate the manifold, the amount of two fluoroquinolones in a fortified blank milk sample was determined. The results of the intra- and inter-day precision of multiple extractions from the fortified milk samples resulted in precisions better than 9.0% (RSD) and confirmed that the arrangement of the semiautomated manifold could adequately be used in solid-phase extraction with commercial cartridges. Copyright © 2013 Elsevier B.V. All rights reserved.
Alkaloid profiles of Mimosa tenuiflora and associated methods of analysis

USDA-ARS?s Scientific Manuscript database

The alkaloid contents of the leaves and seeds of M. tenuiflora collected from northeastern Brazil were studied. Alkaloids were isolated by classical acid/base extraction procedures and by cation exchange solid phase extraction. The crude alkaloid fractions were then analysed by thin layer chromatogr...
High temperature coercive field behavior of Fe-Zr powder

NASA Astrophysics Data System (ADS)

Mishra, Debabrata; Perumal, A.; Srinivasan, A.

2009-04-01

We report the investigation of high temperature coercive field behavior of Fe80Zr20 nanocrystalline alloy powder having two-phase microstructure prepared by mechanical alloying process. Thermomagnetization measurement shows the presence of two different magnetic phase transitions corresponding to the amorphous matrix and nonequilibrium Fe(Zr) solid solution. Temperature dependent coercivity exhibits a sharp increase in its value close to the Curie temperature of the amorphous matrix. This feature is attributed to the loss of intergranular ferromagnetic exchange coupling between the nanocrystallites due to the paramagnetic nature of the amorphous matrix. The temperature dependent coercive field behavior is ascribed to the variations in both the effective anisotropy and the exchange stiffness constant with temperature.
Mixed-mode isolation of triazine metabolites from soil and aquifer sediments using automated solid-phase extraction

USGS Publications Warehouse

Mills, M.S.; Thurman, E.M.

1992-01-01

Reversed-phase isolation and ion-exchange purification were combined in the automated solid-phase extraction of two polar s-triazine metabolites, 2-amino-4-chloro-6-(isopropylamino)-s-triazine (deethylatrazine) and 2-amino-4-chloro-6-(ethylamino)-s-triazine (deisopropylatrazine) from clay-loam and slit-loam soils and sandy aquifer sediments. First, methanol/ water (4/1, v/v) soil extracts were transferred to an automated workstation following evaporation of the methanol phase for the rapid reversed-phase isolation of the metabolites on an octadecylresin (C18). The retention of the triazine metabolites on C18 decreased substantially when trace methanol concentrations (1%) remained. Furthermore, the retention on C18 increased with decreasing aqueous solubility and increasing alkyl-chain length of the metabolites and parent herbicides, indicating a reversed-phase interaction. The analytes were eluted with ethyl acetate, which left much of the soil organic-matter impurities on the resin. Second, the small-volume organic eluate was purified on an anion-exchange resin (0.5 mL/min) to extract the remaining soil pigments that could foul the ion source of the GC/MS system. Recoveries of the analytes were 75%, using deuterated atrazine as a surrogate, and were comparable to recoveries by soxhlet extraction. The detection limit was 0.1 ??g/kg with a coefficient of variation of 15%. The ease and efficiency of this automated method makes it viable, practical technique for studying triazine metabolites in the environment.
Mobility of Heavy Metals (Pb, Cd, Zn) in the Pampeano and Puelche Aquifers, Argentina: Partition and Retardation Coefficients.

PubMed

Jakomin, L M; Marbán, L; Grondona, S; Glok Galli, M; Martínez, D E

2015-09-01

The prediction about metals behaviour in soil requires knowledge on their solid-liquid partitioning. Usually it is expressed with an empirical distribution coefficient or Kd, which gives the ratio of the metal concentration in the solid phase to that in the solution. Kd values have been determined for Zn, Pb and Cd from samples representing the two most exploited aquifers in Argentina, Pampeano and Puelche, at three different locations in the province of Buenos Aires. The Pampeano aquifer presented higher Kd values than the Puelche aquifer. Comparing Kd values, different relationships could be observed: (a) Pampeano aquifer: Pb > Zn > Cd, and (b) Puelche aquifer: Pb > Cd > Zn. Kd for Cd seems to be linked to cationic exchange capacity, but solid phases precipitation can be more determining for Pb and Zn.
Solid-phase extraction microfluidic devices for matrix removal in trace element assay of actinide materials

DOE PAGES

Gao, Jun; Manard, Benjamin Thomas; Castro, Alonso; ...

2017-02-02

Advances in sample nebulization and injection technology have significantly reduced the volume of solution required for trace impurity analysis in plutonium and uranium materials. Correspondingly, we have designed and tested a novel chip-based microfluidic platform, containing a 100-µL or 20-µL solid-phase microextraction column, packed by centrifugation, which supports nuclear material mass and solution volume reductions of 90% or more compared to standard methods. Quantitative recovery of 28 trace elements in uranium was demonstrated using a UTEVA chromatographic resin column, and trace element recovery from thorium (a surrogate for plutonium) was similarly demonstrated using anion exchange resin AG MP-1. Of ninemore » materials tested, compatibility of polyvinyl chloride (PVC), polypropylene (PP), and polytetrafluoroethylene (PTFE) chips with the strong nitric acid media was highest. Finally, the microcolumns can be incorporated into a variety of devices and systems, and can be loaded with other solid-phase resins for trace element assay in high-purity metals.« less
Solid-phase extraction microfluidic devices for matrix removal in trace element assay of actinide materials

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

Gao, Jun; Manard, Benjamin Thomas; Castro, Alonso

Advances in sample nebulization and injection technology have significantly reduced the volume of solution required for trace impurity analysis in plutonium and uranium materials. Correspondingly, we have designed and tested a novel chip-based microfluidic platform, containing a 100-µL or 20-µL solid-phase microextraction column, packed by centrifugation, which supports nuclear material mass and solution volume reductions of 90% or more compared to standard methods. Quantitative recovery of 28 trace elements in uranium was demonstrated using a UTEVA chromatographic resin column, and trace element recovery from thorium (a surrogate for plutonium) was similarly demonstrated using anion exchange resin AG MP-1. Of ninemore » materials tested, compatibility of polyvinyl chloride (PVC), polypropylene (PP), and polytetrafluoroethylene (PTFE) chips with the strong nitric acid media was highest. Finally, the microcolumns can be incorporated into a variety of devices and systems, and can be loaded with other solid-phase resins for trace element assay in high-purity metals.« less
The Onset of Double Diffusive Convection in a Viscoelastic Fluid-Saturated Porous Layer with Non-Equilibrium Model

PubMed Central

Yang, Zhixin; Wang, Shaowei; Zhao, Moli; Li, Shucai; Zhang, Qiangyong

2013-01-01

The onset of double diffusive convection in a viscoelastic fluid-saturated porous layer is studied when the fluid and solid phase are not in local thermal equilibrium. The modified Darcy model is used for the momentum equation and a two-field model is used for energy equation each representing the fluid and solid phases separately. The effect of thermal non-equilibrium on the onset of double diffusive convection is discussed. The critical Rayleigh number and the corresponding wave number for the exchange of stability and over-stability are obtained, and the onset criterion for stationary and oscillatory convection is derived analytically and discussed numerically. PMID:24312193
The onset of double diffusive convection in a viscoelastic fluid-saturated porous layer with non-equilibrium model.

PubMed

Yang, Zhixin; Wang, Shaowei; Zhao, Moli; Li, Shucai; Zhang, Qiangyong

2013-01-01

The onset of double diffusive convection in a viscoelastic fluid-saturated porous layer is studied when the fluid and solid phase are not in local thermal equilibrium. The modified Darcy model is used for the momentum equation and a two-field model is used for energy equation each representing the fluid and solid phases separately. The effect of thermal non-equilibrium on the onset of double diffusive convection is discussed. The critical Rayleigh number and the corresponding wave number for the exchange of stability and over-stability are obtained, and the onset criterion for stationary and oscillatory convection is derived analytically and discussed numerically.
Thermodynamically constrained correction to ab initio equations of state

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

French, Martin; Mattsson, Thomas R.

2014-07-07

We show how equations of state generated by density functional theory methods can be augmented to match experimental data without distorting the correct behavior in the high- and low-density limits. The technique is thermodynamically consistent and relies on knowledge of the density and bulk modulus at a reference state and an estimation of the critical density of the liquid phase. We apply the method to four materials representing different classes of solids: carbon, molybdenum, lithium, and lithium fluoride. It is demonstrated that the corrected equations of state for both the liquid and solid phases show a significantly reduced dependence ofmore » the exchange-correlation functional used.« less
Measuring surface-area-to-volume ratios in soft porous materials using laser-polarized xenon interphase exchange nuclear magnetic resonance

NASA Technical Reports Server (NTRS)

Butler, J. P.; Mair, R. W.; Hoffmann, D.; Hrovat, M. I.; Rogers, R. A.; Topulos, G. P.; Walsworth, R. L.; Patz, S.

2002-01-01

We demonstrate a minimally invasive nuclear magnetic resonance (NMR) technique that enables determination of the surface-area-to-volume ratio (S/V) of soft porous materials from measurements of the diffusive exchange of laser-polarized 129Xe between gas in the pore space and 129Xe dissolved in the solid phase. We apply this NMR technique to porous polymer samples and find approximate agreement with destructive stereological measurements of S/V obtained with optical confocal microscopy. Potential applications of laser-polarized xenon interphase exchange NMR include measurements of in vivo lung function in humans and characterization of gas chromatography columns.
A novel technique to determine cobalt exchangeability in soils using isotope dilution.

PubMed

Wendling, Laura A; Kirby, Jason K; McLaughlin, Michael J

2008-01-01

The environmental risk posed by Co contamination is largely a function of its oxidation state. Our objective was to assess the potential biological availability of Co and the reactions and fate of soluble Co(II) after addition to soils with varying physical and chemical characteristics. A potential risk in quantifying exchangeable Co in soils using isotope dilution techniques is the possible presence of two species of Co in soil solution and adsorbed on soil solid phases [Co(II) and Co(III)], coupled with the possibility that when an isotope of Co is added it may undergo a change in oxidation state during the measurement phase. In this study, we have utilized an isotope dilution technique with cation exchange and high-performance liquid chromatography-inductively coupled plasma-mass spectrometry to determine the isotopically exchangeable Co fraction in several soils with varying characteristics such as differing Al, Fe, and Mn oxide content; pH; and organic carbon content. The application of the cation exchange procedure adjusts measurements of isotopically exchangeable Co to correct for the presence of non-exchangeable 57Co not in equilibrium with the solution phase. Results indicated that oxidation of added 57Co(II) to 57Co(III) or precipitation of 57Co(II) may occur on the surfaces of some soils, particularly those with a high pH or substantial quantities of Mn oxide minerals. No detectable Co(III)(aq) was found in the aqueous extracts of the soils examined.
Beyond the random-phase approximation for the electron correlation energy: the importance of single excitations.

PubMed

Ren, Xinguo; Tkatchenko, Alexandre; Rinke, Patrick; Scheffler, Matthias

2011-04-15

The random-phase approximation (RPA) for the electron correlation energy, combined with the exact-exchange (EX) energy, represents the state-of-the-art exchange-correlation functional within density-functional theory. However, the standard RPA practice--evaluating both the EX and the RPA correlation energies using Kohn-Sham (KS) orbitals from local or semilocal exchange-correlation functionals--leads to a systematic underbinding of molecules and solids. Here we demonstrate that this behavior can be corrected by adding a "single excitation" contribution, so far not included in the standard RPA scheme. A similar improvement can also be achieved by replacing the non-self-consistent EX total energy by the corresponding self-consistent Hartree-Fock total energy, while retaining the RPA correlation energy evaluated using KS orbitals. Both schemes achieve chemical accuracy for a standard benchmark set of noncovalent intermolecular interactions.
Power module packaging with double sided planar interconnection and heat exchangers

DOEpatents

Liang, Zhenxian; Marlino, Laura D.; Ning, Puqi; Wang, Fei

2015-05-26

A double sided cooled power module package having a single phase leg topology includes two IGBT and two diode semiconductor dies. Each IGBT die is spaced apart from a diode semiconductor die, forming a switch unit. Two switch units are placed in a planar face-up and face-down configuration. A pair of DBC or other insulated metallic substrates is affixed to each side of the planar phase leg semiconductor dies to form a sandwich structure. Attachment layers are disposed on outer surfaces of the substrates and two heat exchangers are affixed to the substrates by rigid bond layers. The heat exchangers, made of copper or aluminum, have passages for carrying coolant. The power package is manufactured in a two-step assembly and heating process where direct bonds are formed for all bond layers by soldering, sintering, solid diffusion bonding or transient liquid diffusion bonding, with a specially designed jig and fixture.

Analytical modeling of localized surface plasmon resonance in heterostructure copper sulfide nanocrystals

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

Caldwell, Andrew H.; Ha, Don-Hyung; Robinson, Richard D., E-mail: rdr82@cornell.edu

2014-10-28

Localized surface plasmon resonance (LSPR) in semiconductor nanocrystals is a relatively new field of investigation that promises greater tunability of plasmonic properties compared to metal nanoparticles. A novel process by which the LSPR in semiconductor nanocrystals can be altered is through heterostructure formation arising from solution-based cation exchange. Herein, we describe the development of an analytical model of LSPR in heterostructure copper sulfide-zinc sulfide nanocrystals synthesized via a cation exchange reaction between copper sulfide (Cu{sub 1.81}S) nanocrystals and Zn ions. The cation exchange reaction produces dual-interface, heterostructure nanocrystals in which the geometry of the copper sulfide phase can be tunedmore » from a sphere to a thin disk separating symmetrically-grown sulfide (ZnS) grains. Drude model electronic conduction and Mie-Gans theory are applied to describe how the LSPR wavelength changes during cation exchange, taking into account the morphology evolution and changes to the local permittivity. The results of the modeling indicate that the presence of the ZnS grains has a significant effect on the out-of-plane LSPR mode. By comparing the results of the model to previous studies on solid-solid phase transformations of copper sulfide in these nanocrystals during cation exchange, we show that the carrier concentration is independent of the copper vacancy concentration dictated by its atomic phase. The evolution of the effective carrier concentration calculated from the model suggests that the out-of-plane resonance mode is dominant. The classical model was compared to a simplified quantum mechanical model which suggested that quantum mechanical effects become significant when the characteristic size is less than ∼8 nm. Overall, we find that the analytical models are not accurate for these heterostructured semiconductor nanocrystals, indicating the need for new model development for this emerging field.« less
Assessing the performance of the random phase approximation for exchange and superexchange coupling constants in magnetic crystalline solids

NASA Astrophysics Data System (ADS)

Olsen, Thomas

2017-09-01

The random phase approximation (RPA) for total energies has previously been shown to provide a qualitatively correct description of static correlation in molecular systems, where density functional theory (DFT) with local functionals are bound to fail. This immediately poses the question of whether the RPA is also able to capture the correct physics of strongly correlated solids such as Mott insulators. Due to strong electron localization, magnetic interactions in such systems are dominated by superexchange, which in the simplest picture can be regarded as the analog of static correlation for molecules. In this paper, we investigate the performance of the RPA for evaluating both superexchange and direct exchange interactions in the magnetic solids NiO, MnO, Na3Cu2SbO6,Sr2CuO3,Sr2CuTeO6 , and a monolayer of CrI3, which were chosen to represent a broad variety of magnetic interactions. It is found that the RPA can accurately correct the large errors introduced by Hartree-Fock, independent of the input orbitals used for the perturbative expansion. However, in most cases, accuracies similar to RPA can be obtained with DFT+U, which is significantly simpler from a computational point of view.
Dendronization-induced phase-transfer, stabilization and self-assembly of large colloidal Au nanoparticles

NASA Astrophysics Data System (ADS)

Malassis, Ludivine; Jishkariani, Davit; Murray, Christopher B.; Donnio, Bertrand

2016-07-01

The phase-transfer of CTAB-coated aqueous, spherical gold nanoparticles, with metallic core diameters ranging from ca. 27 to 54 nm, into organic solvents by exchanging the primitive polar bilayer with lipophilic, disulfide dendritic ligands is reported. The presence of such a thick nonpolar organic shell around these large nanoparticles enhances their stabilization against aggregation, in addition to enabling their transfer into a variety of solvents such as chloroform, toluene or tetrahydrofuran. Upon the slow evaporation of a chloroform suspension deposited on a solid support, the dendronized hybrids were found to self-assemble into ring structures of various diameters. Moreover, their self-assembly at the liquid-air interface affords the formation of fairly long-range ordered monolayers, over large areas, that can then be entirely transferred onto solid substrates.The phase-transfer of CTAB-coated aqueous, spherical gold nanoparticles, with metallic core diameters ranging from ca. 27 to 54 nm, into organic solvents by exchanging the primitive polar bilayer with lipophilic, disulfide dendritic ligands is reported. The presence of such a thick nonpolar organic shell around these large nanoparticles enhances their stabilization against aggregation, in addition to enabling their transfer into a variety of solvents such as chloroform, toluene or tetrahydrofuran. Upon the slow evaporation of a chloroform suspension deposited on a solid support, the dendronized hybrids were found to self-assemble into ring structures of various diameters. Moreover, their self-assembly at the liquid-air interface affords the formation of fairly long-range ordered monolayers, over large areas, that can then be entirely transferred onto solid substrates. Electronic supplementary information (ESI) available: TEM microscope images. See DOI: 10.1039/c6nr03404g
Soil solution phosphorus turnover: derivation, interpretation, and insights from a global compilation of isotope exchange kinetic studies

NASA Astrophysics Data System (ADS)

Helfenstein, Julian; Jegminat, Jannes; McLaren, Timothy I.; Frossard, Emmanuel

2018-01-01

The exchange rate of inorganic phosphorus (P) between the soil solution and solid phase, also known as soil solution P turnover, is essential for describing the kinetics of bioavailable P. While soil solution P turnover (Km) can be determined by tracing radioisotopes in a soil-solution system, few studies have done so. We believe that this is due to a lack of understanding on how to derive Km from isotopic exchange kinetic (IEK) experiments, a common form of radioisotope dilution study. Here, we provide a derivation of calculating Km using parameters obtained from IEK experiments. We then calculated Km for 217 soils from published IEK experiments in terrestrial ecosystems, and also that of 18 long-term P fertilizer field experiments. Analysis of the global compilation data set revealed a negative relationship between concentrations of soil solution P and Km. Furthermore, Km buffered isotopically exchangeable P in soils with low concentrations of soil solution P. This finding was supported by an analysis of long-term P fertilizer field experiments, which revealed a negative relationship between Km and phosphate-buffering capacity. Our study highlights the importance of calculating Km for understanding the kinetics of P between the soil solid and solution phases where it is bioavailable. We argue that our derivation can also be used to calculate soil solution turnover of other environmentally relevant and strongly sorbing elements that can be traced with radioisotopes, such as zinc, cadmium, nickel, arsenic, and uranium.
Synthesis of ion-exchange resin for selective thorium and uranyl ions sorption

NASA Astrophysics Data System (ADS)

Konovalov, Konstantin; Sachkov, Victor

2017-11-01

In this work, the method of ion-exchange resin synthesis selective to radionuclides (uranium and thorium) is presented. The method includes synthesis of polymeric styrene-divinylbenzene macroporous matrix with size of 0.1-0.2 mm, and its subsequent transformation by nitration and then reduction by tin (II) chloride. For passivation of active primary amines partially oxidation by oxygen from air is used. Obtained ion-exchange resin has ratio of sorption sum U+Th to sorption sum of other total rare-earth elements as 1:1.88 at ratio of solid to liquid phase 1:200. The proposed method of ion-exchange resin synthesis is scaled-up for laboratory reactors with volume of 5 and 50 liters.
Sublimation systems and associated methods

DOEpatents

Turner, Terry D.; McKellar, Michael G.; Wilding, Bruce M.

2016-02-09

A system for vaporizing and sublimating a slurry comprising a fluid including solid particles therein. The system includes a first heat exchanger configured to receive the fluid including solid particles and vaporize the fluid and a second heat exchanger configured to receive the vaporized fluid and solid particles and sublimate the solid particles. A method for vaporizing and sublimating a fluid including solid particles therein is also disclosed. The method includes feeding the fluid including solid particles to a first heat exchanger, vaporizing the fluid, feeding the vaporized fluid and solid particles to a second heat exchanger and sublimating the solid particles. In some embodiments the fluid including solid particles is liquid natural gas or methane including solid carbon dioxide particles.
A transferable force field for CdS-CdSe-PbS-PbSe solid systems

NASA Astrophysics Data System (ADS)

Fan, Zhaochuan; Koster, Rik S.; Wang, Shuaiwei; Fang, Changming; Yalcin, Anil O.; Tichelaar, Frans D.; Zandbergen, Henny W.; van Huis, Marijn A.; Vlugt, Thijs J. H.

2014-12-01

A transferable force field for the PbSe-CdSe solid system using the partially charged rigid ion model has been successfully developed and was used to study the cation exchange in PbSe-CdSe heteronanocrystals [A. O. Yalcin et al., "Atomic resolution monitoring of cation exchange in CdSe-PbSe heteronanocrystals during epitaxial solid-solid-vapor growth," Nano Lett. 14, 3661-3667 (2014)]. In this work, we extend this force field by including another two important binary semiconductors, PbS and CdS, and provide detailed information on the validation of this force field. The parameterization combines Bader charge analysis, empirical fitting, and ab initio energy surface fitting. When compared with experimental data and density functional theory calculations, it is shown that a wide range of physical properties of bulk PbS, PbSe, CdS, CdSe, and their mixed phases can be accurately reproduced using this force field. The choice of functional forms and parameterization strategy is demonstrated to be rational and effective. This transferable force field can be used in various studies on II-VI and IV-VI semiconductor materials consisting of CdS, CdSe, PbS, and PbSe. Here, we demonstrate the applicability of the force field model by molecular dynamics simulations whereby transformations are initiated by cation exchange.
Determination of thallium at ultra-trace levels in water and biological samples using solid phase spectrophotometry

NASA Astrophysics Data System (ADS)

Amin, Alaa S.; El-Sharjawy, Abdel-Azeem M.; Kassem, Mohammed A.

2013-06-01

A new simple, very sensitive, selective and accurate procedure for the determination of trace amounts of thallium(III) by solid-phase spectrophotometry (SPS) has been developed. The procedure is based on fixation of Tl(III) as quinalizarin ion associate on a styrene-divinylbenzene anion-exchange resin. The absorbance of resin sorbed Tl(III) ion associate is measured directly at 636 and 830 nm. Thallium(I) was determined by difference measurements after oxidation of Tl(I) to Tl(III) with bromine. Calibration is linear over the range 0.5-12.0 μg L-1 of Tl(III) with relative standard deviation (RSD) of 1.40% (n = 10). The detection and quantification limits are 150 and 495 ng L-1 using 0.6 g of the exchanger. The molar absorptivity and Sandell sensitivity are also calculated and found to be 1.31 × 107 L mol-1 cm-1 and 0.00156 ng cm-2, respectively. The proposed procedure has been successfully applied to determine thallium in water, urine and serum samples.
Determination of thallium at ultra-trace levels in water and biological samples using solid phase spectrophotometry.

PubMed

Amin, Alaa S; El-Sharjawy, Abdel-Azeem M; Kassem, Mohammed A

2013-06-01

A new simple, very sensitive, selective and accurate procedure for the determination of trace amounts of thallium(III) by solid-phase spectrophotometry (SPS) has been developed. The procedure is based on fixation of Tl(III) as quinalizarin ion associate on a styrene-divinylbenzene anion-exchange resin. The absorbance of resin sorbed Tl(III) ion associate is measured directly at 636 and 830 nm. Thallium(I) was determined by difference measurements after oxidation of Tl(I) to Tl(III) with bromine. Calibration is linear over the range 0.5-12.0 μg L(-1) of Tl(III) with relative standard deviation (RSD) of 1.40% (n=10). The detection and quantification limits are 150 and 495 ng L(-1) using 0.6 g of the exchanger. The molar absorptivity and Sandell sensitivity are also calculated and found to be 1.31×10(7) L mol(-1)cm(-1) and 0.00156 ng cm(-2), respectively. The proposed procedure has been successfully applied to determine thallium in water, urine and serum samples. Copyright © 2013 Elsevier B.V. All rights reserved.
Fiber Optic Couplers

DTIC Science & Technology

1981-01-01

exchange and diffusion systems have been studied. The approaches we have tried at HRL include: (1) Li2SO2-K2so4 eutectic salt melt/soda lime glass (2...LiC1-KCL eutectic salt melt/soda lime glass (3) Ag metal field-assisted diffusion (solid phase)/soda lime glass (4) AgNO3 melt/soda lime glass (with...measurements were made of the throughput of guides formed by the ion exchange of soda lime glass in Li2SO4-K2S04 eutectic salt baths. The results of the
Near-Blackbody Enclosed Particle-Receiver Development

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

Ma, Zhiwen; Sakadjian, Bartev

2015-12-01

This 3-year project develops a technology using gas/solid, two-phase flow as a heat-transfer fluid and separated, stable, solid particles as a thermal energy storage (TES) medium for a concentrating solar power (CSP) plant, to address the temperature, efficiency, and cost barriers associated with current molten-salt CSP systems. This project focused on developing a near-blackbody particle receiver and an integrated fluidized-bed heat exchanger with auxiliary components to achieve greater than 20% cost reduction over current CSP plants, and to provide the ability to drive high-efficiency power cycles.
Optimized heat exchange in a CO2 de-sublimation process

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

Baxter, Larry; Terrien, Paul; Tessier, Pascal

The present invention is a process for removing carbon dioxide from a compressed gas stream including cooling the compressed gas in a first heat exchanger, introducing the cooled gas into a de-sublimating heat exchanger, thereby producing a first solid carbon dioxide stream and a first carbon dioxide poor gas stream, expanding the carbon dioxide poor gas stream, thereby producing a second solid carbon dioxide stream and a second carbon dioxide poor gas stream, combining the first solid carbon dioxide stream and the second solid carbon dioxide stream, thereby producing a combined solid carbon dioxide stream, and indirectly exchanging heat betweenmore » the combined solid carbon dioxide stream and the compressed gas in the first heat exchanger.« less
Separation Method for Oxygen Mass Transport Coefficient in Two Phase Porous Air Electrodes - Transport in Gas and Solid Polymer or Liquid Electrolyte Phases

DTIC Science & Technology

2013-08-06

of the problem studied Proton exchange membrane fuel cells ( PEMFCs ) are the most promising candidate systems for alternative electricity...characteristic. The limiting current can be used as a tool to study mass transport phenomena in PEMFC because it can provide experimental data for the...coefficient for PEMFCs under in situ conditions based on the galvanostatic discharge of a cell with an interrupted reactant supply. The results indicated
Liquid chromatographic determination of the cyanobacterial toxin beta-n-methylamino-L-alanine in algae food supplements, freshwater fish, and bottled water.

PubMed

Scott, Peter M; Niedzwiadek, Barbara; Rawn, Dorothea F K; Lau, Ben P-Y

2009-08-01

Beta-N-Methylamino-L-alanine (BMAA) is a neurotoxin originally found in cycad seeds and now known to be produced by many species of freshwater and marine cyanobacteria. We developed a method for its determination in blue-green algae (BGA) food supplements, freshwater fish, and bottled water by using a strong cation-exchange, solid-phase extraction column for cleanup after 0.3 M trichloroacetic acid extraction of BGA supplements and fish. Bottled water was applied directly onto the solid-phase extraction column. For analysis of carbonated water, sonication and pH adjustment to 1.5 were needed. To determine protein-bound BMAA, the protein pellet left after extraction of the BGA supplement and fish was hydrolyzed by boiling with 6 M hydrochloric acid; BMAA was cleaned up on a C18 column and a strong cation-exchange, solid-phase extraction column. Determination of BMAA was by liquid chromatography of the fluorescent derivative formed with 9-fluorenylmethyl chloroformate. The method was validated by recovery experiments using spiking levels of 1.0 to 10 microg/g for BGA supplements, 0.5 to 5.0 microg/g for fish, and 0.002 microg/g for bottled water; mean recoveries were in the range of 67 to 89% for BGA supplements and fish, and 59 to 92% for bottled water. Recoveries of BMAA from spiked extracts of hydrolyzed protein from BGA supplements and fish ranged from 66 to 83%. The cleanup developed provides a useful method for surveying foods and supplements for BMAA and protein-bound BMAA.
Effects of the interaction range on structural phases of flexible polymers.

PubMed

Gross, J; Neuhaus, T; Vogel, T; Bachmann, M

2013-02-21

We systematically investigate how the range of interaction between non-bonded monomers influences the formation of structural phases of elastic, flexible polymers. Massively parallel replica-exchange simulations of a generic, coarse-grained model, performed partly on graphics processing units and in multiple-gaussian modified ensembles, pave the way for the construction of the structural phase diagram, parametrized by interaction range and temperature. Conformational transitions between gas-like, liquid, and diverse solid (pseudo) phases are identified by microcanonical statistical inflection-point analysis. We find evidence for finite-size effects that cause the crossover of "collapse" and "freezing" transitions for very short interaction ranges.
The Phase Behavior of γ-Oryzanol and β-Sitosterol in Edible Oil.

PubMed

Sawalha, Hassan; Venema, Paul; Bot, Arjen; Flöter, Eckhard; Adel, Ruud den; van der Linden, Erik

The phase behavior of binary mixtures of γ-oryzanol and β-sitosterol and ternary mixtures of γ-oryzanol and β-sitosterol in sunflower oil was studied. Binary mixtures of γ-oryzanol and β-sitosterol show double-eutectic behavior. Complex phase behavior with two intermediate mixed solid phases was derived from differential scanning calorimetry (DSC) and small-angle X-ray scattering (SAXS) data, in which a compound that consists of γ-oryzanol and β-sitosterol molecules at a specific ratio can be formed. SAXS shows that the organization of γ-oryzanol and β-sitosterol in the mixed phases is different from the structure of tubules in ternary systems. Ternary mixtures including sunflower oil do not show a sudden structural transition from the compound to a tubule, but a gradual transition occurs as γ-oryzanol and β-sitosterol are diluted in edible oil. The same behavior is observed when melting binary mixtures of γ-oryzanol and β-sitosterol at higher temperatures. This indicates the feasibility of having an organogelling agent in dynamic exchange between solid and liquid phase, which is an essential feature of triglyceride networks.
Environmental solid particle effects on compressor cascade performance

NASA Technical Reports Server (NTRS)

Tabakoff, W.; Balan, C.

1982-01-01

The effect of suspended solid particles on the performance of the compressor cascade was investigated experimentally in a specially built cascade tunnel, using quartz sand particles. The cascades were made of NACA 65(10)10 airfoils. Three cascades were tested, one accelerating cascade and two diffusing cascades. The theoretical analysis assumes inviscid and incompressible two dimensional flow. The momentum exchange between the fluid and the particle is accounted for by the interphase force terms in the fluid momentum equation. The modified fluid phase momentum equations and the continuity equation are reduced to the conventional stream function vorticity formulation. The method treats the fluid phase in the Eulerian system and the particle phase in Lagrangian system. The experimental results indicate a small increase in the blade surface static pressures, while the theoretical results indicate a small decrease. The theoretical analysis, also predicts the loss in total pressure associated with the particulate flow through the cascade.
Analysis of imazaquin in soybeans by solid-phase extraction and high-performance liquid chromatography.

PubMed

Guo, C; Hu, J-Y; Chen, X-Y; Li, J-Z

2008-02-01

An analytical method for the determination imazaquin residues in soybeans was developed. The developed liquid/liquid partition and strong anion exchange solid-phase extraction procedures provide the effective cleanup, removing the greatest number of sample matrix interferences. By optimizing mobile-phase pH water/acetonitrile conditions with phosphoric acid, using a C-18 reverse-phase chromatographic column and employing ultraviolet detection, excellent peak resolution was achieved. The combined cleanup and chromatographic method steps reported herein were sensitive and reliable for determining the imazaquin residues in soybean samples. This method is characterized by recovery >88.4%, precision <6.7% CV, and sensitivity of 0.005 ppm, in agreement with directives for method validation in residue analysis. Imazaquin residues in soybeans were further confirmed by high performance liquid chromatography-mass spectrometry (LC-MS). The proposed method was successfully applied to the analysis of imazaquin residues in soybean samples grown in an experimental field after treatments of imazaquin formulation.
The distribution and adsorption behavior of aliphatic amines in marine and lacustrine sediments

NASA Astrophysics Data System (ADS)

Wang, Xu-chen; Lee, Cindy

1990-10-01

The methylated amines—monomethyl-, dimethyl-, and trimethyl amine (MMA, DMA, TMA)—are commonly found in aquatic environments, apparently as a result of decomposition processes. Adsorption of these amines to clay minerals and organic matter significantly influences their distribution in sediments. Laboratory measurements using 14C-radiolabelled amines and application of a linear partitioning model resulted in calculated adsorption coefficients of 2.4-4.7 (MMA), 3.3 (DMA), and 3.3-4.1 (TMA). Further studies showed that adsorption of amines is influenced by salinity of the porewaters, and clay mineral and organic matter content of the sediment solid phase. Concentrations of monomethyl- and dimethyl amine were measured in the porewaters and the solid phase of sediment samples collected from Flax Pond and Lake Ronkonkoma (NY), Long Island Sound, and the coastal Peru upwelling area. These two amines were present in all sediments investigated. A clear seasonal increase in the solid-phase concentration of MMA and DMA in Flax Pond sediments was likely related to the annual senescence of salt marsh grasses, either directly as a source of these compounds or indirectly by providing additional exchange capacity to the sediments. The distribution of amines in the solid and dissolved phases observed in all sediments investigated suggests that the distribution of these compounds results from a balance among production, decomposition, and adsorption processes.
Porous solid ion exchange wafer for immobilizing biomolecules

DOEpatents

Arora, Michelle B.; Hestekin, Jamie A.; Lin, YuPo J.; St. Martin, Edward J.; Snyder, Seth W.

2007-12-11

A porous solid ion exchange wafer having a combination of a biomolecule capture-resin and an ion-exchange resin forming a charged capture resin within said wafer. Also disclosed is a porous solid ion exchange wafer having a combination of a biomolecule capture-resin and an ion-exchange resin forming a charged capture resin within said wafer containing a biomolecule with a tag. A separate bioreactor is also disclosed incorporating the wafer described above.

Normal and anomalous nuclear spin-lattice relaxation at high temperatures in Sc-H(D), Y-H, and Lu-H solid solutions

NASA Astrophysics Data System (ADS)

Barnes, R. G.; Han, J.-W.; Torgeson, D. R.; Baker, D. B.; Conradi, M. S.; Norberg, R. E.

1995-02-01

We report the results of measurements of the proton (1H) spin-lattice relaxation rate R1 at high temperatures (to ~1400 K) in the hcp (α) solid-solution phases of the Sc-H, Y-H, and Lu-H systems, and of R1(45Sc) in Sc-H and Sc-D solid solutions. The latter measurements show unambiguous evidence of an anomalous increase at ~1000 K, whereas R1(1H) shows no such increase at any temperature. This behavior of R1(1H) contrasts with that in the bcc V-H, etc., solid solutions where anomalous relaxation occurs below ~1000 K, and in all investigated metal dihydride phases, MH2-x. The anomalous R1(1H) behavior in α-VHx, α-NbHx, etc., may be understood in terms of fast spin relaxation in the H2 gas in equilibrium with the solid, mediated by fast gas-solid exchange of hydrogen. However, in the present systems, α-ScHx, α-YHx, etc., the H2 gas pressure in equilibrium with the hcp systems is extremely low, resulting in negligible H2 concentration in the gas phase, and consequently a negligible contribution to R1(1H). In contrast, some of the present measurements indicate that the R1(45Sc) anomaly does result from the hydrogen content of the metal, but the mechanism remains unexplained.
Solid phase microbial fuel cell (SMFC) for harnessing bioelectricity from composite food waste fermentation: influence of electrode assembly and buffering capacity.

PubMed

Mohan, S Venkata; Chandrasekhar, K

2011-07-01

Solid phase microbial fuel cells (SMFC; graphite electrodes; open-air cathode) were designed to evaluate the potential of bioelectricity production by stabilizing composite canteen based food waste. The performance was evaluated with three variable electrode-membrane assemblies. Experimental data depicted feasibility of bioelectricity generation from solid state fermentation of food waste. Distance between the electrodes and presence of proton exchange membrane (PEM) showed significant influence on the power yields. SMFC-B (anode placed 5 cm from cathode-PEM) depicted good power output (463 mV; 170.81 mW/m(2)) followed by SMFC-C (anode placed 5 cm from cathode; without PEM; 398 mV; 53.41 mW/m(2)). SMFC-A (PEM sandwiched between electrodes) recorded lowest performance (258 mV; 41.8 mW/m(2)). Sodium carbonate amendment documented marked improvement in power yields due to improvement in the system buffering capacity. SMFCs operation also documented good substrate degradation (COD, 76%) along with bio-ethanol production. The operation of SMFC mimicked solid-sate fermentation which might lead to sustainable solid waste management practices. Copyright © 2011 Elsevier Ltd. All rights reserved.
EFFECTS OF PH AND COMPETING ANIONS ON THE SPECIATION OF ARSENIC IN FIXED IONIC STRENGTH SOLUTIONS BY SOLID PHASE EXTRACTION CARTRIDGES

EPA Science Inventory

Anion-exchange resins (AERs) separate As(V) and As(lIl) in solution by retaining As(V) and allowing As(lIl) to pass through. AERs offer several advantages including portability, ease of use, and affordability (relative to other As speciation methods). The use of AERs for the inst...
Application of mixed-mode, solid-phase extraction in environmental and clinical chemistry. Combining hydrogen-bonding, cation-exchange and Van der Waals interactions

USGS Publications Warehouse

Mills, M.S.; Thurman, E.M.; Pedersen, M.J.

1993-01-01

Silica- and styrene-divinylbenzene-based mixed-mode resins that contain C8, C18 and sulphonated cation-exchange groups were compared for their efficiency in isolation of neutral triazine compounds from water and of the basic drug, benzoylecgonine, from urine. The triazine compounds were isolated by a combination of Van der Waals and hydrogen-bonding interactions, and benzoylecgonine was isolated by Van der Waals interactions and cation exchange. All analytes were eluted with a polar organic solvent contaning 2% ammonium hydroxide. Larger recoveries (95%) were achieved on copolymerized mixed-mode resins where C18 and sulfonic acid are in closer proximity than on 'blended' mixed-mode resins (60-70% recovery).
Coercivity and Exchange Bias Study of Polycrystalline Hollow Nanoparticles

NASA Astrophysics Data System (ADS)

Bah, Mohamed Alpha

Magnetic nanoparticles (NPs) have the potential to be useful in a variety of applications such as biomedical instruments, catalysis, sensing, recording information, etc. These nanoparticles exhibit remarkably different properties compared to their bulk counter parts. Synthesis of magnetic NPs with the right morphology, phase, size and surface functionality, as well as their usage for specific applications are challenging in terms of efficiency and safety. Morphology wise, there have been numerous reports on magnetic nanoparticles where morphologies such as core/shell, hollow, solid, etc., have been explored. It has been shown that morphology affects the magnetic response. Achieving the right crystal structure with required morphology and the magnetic behavior of the nanoparticle phases determines the magnetic response of the structure. For example, in the case of core/shell NPs various ferromagnetic (FM), ferrimagnetic (FiM), and antiferromagnetic (AFM) core and shell combinations have been reported. In these cases, interesting and strikingly different features, such as unusually high spin glass transition temperature, large exchange bias, finite size effects, magnetic proximity effects, unusual trend of blocking temperature as function of average crystal size, etc., have been reported. More specifically, the morphology of core/shell nanoparticles provides added degrees of freedom compared to conventional solid magnetic nanoparticles, including variations in the size, phase and material of the core and shell of the particle, etc. which helps enhance their magnetic properties. Similar to traditional core/shell nanoparticles, inverted core/shell having a FiM or FM order above the Curie temperature (TC) of the shell has been reported where the Neel temperature (TN) is comparable with the bulk value and there is nonmonotonic dependence of the coercive field (HC) and exchange bias (HEB) on the core diameter. In addition to the core/shell morphology, nanoparticles with hollow morphology are also of interest to the scientific community. For such cases, surface spin glass transition enhancements have been reported due to the presence of the additional inner surface. CoFe2O4, NiFe 2O4 and gamma-Fe2O3 hollow nanoparticles exhibit strikingly contrasting magnetic behavior compared to bulk and conventional solid particles; similar behavior was also observed in core/shell nanoparticles. Structurally, hollow polycrystalline nanoparticles are composed of multiple crystallographic domains. This random orientation of the crystallographic domains also causes randomization of the local anisotropy axes. Hence the overall effect of this morphology on the magnetic properties is exhibited through the high coercivity, relatively high temperature magnetic irreversibility, lack of magnetic saturation, high blocking temperature, etc. Over the years, extensive work on core/shell nanoparticles have been carried out to understand their exchange bias phenomenon and the effect on coercivity. Recently, focus has been given to hollow polycrystalline nanoparticles for the reason mentioned above. This thesis investigates the root cause for the above-mentioned effects on the coercivity and exchange bias. Since hollow nanoparticles with polycrystalline structure have shown to exhibit different and improved magnetic behavior compared to bulk and other conventional solid particles, they will be the focus of our investigation. First, extensive field and temperature dependent magnetic study on polycrystalline hollow nickel ferrite (NiFe2O4) have revealed the effect of the presence of inner surface in a single oxide nanoparticle. Second, the effect of having multiple oxides with different magnetic properties (i.e. FM and AFM) in a single nanoparticle, while maintaining a hollow morphology was investigated by studying polycrystalline hollow gamma-Mn2O3 and MnO nanoparticles. Studies on various conventional solid manganese oxide nanoparticles have already been reported. Therefore, focus was only made on the fabrication and magnetic study of hollow polycrystalline manganese oxide, with a comparison of the results to those from solid nanoparticles already available in literature. A conclusion was drawn to the importance of the coupling of different magnetic phases (i.e. FM and AFM, FiM and AFM, or SG and AFM), in contrast to just having one single oxide in the hollow nanoparticles. Finally, the importance of this coupling as compared to the increase of surface-to-volume ratio was evaluated in CoO/Co3O4/CoFe2O4 polycrystalline hollow nanoparticles by varying the AFM phase (CoO/Co 3O4) in the nanoparticles and observing how the magnetic properties varied. This system helped address the effect of the coupling between different magnetic phases, super-exchange interaction, and proximity effect.
Solid-support substrates for plant growth at a lunar base

NASA Technical Reports Server (NTRS)

Ming, D. W.; Galindo, C.; Henninger, D. L.

1990-01-01

Zeoponics is only in its developmental stages at the Johnson Space Center and is defined as the cultivation of plants in zeolite substrates that contain several essential plant growth cations on their exchange sites, and have minor amounts of mineral phases and/or anion-exchange resins that supply essential plant growth anions. Zeolites are hydrated aluminosilicates of alkali and alkaline earth cations with the ability to exchange most of their constituent exchange cations as well as hydrate/dehydrate without change to their structural framework. Because zeolites have extremely high cation exchange capabilities, they are very attractive media for plant growth. It is possible to partially or fully saturate plant-essential cations on zeolites. Zeoponic systems will probably have their greatest applications at planetary bases (e.g., lunar bases). Lunar raw materials will have to be located that are suited for the synthesis of zeolites and other exchange resings. Lunar 'soil' simulants have been or are being prepared for zeolite/smectite synthesis and 'soil' dissolution studies.
Determination of artificial sweeteners in water samples by solid-phase extraction and liquid chromatography-tandem mass spectrometry.

PubMed

Ordóñez, Edgar Y; Quintana, José Benito; Rodil, Rosario; Cela, Rafael

2012-09-21

The development and performance evaluation of an analytical method for the determination of six artificial sweeteners in environmental waters using solid-phase extraction (SPE) followed by liquid chromatography-tandem mass spectrometry are presented. To this end, different SPE alternatives have been evaluated: polymeric reversed-phase (Oasis HLB, Env+, Plexa and Strata X), and mixed-mode with either weak (Oasis WAX) or strong anionic-exchange (Oasis MAX and Plexa PAX) sorbents. Among them, reversed-phase sorbents, particularly Oasis HLB and Strata X, showed the best performance. Oasis HLB provided good trueness (recoveries: 73-112%), precision (RSD<10%) and limits of quantification (LOQ: 0.01-0.5 μg/L). Moreover, two LC separation mechanisms were evaluated: reversed-phase (RPLC) and hydrophilic interaction (HILIC), with RPLC providing better performance than HILIC. The final application of the method showed the presence of acesulfame, cyclamate, saccharin and sucralose in the wastewater and surface water samples analyzed at concentrations up to 54 μg/L. Copyright © 2012 Elsevier B.V. All rights reserved.
In Situ Neutron Diffraction Studies of the Ion Exchange Synthesis Mechanism of Li2Mg2P3O9N: Evidence for a Hidden Phase Transition.

PubMed

Liu, Jue; Whitfield, Pamela S; Saccomanno, Michael R; Bo, Shou-Hang; Hu, Enyuan; Yu, Xiqian; Bai, Jianming; Grey, Clare P; Yang, Xiao-Qing; Khalifah, Peter G

2017-07-12

Motivated by predictions made using a bond valence sum difference map (BVS-DM) analysis, the novel Li-ion conductor Li 2 Mg 2 P 3 O 9 N was synthesized by ion exchange from a Na 2 Mg 2 P 3 O 9 N precursor. Impedance spectroscopy measurements indicate that Li 2 Mg 2 P 3 O 9 N has a room temperature Li-ion conductivity of about 10 -6 S/cm (comparable to LiPON), which is 6 orders of magnitude higher than the extrapolated Na-ion conductivity of Na 2 Mg 2 P 3 O 9 N at this temperature. The structure of Li 2 Mg 2 P 3 O 9 N was determined from ex situ synchrotron and time-of-flight neutron diffraction data to retain the P2 1 3 space group, though with a cubic lattice parameter of a = 9.11176(8) Å that is significantly smaller than the a = 9.2439(1) Å of Na 2 Mg 2 P 3 O 9 N. The two Li-ion sites are found to be very substantially displaced (∼0.5 Å) relative to the analogous Na sites in the precursor phase. The non-molten salt ion exchange method used to prepare Li 2 Mg 2 P 3 O 9 N produces a minimal background in powder diffraction experiments, and was therefore exploited for the first time to follow a Li + /Na + ion exchange reaction using in situ powder neutron diffraction. Lattice parameter changes during ion exchange suggest that the reaction proceeds through a Na 2-x Li x Mg 2 P 3 O 9 N solid solution (stage 1) followed by a two-phase reaction (stage 2) to form Li 2 Mg 2 P 3 O 9 N. However, full Rietveld refinements of the in situ neutron diffraction data indicate that the actual transformation mechanism is more complex and instead involves two thermodynamically distinct solid solutions in which the Li exclusively occupies the Li1 site at low Li contents (stage 1a) and then migrates to the Li3 site at higher Li contents (stage 1b), a crossover driven by the different signs of the local volume change at these sites. In addition to highlighting the importance of obtaining full structural data in situ throughout the ion exchange process, these results provide insights into the general question of what constitutes a thermodynamic phase.
In Situ Neutron Diffraction Studies of the Ion Exchange Synthesis Mechanism of Li 2Mg 2P 3O 9N: Evidence for a Hidden Phase Transition

DOE PAGES

Liu, Jue; Whitfield, Pamela S.; Saccomanno, Michael R.; ...

2017-06-06

Motivated by predictions made using a bond valence sum difference map (BVS-DM) analysis, the novel Li-ion conductor Li 2Mg 2P 3O 9N was synthesized in this paper by ion exchange from a Na 2Mg 2P 3O 9N precursor. Impedance spectroscopy measurements indicate that Li 2Mg 2P 3O 9N has a room temperature Li-ion conductivity of about 10 –6 S/cm (comparable to LiPON), which is 6 orders of magnitude higher than the extrapolated Na-ion conductivity of Na 2Mg 2P 3O 9N at this temperature. The structure of Li 2Mg 2P 3O 9N was determined from ex situ synchrotron and time-of-flight neutronmore » diffraction data to retain the P2 13 space group, though with a cubic lattice parameter of a = 9.11176(8) Å that is significantly smaller than the a = 9.2439(1) Å of Na 2Mg 2P 3O 9N. The two Li-ion sites are found to be very substantially displaced (~0.5 Å) relative to the analogous Na sites in the precursor phase. The non-molten salt ion exchange method used to prepare Li 2Mg 2P 3O 9N produces a minimal background in powder diffraction experiments, and was therefore exploited for the first time to follow a Li +/Na + ion exchange reaction using in situ powder neutron diffraction. Lattice parameter changes during ion exchange suggest that the reaction proceeds through a Na 2–xLi xMg 2P 3O 9N solid solution (stage 1) followed by a two-phase reaction (stage 2) to form Li 2Mg 2P 3O 9N. However, full Rietveld refinements of the in situ neutron diffraction data indicate that the actual transformation mechanism is more complex and instead involves two thermodynamically distinct solid solutions in which the Li exclusively occupies the Li1 site at low Li contents (stage 1a) and then migrates to the Li3 site at higher Li contents (stage 1b), a crossover driven by the different signs of the local volume change at these sites. Finally, in addition to highlighting the importance of obtaining full structural data in situ throughout the ion exchange process, these results provide insights into the general question of what constitutes a thermodynamic phase.« less
In Situ Neutron Diffraction Studies of the Ion Exchange Synthesis Mechanism of Li 2Mg 2P 3O 9N: Evidence for a Hidden Phase Transition

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

Liu, Jue; Whitfield, Pamela S.; Saccomanno, Michael R.

Motivated by predictions made using a bond valence sum difference map (BVS-DM) analysis, the novel Li-ion conductor Li 2Mg 2P 3O 9N was synthesized in this paper by ion exchange from a Na 2Mg 2P 3O 9N precursor. Impedance spectroscopy measurements indicate that Li 2Mg 2P 3O 9N has a room temperature Li-ion conductivity of about 10 –6 S/cm (comparable to LiPON), which is 6 orders of magnitude higher than the extrapolated Na-ion conductivity of Na 2Mg 2P 3O 9N at this temperature. The structure of Li 2Mg 2P 3O 9N was determined from ex situ synchrotron and time-of-flight neutronmore » diffraction data to retain the P2 13 space group, though with a cubic lattice parameter of a = 9.11176(8) Å that is significantly smaller than the a = 9.2439(1) Å of Na 2Mg 2P 3O 9N. The two Li-ion sites are found to be very substantially displaced (~0.5 Å) relative to the analogous Na sites in the precursor phase. The non-molten salt ion exchange method used to prepare Li 2Mg 2P 3O 9N produces a minimal background in powder diffraction experiments, and was therefore exploited for the first time to follow a Li +/Na + ion exchange reaction using in situ powder neutron diffraction. Lattice parameter changes during ion exchange suggest that the reaction proceeds through a Na 2–xLi xMg 2P 3O 9N solid solution (stage 1) followed by a two-phase reaction (stage 2) to form Li 2Mg 2P 3O 9N. However, full Rietveld refinements of the in situ neutron diffraction data indicate that the actual transformation mechanism is more complex and instead involves two thermodynamically distinct solid solutions in which the Li exclusively occupies the Li1 site at low Li contents (stage 1a) and then migrates to the Li3 site at higher Li contents (stage 1b), a crossover driven by the different signs of the local volume change at these sites. Finally, in addition to highlighting the importance of obtaining full structural data in situ throughout the ion exchange process, these results provide insights into the general question of what constitutes a thermodynamic phase.« less
Determination of a flame retardant hydrolysis product in human urine by SPE and LC-MS. Comparison of molecularly imprinted solid-phase extraction with a mixed-mode anion exchanger.

PubMed

Möller, Kristina; Crescenzi, Carlo; Nilsson, Ulrika

2004-01-01

Diphenyl phosphate is a hydrolysis product and possible metabolite of the flame retardant and plasticiser additive triphenyl phosphate. A molecularly imprinted polymer solid-phase extraction (MISPE) method for extracting diphenyl phosphate from aqueous solutions has been developed and compared with SPE using a commercially available mixed-mode anion exchanger. The imprinted polymer was prepared using 2-vinylpyridine (2-Vpy) as the functional monomer, ethylene glycol dimethacrylate (EGDMA) as the cross-linker, and a structural analogue of the analyte as the template molecule. The imprinted polymer was evaluated for use as a SPE sorbent, in tests with both aqueous standards and spiked urine samples, by comparing recovery and breakthrough data obtained using the imprinted form of the polymer and a non-imprinted form (NIP). Extraction from aqueous solutions resulted in more than 80% recovery. Adsorption by the molecularly imprinted polymer (MIP) was non-selective, but selectivity was achieved by selective desorption in the wash steps. Diphenyl phosphate could also be selectively extracted from urine samples, although the urine matrix reduced the capacity of the MISPE cartridges. Recoveries from urine extraction were higher than 70%. It was important to control pH during sample loading. The MISPE method was found to yield a less complex LC-ESI-MS chromatogram of the urine extracts compared with the mixed-mode anion-exchanger method. An LC-ESI-MS method using a Hypercarb LC column with a graphitised carbon stationary phase was also evaluated for organophosphate diesters. LC-ESI-MS using negative-ion detection in selected ion monitoring (SIM) mode was shown to be linear for diphenyl phosphate in the range 0.08-20 ng microL(-1).
A stable perovskite electrolyte in moist air for Li-ion batteries.

PubMed

Li, Yutao; Xu, Henghui; Chien, Po-Hsiu; Wu, Nan; Xin, Sen; Xue, Leigang; Park, Kyusung; Hu, Yan-Yan; Goodenough, John B

2018-05-07

Solid-oxide Li+ electrolytes of a rechargeable cell are generally sensitive to moisture in the air, H+ exchanges for the mobile Li+ of the electrolyte and forms insulating surface phases at the electrolyte interfaces and in the grain boundaries of a polycrystalline membrane. These surface phases dominate the total interfacial resistance of a conventional rechargeable cell having a solid-electrolyte separator. We report a new perovskite Li+ solid electrolyte, Li0.38Sr0.44Ta0.7Hf0.3O2.95F0.05, having a Li-ion conductivity σLi = 4.8×10-4 S cm-1 at 25 oC that does not react with water having 3≤pH≤14. The solid electrolyte with a thin Li+-conducting polymer on its surface to prevent reduction of Ta5+ is wet by metallic lithium and provides low-impedance dendrite-free plating/stripping of a lithium anode. It is also stable on contact with a composite polymer cathode. With this solid electrolyte, we demonstrate excellent cycling performance of an all-solid-state Li/LiFePO4 cell, a Li-S cell with a polymer-gel cathode, and a supercapacitor. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Operando Solid-State NMR Observation of Solvent-Mediated Adsorption-Reaction of Carbohydrates in Zeolites

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

Qi, Long; Alamillo, Ricardo; Elliott, William A.

Liquid-phase processing of molecules using heterogeneous catalysts – an important strategy for obtaining renewable chemicals sustainably from biomass – involves reactions that occur at solid-liquid interfaces. In glucose isomerization catalyzed by basic faujasite zeolites, the catalytic activity depends strongly on the solvent composition: initially, it declines precipitously when water is mixed with a small amount of the organic co-solvent γ-valerolactone (GVL), then recovers as the GVL content increases. Using solid-state 13C NMR spectroscopy, we observed glucose isomers located inside the zeolite pores directly, and followed their transformations into fructose and mannose in real time. At low GVL concentrations, glucose ismore » depleted in the zeolite pores relative to the liquid phase, while higher GVL concentrations in solution drive glucose inside the pores, resulting in up to a 32 enhancement in the local glucose concentration. Although their populations exchange rapidly, molecules present at the reactive interface experience a significantly different environment from the bulk solution.« less
Quantum phase transition between cluster and antiferromagnetic states

NASA Astrophysics Data System (ADS)

Son, W.; Amico, L.; Fazio, R.; Hamma, A.; Pascazio, S.; Vedral, V.

2011-09-01

We study a Hamiltonian system describing a three-spin-1/2 cluster-like interaction competing with an Ising-like exchange. We show that the ground state in the cluster phase possesses symmetry protected topological order. A continuous quantum phase transition occurs as result of the competition between the cluster and Ising terms. At the critical point the Hamiltonian is self-dual. The geometric entanglement is also studied and used to investigate the quantum phase transition. Our findings in one dimension corroborate the analysis of the two-dimensional generalization of the system, indicating, at a mean-field level, the presence of a direct transition between an antiferromagnetic and a valence bond solid ground state.
On-line packed magnetic in-tube solid phase microextraction of acidic drugs such as naproxen and indomethacin by using Fe3O4@SiO2@layered double hydroxide nanoparticles with high anion exchange capacity.

PubMed

Shamsayei, Maryam; Yamini, Yadollah; Asiabi, Hamid; Safari, Meysam

2018-02-22

The authors describe a 3-component nanoparticle system composed of a silica-coated magnetite (Fe 3 O 4 ) core and a layered double (Cu-Cr) hydroxide nanoplatelet shell. The sorbent has a high anion exchange capacity for extraction anionic species. A simple online system, referred to as "on-line packed magnetic-in-tube solid phase microextraction" was designed. The nanoparticles were placed in a stainless steel cartridge via dry packing. The cartridge was then applied to the preconcentration acidic drugs including naproxen and indomethacin from urine and plasma. Extraction and desorption times, pH values of the sample solution and flow rates of sample solution and eluent were optimized. Analytes were then quantified by HPLC with UV detection. Under optimal conditions, the limits of detection range from 70 to 800 ng L -1 , with linear responses from 0.1-500 μg L -1 (water samples), 0.6-500 μg L -1 (spiked urine), and 0.9-500 μg L -1 (spiked plasma). The inter- and intra-assay precisions (RSDs, for n = 5) are in the range of 2.2-5.4%, 2.8-4.9%, and 2.0-5.2% at concentration levels of 5, 25 and 50 μg L -1 , respectively. The method was applied to the analysis of the drugs in spiked human urine and plasma, and good results were achieved. Graphical abstract Fe 3 O 4 @SiO 2 @CuCr-LDH magnetic nanoparticles were synthesized and packed in to a stainless steel column. The column was applied to solid phase microextraction of acidic drugs from biological samples.
Magnetic properties in polycrystalline and single crystal Ca-doped LaCoO3

NASA Astrophysics Data System (ADS)

Zeng, R.; Debnath, J. C.; Chen, D. P.; Shamba, P.; Wang, J. L.; Kennedy, S. J.; Campbell, S. J.; Silver, T.; Dou, S. X.

2011-04-01

Polycrystalline (PC) and single crystalline (SC) Ca-doped LaCoO3 (LCCO) samples with the perovskite structure were synthesized by conventional solid-state reaction and the floating-zone growth method. We present the results of a comprehensive investigation of the magnetic properties of the LCCO system. Systematic measurements have been conducted on dc magnetization, ac susceptibility, exchange-bias, and the magnetocaloric effect. These findings suggest that complex structural phases, ferromagnetic (FM), and spin-glass/cluster-spin-glass (CSG), and their transitions exist in PC samples, while there is a much simpler magnetic phase in SC samples. It was also of interest to discover that the CSG induced a magnetic field memory effect and an exchange-bias-like effect, and that a large inverse irreversible magnetocaloric effect exists in this system.
Thermodynamic modeling of Cl(-), NO3(-) and SO4(2-) removal by an anion exchange resin and comparison with Dubinin-Astakhov isotherms.

PubMed

Dron, Julien; Dodi, Alain

2011-03-15

The removal of chloride, nitrate, and sulfate ions from wastewaters by a macroporous ion-exchange resin is studied through the experimental results obtained for six ion exchange systems, OH(-)/Cl(-), OH(-)/NO3(-), OH(-)/SO4(2-), and HCO3(-)/Cl(-), Cl(-)/NO3(-), Cl(-)/SO4(2-). The results are described through thermodynamic modeling, considering either an ideal or a nonideal behavior of the ionic species in the liquid and solid phases. The nonidealities are determined by the Davies equation and Wilson equations in the liquid and solid phases, respectively. The results show that the resin has a strong affinity for all the target ions, and the order of affinity obtained is OH(-) < HCO3(-) < Cl(-) < NO3(-) < SO4(2-). The calculation of the changes in standard Gibbs free energies (ΔG(0)) shows that even though HCO3(-) has a lower affinity to the resin, it may affect the removal of Cl(-), and in the same way that Cl(-) may affect the removal of NO3(-) and SO4(2-). The application of nonidealities in the thermodynamic model leads to an improved fit of the model to the experimental data with average relative deviations below 1.5% except for the OH(-)/SO4(2-) system. On the other hand, considering ideal or nonideal behaviors has no significant impact on the determination of the selectivity coefficients. The thermodynamic modeling is also compared with the Dubinin-Astakhov adsorption isotherms obtained for the same ion exchange systems. Surprisingly, the latter performs significantly better than the ideal thermodynamic model and nearly as well as the nonideal thermodynamic model.
Application of cation-exchange solid-phase extraction for the analysis of amino alcohols from water and human plasma for verification of Chemical Weapons Convention.

PubMed

Kanaujia, Pankaj K; Tak, Vijay; Pardasani, Deepak; Gupta, A K; Dubey, D K

2008-03-28

The analysis of nitrogen containing amino alcohols, which are the precursors and degradation products of nitrogen mustards and nerve agent VX, constitutes an important aspect for verifying the compliance to the CWC (Chemical Weapons Convention). This work devotes on the development of solid-phase extraction method using silica- and polymer-based SCX (strong cation-exchange) and MCX (mixed-mode strong cation-exchange) cartridges for N,N-dialkylaminoethane-2-ols and alkyl N,N-diethanolamines, from water. The extracted analytes were analyzed by GC-MS (gas chromatography-mass spectrometry) in the full scan and selected ion monitoring modes. The extraction efficiencies of SCX and MCX cartridges were compared, and results revealed that SCX performed better. Extraction parameters, such as loading capacity, extraction solvent, its volume, and washing solvent were optimized. Best recoveries were obtained using 2 mL methanol containing 10% NH(4)OH and limits of detection could be achieved up to 5 x 10(-3) microg mL(-1) in the selected ion monitoring mode and 0.01 microg mL(-1) in full scan mode. The method was successfully employed for the detection and identification of amino alcohol present in water sample sent by Organization for Prohibition of Chemical Weapons (OPCW) in the official proficiency tests. The method was also applied to extract the analytes from human plasma. The SCX cartridge showed good recoveries of amino alcohols from human plasma after protein precipitation.
One-dimensional thermohydraulic code THESEUS and its application to chilldown process simulation in two-phase hydrogen flows

NASA Astrophysics Data System (ADS)

Papadimitriou, P.; Skorek, T.

THESUS is a thermohydraulic code for the calculation of steady state and transient processes of two-phase cryogenic flows. The physical model is based on four conservation equations with separate liquid and gas phase mass conservation equations. The thermohydraulic non-equilibrium is calculated by means of evaporation and condensation models. The mechanical non-equilibrium is modeled by a full-range drift-flux model. Also heat conduction in solid structures and heat exchange for the full spectrum of heat transfer regimes can be simulated. Test analyses of two-channel chilldown experiments and comparisons with the measured data have been performed.
Determination of filter pore size for use in HB line phase II production of plutonium oxide

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

Shehee, T.; Crowder, M.; Rudisill, T.

2014-08-01

H-Canyon and HB-Line are tasked with the production of plutonium oxide (PuO 2) from a feed of plutonium (Pu) metal. The PuO 2 will provide feed material for the Mixed Oxide (MOX) Fuel Fabrication Facility. After dissolution of the Pu metal in H-Canyon, plans are to transfer the solution to HB-Line for purification by anion exchange. Anion exchange will be followed by plutonium(IV) oxalate precipitation, filtration, and calcination to form PuO 2. The filtrate solutions, remaining after precipitation, contain low levels of Pu ions, oxalate ions, and may include solids. These solutions are transferred to H-Canyon for disposition. To mitigatemore » the criticality concern of Pu solids in a Canyon tank, past processes have used oxalate destruction or have pre-filled the Canyon tank with a neutron poison. The installation of a filter on the process lines from the HB-Line filtrate tanks to H-Canyon Tank 9.6 is proposed to remove plutonium oxalate solids. This report describes SRNL’s efforts to determine the appropriate pore size for the filters needed to perform this function. Information provided in this report aids in developing the control strategies for solids in the process.« less

Identification of the solid phase in relation to the solubility of nickel in alluvial soils.

PubMed

Barman, Mandira; Datta, S P; Rattan, R K

2014-09-01

The chemical equillibria between nickel (Ni) ion present in soil solution and solid phases govern the solubility vis-a-vis availability of Ni in soil. Therefore, stability of various Ni containing minerals in relation to pH was studied to identify the probable solid phases, which govern the solubility of Ni in some alluvial soils under intensive cultivation in and around Delhi. Free Ni2+ activity (pNi2+) as estimated by Baker soil test, ranged from 13.1 to 16.2. Highest free Ni2+ activity (pNi2+ = 13.1) was recorded in industrial effluent irrigated soil collected from Sonepat, Haryana. Free Ni2+ activity was 13.6 in soil collected from agricultural lands of Keshopur, receiving irrigation through sewage effluents. Soils receiving irrigation through tube well water showed relatively lower free Ni2+ activity (pNi2+ = 14.6 to 16.2). Ni-ferrite in equilibrium with Fe(OH)3 (amorphous) is likely to control the activity of Ni in two intensively Ni contaminated soil having pH around 8. Free Ni2+ activity is likely to be buffered by exchangeable Ni in soils having neutral pH.
Synthesis of biodiesel using local natural zeolite as heterogeneous anion exchange catalyst

NASA Astrophysics Data System (ADS)

Hartono, R.; Wijanarko, A.; Hermansyah, H.

2018-04-01

Production of biodiesel using homogen catalyst: alkaline catalysts, acid catalysts, biocatalysts, and supercritical methanol are very inefficient, because these catalysts have a very high cost production of biodiesel and non-ecofriendly. The heterogeneous catalyst is then used to avoid adverse reaction of biodiesel production. The heterogeneous catalysts used is ion exchanger using natural zeolit catalists bayah banten (ZABBrht) and macroporous lewatit that can be used to produce biodiesel in the solid phase so that the separation is easier and can be used repeatedly. The results of biodiesel reach its optimum in engineering ion exchange catalyst natural zeolit bayah and macroporous lewatit which has been impregnated and calcinated at temperature 60 °C at reaction time 2 hours, are 94.8% and 95.24%, using 100 gr.KOH/100 mL Aquadest.
Natural Radium Detection and Inventory Flux of Isotopes in Particulate and Dissolved Phases of Seawater at Kapar Coastal Area Caused by Coal-Fired Power Plant

NASA Astrophysics Data System (ADS)

Mohamed, N.; Ariffin, N. A. N.; Mohamed, C. A. R.

2016-07-01

Distribution of 226Ra and 228Ra radioactive in marine have been studied at Kapar coastal area that closed to Sultan Salahudin Abdul Aziz Shah (SJSSAS) power station. The concentration level of 226Ra and 228Ra were measured in seawater include total suspended solids (TSSrw) and dissolved phases from September 2006 to February 2008. The measurement technique used for 226Ra and 228Ra was using cation exchange column and counted using Liquid Scintillator Ciunter (LSC). The radioactivities of 226Rasw and 228Rasw in the dissolved phase of seawater ranged from 1.29 ± 0.52 mBq/L - 3.69 ± 1.29 mBq/L and 2.12 ± 0.71 mbq/L - 17.07 ± 6.03 mBq/L respectively. The measurement of radioactivities of radium isotopes in the particulate phase of seawater ranged from 15.62 ± 1.99 Bq/kg - 241.76 ± 100.23 Bq/kg (226Ratsw) and 7.19 ± 3.21 Bq/kg - 879.66 ± 365.74 Bq/kg (228Ratsw). Radium isotopes inventory in this study showed that suspended solid have higher inventory value than seawater and sediment. Study also found that suspended solid play an important role for flux contribution at seawater. Based on the finding, the radioactivity concentration of 226Ra and 228Ra is higher in particulate phase than in dissolved phase.
Investigation of Anion-Exchange and Immunoaffinity Particle-Loaded Membranes for the Isolation of Charged Organic Analytes from Water

USGS Publications Warehouse

Dombrowski, T.R.; Wilson, G.S.; Thurman, E.M.

1998-01-01

Anion-exchange and immunoaffinity particle loaded membranes (PLMs) were investigated as a mechanism for the isolation of charged organic analytes from water. Kinetic properties determined theoretically included dynamic capacity, pressure drop (??P), residence and diffusion times (Tr, Td), and total membrane porosity (???T). These properties were confirmed through experimental evaluation, and the PLM method showed significant improvement over conventional solid-phase extraction (SPE) and ion-exchange formats. Recoveries of more than 90% were observed for a variety of test compounds at flow rates up to 70 mL/min (equipment-limited maximum flow rate). A fast-flow immunoaffinity column was developed using antibodies (Abs) attached to the PLMs. Reproducible recoveries (88% ?? 4%) were observed at flow rates up to 70 mL/min for the antibody (Ab)-loaded PLMs. Findings indicate increased selectivity over anion-exchange PLMs and conventional SPE or ion-exchange methods and rapid Ab-antigen binding rates given the excellent mass-transfer characteristics of the PLMs.
Application of phase-trafficking methods to natural products research.

PubMed

Araya, Juan J; Montenegro, Gloria; Mitscher, Lester A; Timmermann, Barbara N

2010-09-24

A novel simultaneous phase-trafficking approach using spatially separated solid-supported reagents for rapid separation of neutral, basic, and acidic compounds from organic plant extracts with minimum labor is reported. Acidic and basic ion-exchange resins were physically separated into individual sacks ("tea bags") for trapping basic and acidic compounds, respectively, leaving behind in solution neutral components of the natural mixtures. Trapped compounds were then recovered from solid phase by appropriate suspension in acidic or basic solutions. The feasibility of the proposed separation protocol was demonstrated and optimized with an "artificial mixture" of model compounds. In addition, the utility of this methodology was illustrated with the successful separation of the alkaloid skytanthine from Skytanthus acutus Meyen and the main catechins and caffeine from Camellia sinensis L. (Kuntze). This novel approach offers multiple advantages over traditional extraction methods, as it is not labor intensive, makes use of only small quantities of solvents, produces fractions in adequate quantities for biological assays, and can be easily adapted to field conditions for bioprospecting activities.
Application of Phase-Trafficking Methods to Natural Products Research

PubMed Central

Araya, Juan J.; Montenegro, Gloria; Mitscher, Lester A.; Timmermann, Barbara N.

2010-01-01

A novel simultaneous phase-trafficking approach using spatially separated solid-supported reagents (SSR) for rapid separation of neutral, basic, and acidic compounds from organic plant extracts with minimum labor is reported. Acidic and basic ion exchange resins were physically separated into individual sacks (“teabags”) for trapping basic and acidic compounds respectively, leaving behind in solution neutral components of the natural mixtures. Trapped compounds were then recovered from solid phase by appropriate suspension in acidic or basic solutions. The feasibility of the proposed separation protocol was demonstrated and optimized with an “artificial mixture” of model compounds. In addition, the utility of this methodology was illustrated with the successful separation of the alkaloid skytanthine from Skytanthus acutus Meyen and the main catechins and caffeine from Camellia sinensis L. (Kuntze). This novel approach offers multiple advantages over traditional extraction methods, as it is not labor intensive, makes use of only small quantities of solvents, produces fractions in adequate quantities for biological assays, and can be easily adapted to field conditions for bioprospecting activities. PMID:20704309
Explorative solid-phase extraction (E-SPE) for accelerated microbial natural product discovery, dereplication, and purification.

PubMed

Månsson, Maria; Phipps, Richard K; Gram, Lone; Munro, Murray H G; Larsen, Thomas O; Nielsen, Kristian F

2010-06-25

Microbial natural products (NP) cover a high chemical diversity, and in consequence extracts from microorganisms are often complex to analyze and purify. A distribution analysis of calculated pK(a) values from the 34390 records in Antibase2008 revealed that within pH 2-11, 44% of all included compounds had an acidic functionality, 17% a basic functionality, and 9% both. This showed a great potential for using ion-exchange chromatography as an integral part of the separation procedure, orthogonal to the classic reversed-phase strategy. Thus, we investigated the use of an "explorative solid-phase extraction" (E-SPE) protocol using SAX, Oasis MAX, SCX, and LH-20 columns for targeted exploitation of chemical functionalities. E-SPE provides a minimum of fractions (15) for chemical and biological analyses and implicates development into a preparative scale methodology. Overall, this allows fast extract prioritization, easier dereplication, mapping of biological activities, and formulation of a purification strategy.
Cs{sup +} ion exchange kinetics in complex electrolyte solutions using hydrous crystalline silicotitanates

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

Gu, D.; Nguyen, L.; Philip, C.V.

1997-12-01

TAM-5 is a hydrous crystalline sodium silicotitanate inorganic ion exchanger with a high selectivity for Cs{sup +}. The kinetics of Cs{sup +}-Na{sup +} ion exchange using TAM-5 in multicomponent electrolyte solutions were determined using batch experiments. For the powder, which is composed of crystals, a single-phase, homogeneous model fit the data best. For the granules, which were prepared from the powder, a two-phase, heterogeneous model resulted in an excellent fit of the data. Macropore and crystal diffusivities were determined by fitting the model to experimental data collected on the powder and the granules. Intracrystalline diffusivities were concentration dependent and weremore » on the order of 10{sup {minus}19} m{sup 2}/s. Macropore diffusivities were on the order of 10{sup {minus}10} m{sup 2}/s. Resistance to diffusion in the macropores was not significant for granules with diameters less than 15 {micro}m. A two-phase, homogeneous model, where liquid within the pores is in equilibrium with the solid, was also evaluated for the granules. Surprisingly, for the granules, an excellent fit of the data was obtained; however, the effective macropore diffusivity was 1.1 {times} 10{sup {minus}11} m{sup 2}/s, an order of magnitude smaller than the macropore diffusivity found using the two-phase, heterogeneous model.« less
Important aspects in the formulation of solid-fluid debris-flow models. Part I. Thermodynamic implications

NASA Astrophysics Data System (ADS)

Hutter, Kolumban; Schneider, Lukas

2010-06-01

This article points at some critical issues which are connected with the theoretical formulation of the thermodynamics of solid-fluid mixtures of frictional materials. It is our view that a complete thermodynamic exploitation of the second law of thermodynamics is necessary to obtain the proper parameterizations of the constitutive quantities in such theories. These issues are explained in detail in a recently published book by Schneider and Hutter (Solid-Fluid Mixtures of Frictional Materials in Geophysical and Geotechnical Context, 2009), which we wish to advertize with these notes. The model is a saturated mixture of an arbitrary number of solid and fluid constituents which may be compressible or density preserving, which exhibit visco-frictional (visco-hypoplastic) behavior, but are all subject to the same temperature. Mass exchange between the constituents may account for particle size separation and phase changes due to fragmentation and abrasion. Destabilization of a saturated soil mass from the pre- and the post-critical phases of a catastrophic motion from initiation to deposition is modeled by symmetric tensorial variables which are related to the rate independent parts of the constituent stress tensors.
Antiferromagnetic vs. non-magnetic ε phase of solid oxygen. Periodic density functional theory studies using a localized atomic basis set and the role of exact exchange.

PubMed

Ramírez-Solís, A; Zicovich-Wilson, C M; Hernández-Lamoneda, R; Ochoa-Calle, A J

2017-01-25

The question of the non-magnetic (NM) vs. antiferromagnetic (AF) nature of the ε phase of solid oxygen is a matter of great interest and continuing debate. In particular, it has been proposed that the ε phase is actually composed of two phases, a low-pressure AF ε 1 phase and a higher pressure NM ε 0 phase [Crespo et al., Proc. Natl. Acad. Sci. U. S. A., 2014, 111, 10427]. We address this problem through periodic spin-restricted and spin-polarized Kohn-Sham density functional theory calculations at pressures from 10 to 50 GPa using calibrated GGA and hybrid exchange-correlation functionals with Gaussian atomic basis sets. The two possible configurations for the antiferromagnetic (AF1 and AF2) coupling of the 0 ≤ S ≤ 1 O 2 molecules in the (O 2 ) 4 unit cell were studied. Full enthalpy-driven geometry optimizations of the (O 2 ) 4 unit cells were done to study the pressure evolution of the enthalpy difference between the non-magnetic and both antiferromagnetic structures. We also address the evolution of structural parameters and the spin-per-molecule vs. pressure. We find that the spin-less solution becomes more stable than both AF structures above 50 GPa and, crucially, the spin-less solution yields lattice parameters in much better agreement with experimental data at all pressures than the AF structures. The optimized AF2 broken-symmetry structures lead to large errors of the a and b lattice parameters when compared with experiments. The results for the NM model are in much better agreement with the experimental data than those found for both AF models and are consistent with a completely non-magnetic (O 2 ) 4 unit cell for the low-pressure regime of the ε phase.
VQS (vapor-quasiliquid-solid, vapor-quasisolid-solid) mechanism presents a unified foundation for the syntheses of nanotubes, primarily carbon nanotubes

NASA Astrophysics Data System (ADS)

Mohammad, S. Noor

2017-09-01

Nanotubes are synthesized almost entirely by metal-catalyst-free and metal-catalyst-mediated non-eutectic mechanism(s). An investigation has been carried out to understand the basics of this mechanism. Various possible chemical and physical processes involved in nanotube synthesis have been researched. Various components and attributes of nanotube synthesis have been evaluated. Phase transitions, alloy formation, porosity, carrier transport and the fundamentals underlying them have been examined. Nanoparticle surfaces conducive to nanotube synthesis have been examined. The role of surface treatment, which includes oxidation, oxygenation, acid treatment, plasma treatment, water treatment, sputtering, etc in creating such surfaces, has been investigated. The role of surface treatment and phase transitions as functions of temperature, pressure, ambient, contaminants, surface amorphicity, etc in creating diffusion paths for the diffusion of growth species for supersaturation and nucleation has been explored. Interdiffusion of catalyst and source materials, and hence exchange of materials, on the nanoparticle surface, have been elucidated. This exchange of materials on catalyst surface appears to add a new dimension to the synthesis kinetics. Integrated together, they reveal a general mechanism for probably all metal-catalyst-free and metal-catalyst-mediated non-eutectic nanotube synthesis. Available experiments strongly support the proposed mechanism; they suggest that this mechanism has a broad appeal.
From Two-Phase to Three-Phase: The New Electrochemical Interface by Oxide Electrocatalysts

NASA Astrophysics Data System (ADS)

Xu, Zhichuan J.

2018-03-01

Electrochemical reactions typically occur at the interface between a solid electrode and a liquid electrolyte. The charge exchange behaviour between these two phases determines the kinetics of electrochemical reactions. In the past few years, significant advances have been made in the development of metal oxide electrocatalysts for fuel cell and electrolyser reactions. However, considerable gaps remain in the fundamental understanding of the charge transfer pathways and the interaction between the metal oxides and the conducting substrate on which they are located. In particular, the electrochemical interfaces of metal oxides are significantly different from the traditional (metal) ones, where only a conductive solid electrode and a liquid electrolyte are considered. Oxides are insulating and have to be combined with carbon as a conductive mediator. This electrode configuration results in a three-phase electrochemical interface, consisting of the insulating oxide, the conductive carbon, and the liquid electrolyte. To date, the mechanistic insights into this kind of non-traditional electrochemical interface remain unclear. Consequently conventional electrochemistry concepts, established on classical electrode materials and their two-phase interfaces, are facing challenges when employed for explaining these new electrode materials. [Figure not available: see fulltext.
Facet-controlled phase separation in supersaturated Au-Ni nanoparticles upon shape equilibration

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

Herz, A., E-mail: andreas.herz@tu-ilmenau.de, E-mail: dong.wang@tu-ilmenau.de; Rossberg, D.; Hentschel, M.

2015-08-17

Solid-state dewetting is used to fabricate supersaturated, submicron-sized Au-Ni solid solution particles out of thin Au/Ni bilayers by means of a rapid thermal annealing technique. Phase separation in such particles is studied with respect to their equilibrium crystal (or Wulff) shape by subsequent annealing at elevated temperature. It is found that (100) faceting planes of the equilibrated particles are enriched with Ni and (111) faces with Au. Both phases are considered by quantum-mechanical calculations in combination with an error-reduction scheme that was developed to compensate for a missing exchange-correlation potential that would reliably describe both Au and Ni. The observedmore » phase configuration is then related to the minimization of strongly anisotropic elastic energies of Au- and Ni-rich phases and results in a rather unique nanoparticle composite state that is characterized by nearly uniform value of elastic response to epitaxial strains all over the faceted surface. The same conclusion is yielded also by evaluating bi-axial elastic moduli when employing interpolated experimental elastic constants. This work demonstrates a useful route for studying features of physical metallurgy at the mesoscale.« less
Sorption of carboxylic acid from carboxylic salt solutions at PHS close to or above the pK.sub.a of the acid, with regeneration with an aqueous solution of ammonia or low-molecular-weight alkylamine

DOEpatents

King, C. Judson; Tung, Lisa A.

1992-01-01

Carboxylic acids are sorbed from aqueous feedstocks at pHs close to or above the acids' pH.sub.a into a strongly basic organic liquid phase or onto a basic solid adsorbent or moderately basic ion exchange resin. the acids are freed from the sorbent phase by treating it with aqueous alkylamine or ammonia thus forming an alkylammonium or ammonium carobxylate which dewatered and decomposed to the desired carboxylic acid and the alkylamine or ammonia.
Phase stability and magnetic behavior of FeCrCoNiGe high-entropy alloy

NASA Astrophysics Data System (ADS)

Huang, Shuo; Vida, Ádám; Molnár, Dávid; Kádas, Krisztina; Varga, Lajos Károly; Holmström, Erik; Vitos, Levente

2015-12-01

We report an alternative FeCrCoNiGe magnetic material based on FeCrCoNi high-entropy alloy with Curie point far below the room temperature. Investigations are done using first-principles calculations and key experimental measurements. Results show that the equimolar FeCrCoNiGe system is decomposed into a mixture of face-centered cubic and body-centered cubic solid solution phases. The increased stability of the ferromagnetic order in the as-cast FeCrCoNiGe composite, with measured Curie temperature of 640 K, is explained using the exchange interactions.
DOE Office of Scientific and Technical Information (OSTI.GOV)

B.B. Rokhman

A two-dimensional stationary model of motion, heat and mass exchange, and chemical reaction of polydisperse coke and ash particles in ascending gas-suspension flow has been constructed with allowance for the turbulent and pseudo turbulent mechanisms of transfer in the dispersed phase. The system of equations that describes motion and heat transfer in the solid phase has been closed at the level of the equations for the second moments of velocity and temperature pulsations, whereas the momentum equations of the carrying medium have been closed using the equation for turbulent gas energy, which allows for the influence of the particles andmore » heterogeneous reactions.« less
Review of Fuel Cell Technologies for Military Land Vehicles

DTIC Science & Technology

2014-09-01

fuel cell technologies for APUs are Proton Exchange Membrane Fuel Cells ( PEMFC ), direct methanol fuel cells and Solid Oxide Fuel Cells (SOFC). The...6 4.2 Proton Exchange Membrane Fuel Cells ( PEMFC ...OEM Original Equipment Manufacturer PEM Proton Exchange Membrane PEMFC Proton Exchange Membrane Fuel Cell SOFC Solid Oxide Fuel Cell TRL Technical
Using natural distributions of short-lived radium isotopes to quantify groundwater discharge and recharge

USGS Publications Warehouse

Krest, J.M.; Harvey, J.W.

2003-01-01

Radium activity in pore water of wetland sediments often differs from the amount expected from local production, decay, and exchange with solid phases. This disequilibrium results from vertical transport of radium with groundwater that flows between the underlying aquifer and surface water. In situations where groundwater recharge or discharge is significant, the rate of vertical water flow through wetland sediment can be determined from the radium disequilibrium by a combined model of transport, production, decay, and exchange with solid phases. We have developed and tested this technique at three sites in the freshwater portion of the Everglades by quantifying vertical advective velocities in areas with persistent groundwater recharge or discharge and estimating a coefficient of dispersion at a site that is subject to reversals between recharge and discharge. Groundwater velocities (v) were determined to be between 0 and -0.5 cm d-1 for a recharge site and 1.5 ?? 0.4 cm d-1 for a discharge site near Levee 39 in the Everglades. Strong gradients in 223Ra and 224Ra usually occurred at the base of the peat layer, which avoided the problems of other tracers (e.g., chloride) for which greatest sensitivity occurs near the peat surface - a zone readily disturbed by processes unrelated to groundwater flow. This technique should be easily applicable to any wetland system with different production rates of these isotopes in distinct sedimentary layers or surface water. The approach is most straightforward in systems where constant pore-water ionic strength can be assumed, simplifying the modeling of radium exchange.
Applications of reversible covalent chemistry in analytical sample preparation.

PubMed

Siegel, David

2012-12-07

Reversible covalent chemistry (RCC) adds another dimension to commonly used sample preparation techniques like solid-phase extraction (SPE), solid-phase microextraction (SPME), molecular imprinted polymers (MIPs) or immuno-affinity cleanup (IAC): chemical selectivity. By selecting analytes according to their covalent reactivity, sample complexity can be reduced significantly, resulting in enhanced analytical performance for low-abundance target analytes. This review gives a comprehensive overview of the applications of RCC in analytical sample preparation. The major reactions covered include reversible boronic ester formation, thiol-disulfide exchange and reversible hydrazone formation, targeting analyte groups like diols (sugars, glycoproteins and glycopeptides, catechols), thiols (cysteinyl-proteins and cysteinyl-peptides) and carbonyls (carbonylated proteins, mycotoxins). Their applications range from low abundance proteomics to reversible protein/peptide labelling to antibody chromatography to quantitative and qualitative food analysis. In discussing the potential of RCC, a special focus is on the conditions and restrictions of the utilized reaction chemistry.
Reactive Transport of Marcellus Shale Waters in Natural Aquifers: the Role of Mineralogical Compositions and Spatial Distribution Patterns

NASA Astrophysics Data System (ADS)

Cai, Z.; Wen, H.; Li, L.

2017-12-01

Accidental release of Marcellus Shale waters (MSW) can release high concentrations of chemicals that can deteriorate groundwater quality. It is important to understand the reactive transport and fate of chemicals from MSW. Natural aquifers typically have complex mineralogical compositions and are heterogeneous with large spatial variation in terms of physical and geochemical properties. To investigate the effects of mineralogical compositions, flow-through experiments and reactive transport modeling were carried out using 3 large columns (5 cm×50 cm, Quartz, Calcite, and Vermiculite). Results indicate calcite immobilizes heavy metals by precipitation and solid solution partitioning (coprecipitation). Vermiculite retards heavy metals through ion exchange. The sorbed chemicals however slowly release back to the groundwater. Na and Ca transport similarly to Br in Qtz and Cal columns however become sorbed in Vrm column during release through ion exchange by 27.8% and 46.5%, respectively and later slowly release back to aqueous phase. To understand the role of mineral spatial patterns, three 2D flow-cell (40 cm×12 cm×1 cm) experiments were carried out. All flow cells have the same clay mass within quartz matrix but different spatial patterns characterized by the relative length of the clay zone ( 0, ¼, ½) of the domain length (L). Results show that in the uniform column, ion exchange dominates and most Ba sorbs to the solid phase, to an extent Ba cannot precipitate out with SO4 as barite. In 1/2-Zone, however, most Ba precipitates as barite. In 1/4-Zone, both ion exchange and mineral precipitation occur. In general, the 1/2-Zone has the smallest ion exchange capacity for other species including Na, Ca, Mg, K and heavy metals (Mn, Cu, Zn, Cd and Pb) as well. Our flow cell experiment emphasizes the importance of mineral spatial patterns in regulating not only reaction rates but also the type of reactions in controlling the reactive transport of MSW chemicals. The column study suggests in carbonate rich aquifers, carbonate facilitate natural attenuation. In clay-rich aquifers, such as sandstone aquifers, clay helps alleviate the cation during MSW release however these sorbed cations will ultimately release back to the aqueous phase. In sand and gravel aquifers, mixing process primarily controls the concentration level.

Transient changes in milk production efficiency and bacterial community composition resulting from near-total exchange of ruminal contents between high- and low-efficiency Holstein cows.

PubMed

Weimer, Paul J; Cox, Madison S; Vieira de Paula, Tania; Lin, Miao; Hall, Mary Beth; Suen, Garret

2017-09-01

The objectives of this study were to determine if milk production efficiency (MPE) is altered by near-total exchange of ruminal contents between high- (HE) and low-MPE (LE) cows and to characterize ruminal bacterial community composition (BCC) before exchange and over time postexchange. Three pairs of ruminally cannulated, third-lactation cows were selected whose MPE (energy-corrected milk per unit of dry matter intake) differed over their first 2 lactations. Approximately 95% of ruminal contents were exchanged between cows within each pair. Ruminal pH and volatile fatty acid (VFA) profiles, along with BCC (characterized by sequencing of the variable 4 region of 16S rRNA genes), were assessed just before feeding on d -8, -7, -5, -4, -1, 1, 2, 3, 7, 10, 14, 21, 28, 35, 42, and 56, relative to the exchange date. High-MPE cows had higher total ruminal VFA concentrations, higher molar percentages of propionate and valerate, and lower molar percentages of acetate and butyrate than did LE cows, and re-established these differences 1 d after contents exchange. Across all LE cows, MPE increased during 7 d postexchange but declined thereafter. Two of the 3 HE cows displayed decreases in MPE following introduction of the ruminal contents from the corresponding LE cow, but MPE increased in the third HE cow, which was determined to be an outlier. For all 6 cows, both liquid- and solids-associated BCC differed between individuals within a pair before contents exchange. Upon exchange, BCC of both phases in all 3 pairs was more similar to that of the donor inoculum than to preexchange host BCC. For 5 of 6 cows, the solids-associated community returned within 10 d to more resemble the preexchange community of that host than that of the donor community. Individual variability before the exchange was greater in liquids than in solids, as was the variability in response of bacterial communities to the exchange. Individual cows varied in their response, but generally moved toward re-establishment of their preexchange communities by 10 d after contents exchange. By contrast, ruminal pH and VFA profiles returned to preexchange levels within 1 d. Despite the small number of cows studied, the data suggest an apparent role for the ruminal bacterial community as a determinant of MPE. Copyright © 2017 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.
Solid-phase partitioning of mercury in artisanal gold mine tailings from selected key areas in Mindanao, Philippines, and its implications for mercury detoxification.

PubMed

Opiso, Einstine M; Aseneiro, John Paul J; Banda, Marybeth Hope T; Tabelin, Carlito B

2018-03-01

The solid-phase partitioning of mercury could provide necessary data in the identification of remediation techniques in contaminated artisanal gold mine tailings. This study was conducted to determine the total mercury content of mine wastes and identify its solid-phase partitioning through selective sequential extraction coupled with cold vapour atomic absorption spectroscopy. Samples from mine tailings and the carbon-in-pulp (CIP) process were obtained from selected key areas in Mindanao, Philippines. The results showed that mercury use is still prevalent among small-scale gold miners in the Philippines. Tailings after ball mill-gravity concentration (W-BM and Li-BM samples) from Mt Diwata and Libona contained high levels of mercury amounting to 25.024 and 6.5 mg kg -1 , respectively. The most prevalent form of mercury in the mine tailings was elemental/amalgamated mercury, followed by water soluble, exchangeable, organic and strongly bound phases, respectively. In contrast, mercury content of carbon-in-pulp residues were significantly lower at only 0.3 and 0.06 mg kg -1 for P-CIP (Del Pilar) and W-CIP (Mt Diwata), respectively. The bulk of mercury in P-CIP samples was partitioned in residual fraction while in W-CIP samples, water soluble mercury predominated. Overall, this study has several important implications with regards to mercury detoxification of contaminated mine tailings from Mindanao, Philippines.
Systematic Assessment of Seven Solvent and Solid-Phase Extraction Methods for Metabolomics Analysis of Human Plasma by LC-MS

NASA Astrophysics Data System (ADS)

Sitnikov, Dmitri G.; Monnin, Cian S.; Vuckovic, Dajana

2016-12-01

The comparison of extraction methods for global metabolomics is usually executed in biofluids only and focuses on metabolite coverage and method repeatability. This limits our detailed understanding of extraction parameters such as recovery and matrix effects and prevents side-by-side comparison of different sample preparation strategies. To address this gap in knowledge, seven solvent-based and solid-phase extraction methods were systematically evaluated using standard analytes spiked into both buffer and human plasma. We compared recovery, coverage, repeatability, matrix effects, selectivity and orthogonality of all methods tested for non-lipid metabolome in combination with reversed-phased and mixed-mode liquid chromatography mass spectrometry analysis (LC-MS). Our results confirmed wide selectivity and excellent precision of solvent precipitations, but revealed their high susceptibility to matrix effects. The use of all seven methods showed high overlap and redundancy which resulted in metabolite coverage increases of 34-80% depending on LC-MS method employed as compared to the best single extraction protocol (methanol/ethanol precipitation) despite 7x increase in MS analysis time and sample consumption. The most orthogonal methods to methanol-based precipitation were ion-exchange solid-phase extraction and liquid-liquid extraction using methyl-tertbutyl ether. Our results help facilitate rational design and selection of sample preparation methods and internal standards for global metabolomics.
Systematic Assessment of Seven Solvent and Solid-Phase Extraction Methods for Metabolomics Analysis of Human Plasma by LC-MS

PubMed Central

Sitnikov, Dmitri G.; Monnin, Cian S.; Vuckovic, Dajana

2016-01-01

The comparison of extraction methods for global metabolomics is usually executed in biofluids only and focuses on metabolite coverage and method repeatability. This limits our detailed understanding of extraction parameters such as recovery and matrix effects and prevents side-by-side comparison of different sample preparation strategies. To address this gap in knowledge, seven solvent-based and solid-phase extraction methods were systematically evaluated using standard analytes spiked into both buffer and human plasma. We compared recovery, coverage, repeatability, matrix effects, selectivity and orthogonality of all methods tested for non-lipid metabolome in combination with reversed-phased and mixed-mode liquid chromatography mass spectrometry analysis (LC-MS). Our results confirmed wide selectivity and excellent precision of solvent precipitations, but revealed their high susceptibility to matrix effects. The use of all seven methods showed high overlap and redundancy which resulted in metabolite coverage increases of 34–80% depending on LC-MS method employed as compared to the best single extraction protocol (methanol/ethanol precipitation) despite 7x increase in MS analysis time and sample consumption. The most orthogonal methods to methanol-based precipitation were ion-exchange solid-phase extraction and liquid-liquid extraction using methyl-tertbutyl ether. Our results help facilitate rational design and selection of sample preparation methods and internal standards for global metabolomics. PMID:28000704
Magnetic properties of solid oxygen under pressure (Review Article)

NASA Astrophysics Data System (ADS)

Freiman, Yu. A.

2015-11-01

Solid oxygen is a unique crystal combining properties of a simple molecular solid and a magnet. Unlike ordinary magnets, the exchange interaction in solid oxygen acts on a background of weak Van der Waals forces, providing a significant part of the total lattice energy. Therefore, the magnetic and lattice properties of solid oxygen are very closely related. This manifests itself in a very rich phase diagram and numerous anomalies of thermal, magnetic and optical properties. Low-temperature low-pressure α-O2 is a two-sublattice collinear Neel antiferromagnet. At a pressure of ˜6 GPa, α-O2 is transformed into δ-O2, in which three different magnetic structures are realized upon increasing temperature. At ˜8 GPa δ-O2 is transformed into ɛ-O2. In this transition, O2 molecules combine into four-molecule clusters (O2)4. This transformation is accompanied by a magnetic collapse. This review describes the evolution of the magnetic structure with increasing pressure, and analyzes the causes behind this behavior.
Determination of trace iron in the boiler water used in power generation plants by solid-phase spectrophotometry.

PubMed

Sarenqiqige; Maeda, Akihiro; Yoshimura, Kazuhisa

2014-01-01

A sensitive, simple and low-cost determination method for the total iron concentration in boiler water systems of power generation plants was developed by solid phase spectrometry (SPS) using 2,4,6-tris(2-pyridyl)-1,3,5-triazine (TPTZ) as a coloring agent. The reagents and 0.08 cm(3) of a cation exchanger were added to a 50-cm(3) boiler water sample, then mixed for 30 min to adsorb/concentrate the produced Fe(TPTZ)2(2+) colored complex on the solid beads, resulting in a 625 times concentration of the target analyte without any other procedure. The detection limit of 0.1 μg dm(-3) was obtained, and the optimum conditions for the digestion procedure and color developing reaction was investigated and reported. According to the application of this method to real samples, the present SPS method is the best one because of the shorter analysis time, simpler operation and use of very low-cost equipment compared to the conventional methods, such as TPTZ solution spectrophotometric method after a 16 times concentration, ICP-MS and AAS.
Gas phase 1H NMR studies and kinetic modeling of dihydrogen isotope equilibration catalyzed by Ru-nanoparticles under normal conditions: dissociative vs. associative exchange.

PubMed

Limbach, Hans-Heinrich; Pery, Tal; Rothermel, Niels; Chaudret, Bruno; Gutmann, Torsten; Buntkowsky, Gerd

2018-04-25

The equilibration of H2, HD and D2 between the gas phase and surface hydrides of solid organic-ligand-stabilized Ru metal nanoparticles has been studied by gas phase 1H NMR spectroscopy using closed NMR tubes as batch reactors at room temperature and 800 mbar. When two different nanoparticle systems, Ru/PVP (PVP ≡ polyvinylpyrrolidone) and Ru/HDA (HDA ≡ hexadecylamine) were exposed to D2 gas, only the release of HD from the hydride containing surface could be detected in the initial stages of the reaction, but no H2. In the case of Ru/HDA also the reverse experiment was performed where surface deuterated nanoparticles were exposed to H2. In that case, the conversion of H2 into gaseous HD was detected. In order to analyze the experimental kinetic and spectroscopic data, we explored two different mechanisms taking into account potential kinetic and equilibrium H/D isotope effects. Firstly, we explored the dissociative exchange mechanism consisting of dissociative adsorption of dihydrogen, fast hydride surface diffusion and associative desorption of dihydrogen. It is shown that if D2 is the reaction partner, only H2 will be released in the beginning of the reaction, and HD only in later reaction stages. The second mechanism, dubbed here associative exchange consists of the binding of dihydrogen to Ru surface atoms, followed by a H-transfer to or by H-exchange with an adjacent hydride site, and finally of the associative desorption of dihydrogen. In that case, in the exchange with D2, only HD will be released in the beginning of the reaction. Our experimental results are not compatible with the dissociative exchange but can be explained in terms of the associative exchange. Whereas the former will dominate at low temperatures and pressures, the latter will prevail around room temperature and normal pressures where transition metal nanoparticles are generally used as reaction catalysts.
Co-flow anode/cathode supply heat exchanger for a solid-oxide fuel cell assembly

DOEpatents

Haltiner, Jr., Karl J.; Kelly, Sean M.

2005-11-22

In a solid-oxide fuel cell assembly, a co-flow heat exchanger is provided in the flow paths of the reformate gas and the cathode air ahead of the fuel cell stack, the reformate gas being on one side of the exchanger and the cathode air being on the other. The reformate gas is at a substantially higher temperature than is desired in the stack, and the cathode gas is substantially cooler than desired. In the co-flow heat exchanger, the temperatures of the reformate and cathode streams converge to nearly the same temperature at the outlet of the exchanger. Preferably, the heat exchanger is formed within an integrated component manifold (ICM) for a solid-oxide fuel cell assembly.
Solvent exchange in a metal–organic framework single crystal monitored by dynamic in situ X-ray diffraction

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

Cox, Jordan M.; Walton, Ian M.; Bateman, Gage

2017-07-25

Understanding the processes by which porous solid-state materials adsorb and release guest molecules would represent a significant step towards developing rational design principles for functional porous materials. To elucidate the process of liquid exchange in these materials, dynamicin situX-ray diffraction techniques have been developed which utilize liquid-phase chemical stimuli. Using these time-resolved diffraction techniques, the ethanol solvation process in a flexible metal–organic framework [Co(AIP)(bpy) 0.5(H 2O)]·2H 2O was examined. The measurements provide important insight into the nature of the chemical transformation in this system including the presence of a previously unreported neat ethanol solvate structure.
Fractionation and characterization of dissolved organic matter (DOM) in refinery wastewater by revised phase retention and ion-exchange adsorption solid phase extraction followed by ESI FT-ICR MS.

PubMed

Fang, Zhi; He, Chen; Li, Yongyong; Chung, Keng H; Xu, Chunming; Shi, Quan

2017-01-01

Although the progress of high resolution mass spectrometry in the past decade has enabled the molecular characterization of dissolved organic matter (DOM) in water as a whole, fractionation of DOM is necessary for a comprehensive characterization due to its super-complex nature. Here we proposed a method for the fractionation of DOM in a wastewater based on solubility and acidic-basic properties. Solid phase extraction (SPE) cartridges with reversed phase retention and ion-exchange adsorption capacities, namely MAX and MCX, were used in succession to fractionate a petroleum refinery wastewater into four fractions: hydrophobic acid (HOA), hydrophobic neutral (HON), hydrophobic base (HOB), and hydrophilic substance (HIS) fractions. According to the total organic carbon (TOC) analysis, 72.6% (in term of TOC) of DOM was extracted in hydrophobic fractions, in which HON was the most abundant. Hydrophobic extracts were characterized by negative and positive ion electrospray (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), respectively. Compounds with multiple oxygen atoms were predominant in the HOA, which were responded strongly in the negative ESI MS. Nitrogen containing compounds were the major detected species by positive ion ESI in all hydrophobic fractions. The molecular composition of the DOM were discussed based on the FT-ICR MS results. The fractionation provided salt free samples which enables the direct analysis of the fractions by ESI and a deep insight into the molecular composition of DOM in the wastewater. The method is potential for routine evaluation of DOM in industry wastewaters, as well as environmental water samples. Copyright © 2016. Published by Elsevier B.V.
Segmented nanowires displaying locally controllable properties

DOEpatents

Sutter, Eli Anguelova; Sutter, Peter Werner

2013-03-05

Vapor-liquid-solid growth of nanowires is tailored to achieve complex one-dimensional material geometries using phase diagrams determined for nanoscale materials. Segmented one-dimensional nanowires having constant composition display locally variable electronic band structures that are determined by the diameter of the nanowires. The unique electrical and optical properties of the segmented nanowires are exploited to form electronic and optoelectronic devices. Using gold-germanium as a model system, in situ transmission electron microscopy establishes, for nanometer-sized Au--Ge alloy drops at the tips of Ge nanowires (NWs), the parts of the phase diagram that determine their temperature-dependent equilibrium composition. The nanoscale phase diagram is then used to determine the exchange of material between the NW and the drop. The phase diagram for the nanoscale drop deviates significantly from that of the bulk alloy.
Preparation of a reversed-phase/anion-exchange mixed-mode spherical sorbent by Pickering emulsion polymerization for highly selective solid-phase extraction of acidic pharmaceuticals from wastewater.

PubMed

Huang, Chaonan; Li, Yun; Yang, Jiajia; Peng, Junyu; Jin, Jing; Dhanjai; Wang, Jincheng; Chen, Jiping

2017-10-27

The present work represents a simple and effective preparation of a novel mixed-mode anion-exchange (MAX) sorbent based on porous poly[2-(diethylamino)ethyl methacrylate-divinylbenzene] (poly(DEAEMA-DVB)) spherical particles synthesized by one-step Pickering emulsion polymerization. The poly(DEAEMA-DVB) particles were quaternized with 1,4-butanediol diglycidyl ether (BDDE) followed by triethylamine (TEA) via epoxy-amine reaction to offer strong anion exchange properties. The synthesized MAX sorbent was characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy, nitrogen adsorption-desorption measurements and elemental analysis. The MAX sorbent possessed regular spherical shape and narrow diameter distribution (15-35μm), a high IEC of 0.54meq/g, with carbon and nitrogen contents of 80.3% and 1.62%, respectively. Compared to poly(DEAEMA-DVB), the MAX sorbent exhibited decreased S BET (390.5 vs. 515.3m 2 g -1 ), pore volume (0.74 vs. 0.85cm 3 g -1 ) and pore size (16.8 vs. 17.3nm). Moreover, changes of N content for producing the MAX sorbent reveal a successful two-step quaternization, which can be highly related to such a high IEC. Finally, the MAX sorbent was successfully evaluated for selective isolation and purification of some selected acidic pharmaceuticals (ketoprofen, KEP; naproxen, NAP; and ibuprofen, IBP) from neutral (hydrocortisone, HYC), basic (carbamazepine, CAZ; amitriptyline, AMT) pharmaceuticals and other interferences in water samples using solid phase extraction (SPE). An efficient analytical method based on the MAX-based mixed-mode SPE coupled with HPLC-UV was developed for highly selective extraction and cleanup of acidic KEP, NAP and IBP in spiked wastewater samples. The developed method exhibited good sensitivity (0.009-0.085μgL -1 limit of detection), satisfactory recoveries (82.1%-105.5%) and repeatabilities (relative standard deviation < 7.9%, n=3). Copyright © 2017 Elsevier B.V. All rights reserved.
18O/16O in CO2 evolved from goethite during some unusually rapid solid state α-FeOOH to α-Fe2O3 phase transitions: Test of an exchange model for possible use in oxygen isotope analyses of goethite

NASA Astrophysics Data System (ADS)

Yapp, Crayton J.

2015-12-01

The initial ∼60% of an isothermal vacuum dehydration of goethite can commonly be approximated by first order kinetics. Also, natural goethites contain small amounts of an Fe(CO3)OH component in apparent solid solution. The 18O/16O of CO2 evolved from the Fe(CO3)OH during isothermal vacuum dehydrations is related to the 18O/16O of the goethite by an apparent fractionation factor (αapp) that is, in turn, correlated with a first order rate constant, |m|. A kinetic exchange model predicts that αapp should decrease as |m| increases for a range of |m| that corresponds to relatively slow rates of dehydration. This pattern has been observed in published results. In contrast, for rapid rates of dehydration, αapp is predicted to increase with increasing |m|. Isothermal vacuum dehydrations of two natural goethites had unusually large values of |m| and provided serendipitous tests of this rapid-rate prediction. For these experiments, the measured values of αapp were consistent with patterns of variation predicted by the model. This allowed an estimate of the activation energy (E2) of a model parameter, K2, which is the rate constant for oxygen isotope exchange between CO2 and H2O during the solid-state goethite to hematite phase transition. The estimated value of E2 is only ∼9 kJ/mol. Heterogeneous catalysis tends to decrease the activation energies of gas reactions. Consequently, the inferred value of E2 suggests that goethite and/or hematite catalyze oxygen isotope exchange between CO2 and H2O during the solid-state phase change. Yield, δ13C, and δ18O values are routinely measured for increments of CO2 evolved from the Fe(CO3)OH component during isothermal vacuum dehydration of goethite. Model-predicted values of αapp can be combined with plateau δ18O values of the evolved CO2 to estimate the δ18O of the goethite with a less than optimal, but potentially useful, precision of about ±0.8‰. Therefore, a single analytical procedure (incremental dehydration) applied to one aliquot of a sample could provide not only δ13C and mole fractions (X) of the Fe(CO3)OH component, but also hydrogen yield, δD, and the approximate δ18O value of the goethite. Recovery of multiple types of geochemical data from a single aliquot would be particularly useful if the amount of sample available for analysis were limited. Also, the method could be used to estimate the δ18O value of goethite in mixtures of minerals not amenable to selective dissolution - e.g., goethite admixed with hematite.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Nichols, Ralph L.; Seitz, Roger R.; Dixon, Kenneth L.

The Waste Treatment and Immobilization Plant (WTP) at Hanford is being constructed to treat 56 million gallons of radioactive waste currently stored in underground tanks at the Hanford site. Operation of the WTP will generate several solid secondary waste (SSW) streams including used process equipment, contaminated tools and instruments, decontamination wastes, high-efficiency particulate air filters (HEPA), carbon adsorption beds, silver mordenite iodine sorbent beds, and spent ion exchange resins (IXr) all of which are to be disposed in the Integrated Disposal Facility (IDF). An applied research and development program was developed using a phased approach to incrementally develop the informationmore » necessary to support the IDF PA with each phase of the testing building on results from the previous set of tests and considering new information from the IDF PA calculations. This report contains the results from the exploratory phase, Phase 1 and preliminary results from Phase 2. Phase 3 is expected to begin in the fourth quarter of FY17.« less
Heat storage in alloy transformations

NASA Technical Reports Server (NTRS)

Birchenall, C. E.; Gueceri, S. I.; Farkas, D.; Labdon, M. B.; Nagaswami, N.; Pregger, B.

1981-01-01

The feasibility of using metal alloys as thermal energy storage media was determined. The following major elements were studied: (1) identification of congruently transforming alloys and thermochemical property measurements; (2) development of a precise and convenient method for measuring volume change during phase transformation and thermal expansion coefficients; (3) development of a numerical modeling routine for calculating heat flow in cylindrical heat exchangers containing phase change materials; and (4) identification of materials that could be used to contain the metal alloys. Several eutectic alloys and ternary intermetallic phases were determined. A method employing X-ray absorption techniques was developed to determine the coefficients of thermal expansion of both the solid and liquid phases and the volume change during phase transformation from data obtained during one continuous experimental test. The method and apparatus are discussed and the experimental results are presented. The development of the numerical modeling method is presented and results are discussed for both salt and metal alloy phase change media.
Power generation plant integrating concentrated solar power receiver and pressurized heat exchanger

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

Sakadjian, Bartev B; Flynn, Thomas J; Hu, Shengteng

A power plant includes a solar receiver heating solid particles, a standpipe receiving solid particles from the solar receiver, a pressurized heat exchanger heating working fluid by heat transfer through direct contact with heated solid particles flowing out of the bottom of the standpipe, and a flow path for solid particles from the bottom of the standpipe into the pressurized heat exchanger that is sealed by a pressure P produced at the bottom of the standpipe by a column of heated solid particles of height H. The flow path may include a silo or surge tank comprising a pressure vesselmore » connected to the bottom of the standpipe, and a non-mechanical valve. The power plant may further include a turbine driven by heated working fluid discharged from the pressurized heat exchanger, and a compressor driven by the turbine.« less
Hot-water and solid-phase extraction of fluorescent whitening agents in paper materials and infant clothes followed by unequivocal determination with ion-pair chromatography-tandem mass spectrometry.

PubMed

Chen, Hsin-Chang; Ding, Wang-Hsien

2006-03-10

A comprehensive method for the determination of four stilbene-type disulfonate and one distyrylbiphenyl-type fluorescent whitening agents (FWAs) in paper materials (napkin and paper tissue) and infant clothes was developed. FWAs were extracted from paper material and cloth samples using a hot-water extraction, and the aqueous extracts were then preconcentrated with the newly developed Oasis WAX (mixed-mode of weak anion exchange and reversed-phase sorbent) solid-phase extraction cartridge. The analytes were unequivocal determined by ion pair chromatography coupled with negative electrospray ionization-tandem mass spectrometry (HPLC-ESI-MS-MS), applying a di-n-hexyl-ammonium acetate (DHAA) as the ion-pairing reagent in mobile phase. Limits of quantitation (LOQ) were established between 0.2 and 0.9 ng/g in 2 g of samples. Recovery of five FWAs in spiked commercial samples was between 42 and 95% and RSD (n = 3) ranging from 2 to 11%. The method was finally applied to commercial samples, showing that two stilbene-type disulfonates were predominant FWAs detected in napkin and infant cloth samples.
In Situ Tracking Kinetic Pathways of Li+/Na+ Substitution during Ion-Exchange Synthesis of LixNa1.5-xVOPO4F0.5.

PubMed

Park, Young-Uk; Bai, Jianming; Wang, Liping; Yoon, Gabin; Zhang, Wei; Kim, Hyungsub; Lee, Seongsu; Kim, Sung-Wook; Looney, J Patrick; Kang, Kisuk; Wang, Feng

2017-09-13

Ion exchange is a ubiquitous phenomenon central to wide industrial applications, ranging from traditional (bio)chemical separation to the emerging chimie douce synthesis of materials with metastable structure for batteries and other energy applications. The exchange process is complex, involving substitution and transport of different ions under non-equilibrium conditions, and thus difficult to probe, leaving a gap in mechanistic understanding of kinetic exchange pathways toward final products. Herein, we report in situ tracking kinetic pathways of Li + /Na + substitution during solvothermal ion-exchange synthesis of Li x Na 1.5-x VOPO 4 F 0.5 (0 ≤ x ≤ 1.5), a promising multi-Li polyanionic cathode for batteries. The real-time observation, corroborated by first-principles calculations, reveals a selective replacement of Na + by Li + , leading to peculiar Na + /Li + /vacancy orderings in the intermediates. Contradicting the traditional belief of facile topotactic substitution via solid solution reaction, an abrupt two-phase transformation occurs and predominantly governs the kinetics of ion exchange and transport in the 1D polyanionic framework, consequently leading to significant difference of Li stoichiometry and electrochemical properties in the exchanged products. The findings may help to pave the way for rational design of ion exchange synthesis for making new materials.
An experimental study on PEO polymer electrolyte based all-solid-state supercapacitor

NASA Astrophysics Data System (ADS)

Yijing, Yin

Supercapacitors are one of the most important electrochemical energy storage and conversion devices, however low ionic conductivity of solid state polymer electrolytes and the poor accessibility of the ions to the active sites in the porous electrode will cause low performance for all-solid-state supercapacitors and will limit their application. The objective of the dissertation is to improve the performance of all-solid-state supercapactor by improving electrolyte conductivity and solving accessibility problem of the ions to the active sites. The low ionic conductivity (10-8 S/cm) of poly(ethylene oxide) (PEO) limits its application as an electrolyte. Since PEO is a semicrystal polymer and the ion conduction take place mainly in the amorphous regions of the PEO/Lithium salt complex, improvements in the percentage of amorphous phase in PEO or increasing the charge carrier concentration and mobility could increase the ionic conductivity of PEO electrolyte. Hot pressing along with the additions of different lithium salts, inorganic fillers and plasticizers were applied to improve the ionic conductivity of PEO polymer electrolytes. Four electrode methods were used to evaluate the conductivity of PEO based polymer electrolytes. Results show that adding certain lithium salts, inorganic fillers, and plasticizers could improve the ionic conductivity of PEO electrolytes up 10-4 S/cm. Further hot pressing treatment could improve the ionic conductivity of PEO electrolytes up to 10-3 S/cm. The conductivity improvement after hot pressing treatment is elucidated as that the spherulite crystal phase is convert into the fringed micelle crystal phase or the amorphous phase of PEO electrolytes. PEO electrolytes were added into active carbon as a binder and an ion conductor, so as to provide electrodes with not only ion conduction, but also the accessibility of ion to the active sites of electrodes. The NaI/I 2 mediator was added to improve the conductivity of PEO electrolyte and provide pseudocapacitance for all-solid-state supercapacitors. Impedance, cyclic voltammetry, and gavalnostatic charge/discharge measurements were conducted to evaluate the electrochemical performance of PEO polymer electrolytes based all-solid-state supercapacitors. Results demonstrate that the conductivity of PEO electrolyte could be improved to 0.1 S/cm with a mediator concentration of 50wt%. A high conductivity in the PEO electrolyte with mediator is an indication of a high electron exchange rate between the mediator and mediator. The high electron exchange rates at mediator carbon interface and between mediator and mediator are essential in order to obtain a high response rate and high power. This automatically solves the accessibility problem. With the addition of NaI/I2 mediator, the specific capacitance increased more than 30 folds, specific power increased almost 20 folds, and specific energy increased around 10 folds. Further addition of filler to the electrodes along with the mediator could double the specific capacitor and specific power of the all-solid-state supercapacitor. The stability of the corresponded supercapacitor is good within 2000 cycles.
Determination of Triazine Herbicides in Drinking Water by Dispersive Micro Solid Phase Extraction with Ultrahigh-Performance Liquid Chromatography-High-Resolution Mass Spectrometric Detection.

PubMed

Chen, Dawei; Zhang, Yiping; Miao, Hong; Zhao, Yunfeng; Wu, Yongning

2015-11-11

A novel dispersive micro solid phase extraction (DMSPE) method based on a polymer cation exchange material (PCX) was applied to the simultaneous determination of the 30 triazine herbicides in drinking water with ultrahigh-performance liquid chromatography-high-resolution mass spectrometric detection. Drinking water samples were acidified with formic acid, and then triazines were adsorbed by the PCX sorbent. Subsequently, the analytes were eluted with ammonium hydroxide/acetonitrile. The chromatographic separation was performed on an HSS T3 column using water (4 mM ammonium formate and 0.1% formic acid) and acetonitrile (0.1% formic acid) as the mobile phase. The method achieved LODs of 0.2-30.0 ng/L for the 30 triazines, with recoveries in the range of 70.5-112.1%, and the precision of the method was better than 12.7%. These results indicated that the proposed method had the advantages of convenience and high efficiency when applied to the analysis of the 30 triazines in drinking water.

Crystal structure and superconducting properties of KSr2Nb3O10

NASA Astrophysics Data System (ADS)

Kawaguchi, T.; Horigane, K.; Itoh, Y.; Kobayashi, K.; Horie, R.; Kambe, T.; Akimitsu, J.

2018-05-01

We performed X-ray diffraction (XRD) and DC magnetic susceptibility measurements to elucidate the crystal structure and superconducting properties of KSr2Nb3O10. From the diffraction pattern indexing, it was found that KSr2Nb3O10 crystallizes with monoclinic symmetry, space group P21/m(11). We succeeded in preparing high temperature (HT) and low temperature (LT) phases of KSr2Nb3O10 powder samples synthesized by a conventional solid state reaction and an ion-exchange reaction, respectively. Superconductivity was observed at 4 K by Li intercalation and it was found that the superconducting volume fraction of the LT phase ( 1.4%) is clearly larger than that of the HT phase (0.07%).
Assessing the failure of continuum formula for solid-solid drag force using discrete element method in large size ratios

NASA Astrophysics Data System (ADS)

Jalali, Payman; Hyppänen, Timo

2017-06-01

In loose or moderately-dense particle mixtures, the contact forces between particles due to successive collisions create average volumetric solid-solid drag force between different granular phases (of different particle sizes). The derivation of the mathematical formula for this drag force is based on the homogeneity of mixture within the calculational control volume. This assumption especially fails when the size ratio of particles grows to a large value of 10 or greater. The size-driven inhomogeneity is responsible to the deviation of intergranular force from the continuum formula. In this paper, we have implemented discrete element method (DEM) simulations to obtain the volumetric mean force exchanged between the granular phases with the size ratios greater than 10. First, the force is calculated directly from DEM averaged over a proper time window. Second, the continuum formula is applied to calculate the drag forces using the DEM quantities. We have shown the two volumetric forces are in good agreement as long as the homogeneity condition is maintained. However, the relative motion of larger particles in a cloud of finer particles imposes the inhomogeneous distribution of finer particles around the larger ones. We have presented correction factors to the volumetric force from continuum formula.
Strontium-free rare earth perovskite ferrites with fast oxygen exchange kinetics: Experiment and theory

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

DOEpatents

King, C.J.; Tung, L.A.

1992-07-21

Carboxylic acids are sorbed from aqueous feedstocks at pHs close to or above the acids' pH[sub a] into a strongly basic organic liquid phase or onto a basic solid adsorbent or moderately basic ion exchange resin. The acids are freed from the sorbent phase by treating it with aqueous alkylamine or ammonia thus forming an alkylammonium or ammonium carboxylate which dewatered and decomposed to the desired carboxylic acid and the alkylamine or ammonia. 8 figs.
Hydrogen/deuterium exchange, a unique and effective method for MS fragmentation behavior elucidation of ginkgolides and its application to systematic research in Ginkgo biloba.

PubMed

Niu, Xingliang; Luo, Jun; Xu, Deran; Zou, Hongyan; Kong, Lingyi

2017-02-05

Ginkgolides, the main active constituents of Ginkgo biloba, possess significant selectively inhibition on platelet-activating factor and pancreatic lipase and attract wide attention in pharmacological research area. In our study, an effective hydrogen/deuterium (H/D) exchange method was developed by exchanging the α-Hs of lactone groups in ginkgolides with Ds, which was very useful for the elucidation of the fragmentation patterns of ginkgolides in Quadrupole Time-of-flight Mass Spectrometry (Q-TOF-MS), especially in accurately distinguishing the type and position of substituent in framework of ginkgolides. Then, a systematic research strategy for qualitative and quantitative analysis of ginkgolides, based on H/D exchange, tandem solid-phase extraction and LC-Q-TOF-MS, was developed, which was successfully applied in each medicinal part of G. biloba, which indicated that ginkgolide B was the most abundant ginkgolide in the seeds of G. biloba (60.6μg/g). This research was the successful application of H/D exchange in natural products, and proved that H/D exchange is a potential method for analysis research of complex TCMs active constituents. Copyright © 2016 Elsevier B.V. All rights reserved.
Solid-phase extraction of small biologically active peptides on cartridges and microelution 96-well plates from human urine.

PubMed

Semenistaya, Ekaterina; Zvereva, Irina; Krotov, Grigory; Rodchenkov, Grigory

2016-09-01

Currently liquid chromatography - mass spectrometry (LC-MS) analysis after solid-phase extraction (SPE) on weak cation-exchange cartridges is a method of choice for anti-doping analysis of small bioactive peptides such as growth hormone releasing peptides (GHRPs), desmoporessin, LHRH, and TB-500 short fragment. Dilution of urine samples with phosphate buffer for pH adjustment and SPE on weak cation exchange microelution plates was tested as a means to increase throughput of this analysis. Dilution using 200 mM phosphate buffer provides good buffering capacity without affecting the peptides recoveries. SPE on microelution plates was performed on Waters Positive Pressure-96 Processor with subsequent evaporation of eluates in nitrogen flow. Though the use of smaller sample volume decreases the pre-concentration factor and increases the limits of detection of 5 out of 17 detected peptides, the recovery, linearity, and reproducibility of the microelution extraction were comparable with cartridge SPE. The effectiveness of protocols was confirmed by analysis of urine samples containing ipamorelin, and GHRP-6 and its metabolites. SPE after urine sample dilution with buffer can be used for faster sample preparation. The use of microelution plates decreases consumption of solvents and allows processing of up to 96 samples simultaneously. Cartridge SPE with manual рН adjustment remains the best option for confirmation. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.
Intralanthanide Separation on Layered Titanium(IV) Organophosphate Materials via a Selective Transmetalation Process.

PubMed

Zhang, Wenzhong; Hietala, Sami; Khriachtchev, Leonid; Hatanpää, Timo; Doshi, Bhairavi; Koivula, Risto

2018-06-21

The lanthanides (Ln) are an essential part of many advanced technologies. Our societal transformation toward renewable energy drives their ever-growing demand. The similar chemical properties of the Ln pose fundamental difficulties in separating them from each other, yet high purity elements are crucial for specific applications. Here, we propose an intralanthanide separation method utilizing a group of titanium(IV) butyl phosphate coordination polymers as solid-phase extractants. These materials are characterized, and they contain layered structures directed by the hydrophobic interaction of the alkyl chains. The selective Ln uptake results from the transmetalation reaction (framework metal cation exchange), where the titanium(IV) serves as sacrificial coordination centers. The "tetrad effect" is observed from a dilute Ln 3+ mixture. However, smaller Ln 3+ ions are preferentially extracted in competitive binary separation models between adjacent Ln pairs. The intralanthanide ion-exchange selectivity arises synergistically from the coordination and steric strain preferences, both of which follow the reversed Ln contraction order. A one-step aqueous separation of neodymium (Nd) and dysprosium (Dy) is quantitatively achievable by simply controlling the solution pH in a batch mode, translating into a separation factor of greater than 2000 and 99.1% molar purity of Dy in the solid phase. Coordination polymers provide a versatile platform for further exploring selective Ln separation processes via the transmetalation process.
Preparation of magnetic melamine-formaldehyde resin and its application to extract nonsteroidal anti-inflammatory drugs.

PubMed

Xue, Shu-Wen; Li, Jing; Xu, Li

2017-05-01

Magnetic melamine-formaldehyde resin was prepared via water-in-oil emulsification approach by entrapping Fe 3 O 4 magnetic nanoparticles as the core. The preparation of the magnetic resin was optimized by investigating the amount of polyethylene glycol 20000 and Fe 3 O 4 nanoparticles, the concentration of the catalyst (hydrochloric acid), as well as the mechanical stirring rate. The prepared material was characteristic of excellent anion-exchange capacity, good water wettability, and proper magnetism. Its application was demonstrated by magnetic solid-phase extraction of nonsteroidal anti-inflammatory drugs coupled to high performance liquid chromatography-UV analysis. Under the optimal conditions, the proposed method showed broad linear range of 1-5000 ng mL -1 of milk and urine samples, satisfactory reproducibility with intra-day and inter-day relative standard deviations less than 12.4% and 9.7%, respectively, and low limits of detection of 0.2 ng mL -1 for the studied nonsteroidal anti-inflammatory drugs. The developed method was successfully used for the determination of the nonsteroidal anti-inflammatory drugs in spiked urine and milk samples. The magnetic melamine-formaldehyde resin was promising for the sample pretreatment of acidic analytes via anion-exchange interaction with convenient operation from complex sample matrix. Graphical abstract Magnetic solid-phase extraction based on melamine-formaldehyde resin.
Field method for the determination of hexavalent chromium by ultrasonication and strong anion-exchange solid-phase extraction.

PubMed

Wang, J; Ashley, K; Marlow, D; England, E C; Carlton, G

1999-03-01

A simple, fast, sensitive, and economical field method was developed and evaluated for the determination of hexavalent chromium (CrVI) in environmental and workplace air samples. By means of ultrasonic extraction in combination with a strong anion-exchange solid-phase extraction (SAE-SPE) technique, the filtration, isolation, and determination of CrVI in the presence of trivalent chromium (CrIII) and potential interferents was achieved. The method entails (1) ultrasonication in basic ammonium buffer solution to extract CrVI from environmental matrixes; (2) SAE-SPE to separate CrVI from CrIII and interferences; (3) elution/acidification of the eluate; (4) complexation of chromium with 1,5-diphenylcarbazide; and (5) spectrophotometric determination of the colored chromium-diphenylcarbazone complex. Several critical parameters were optimized in order to effect the extraction of both soluble (K2CrO4) and insoluble (PbCrO4) forms of CrVI without inducing CrIII oxidation or CrVI reduction. The method allowed for the dissolution and purification of CrVI from environmental and workplace air sample matrixes for up to 24 samples simultaneously in less than 90 min (including ultrasonication). The results demonstrated that the method was simple, fast, quantitative, and sufficiently sensitive for the determination of occupational exposures of CrVI. The method is applicable for on-site monitoring of CrVI in environmental and industrial hygiene samples.
Controlling electron beam-induced structure modifications and cation exchange in cadmium sulfide-copper sulfide heterostructured nanorods.

PubMed

Zheng, Haimei; Sadtler, Bryce; Habenicht, Carsten; Freitag, Bert; Alivisatos, A Paul; Kisielowski, Christian

2013-11-01

The atomic structure and interfaces of CdS/Cu2S heterostructured nanorods are investigated with the aberration-corrected TEAM 0.5 electron microscope operated at 80 kV and 300 kV applying in-line holography and complementary techniques. Cu2S exhibits a low-chalcocite structure in pristine CdS/Cu2S nanorods. Under electron beam irradiation the Cu2S phase transforms into a high-chalcocite phase while the CdS phase maintains its wurtzite structure. Time-resolved experiments reveal that Cu(+)-Cd(2+) cation exchange at the CdS/Cu2S interfaces is stimulated by the electron beam and proceeds within an undisturbed and coherent sulfur sub-lattice. A variation of the electron beam current provides an efficient way to control and exploit such irreversible solid-state chemical processes that provide unique information about system dynamics at the atomic scale. Specifically, we show that the electron beam-induced copper-cadmium exchange is site specific and anisotropic. A resulting displacement of the CdS/Cu2S interfaces caused by beam-induced cation interdiffusion equals within a factor of 3-10 previously reported Cu diffusion length measurements in heterostructured CdS/Cu2S thin film solar cells with an activation energy of 0.96 eV. © 2013 Elsevier B.V. All rights reserved.
Synthesis and characterization of a new microporous cesium silicotitanate (SNL-B) molecular sieve

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

NYMAN,MAY D.; GU,B.X.; WANG,L.M.

2000-03-20

Ongoing hydrothermal Cs-Ti-Si-O-H{sub 2}O phase investigations has produced several new ternary phases including a novel microporous Cs-silicotitanate molecular sieve, SNL-B with the approximate formula of Cs{sub 3}TiSi{sub 3}O{sub 9.5}{center_dot}3H{sub 2}O. SNL-B is only the second molecular sieve Cs-silicotitanate phase reported to have been synthesized by hydrothermal methods. Crystallites are very small (0.1 x 2 microns) with a blade-like morphology. SNL-B is confirmed to be a 3-dimensional molecular sieve by a variety of characterization techniques (N{sub 2} adsorption, ion exchange, water adsorption/desorption, solid state CP-MAS NMR). SNL-B is able to desorb and adsorb water from its pores while retaining its crystalmore » structure and exchanges Cs cations readily. Additional techniques were used to describe fundamental properties (powder X-ray diffraction, FTIR, {sup 29}Si and {sup 133}/Cs MAS NMR, DTA, SEM/EDS, ion selectivity, and radiation stability). The phase relationships of metastable SNL-B to other hydrothermally synthesized Cs-Ti-Si-O-H{sub 2}O phases are discussed, particularly its relationship to a Cs-silicotitanate analogue of pharmacosiderite, and a novel condensed phase, a polymorph of Cs{sub 2}TiSi{sub 6}O{sub 15}(SNL-A).« less
Ion-exchange solid-phase extraction combined with liquid chromatography-tandem mass spectrometry for the determination of veterinary drugs in organic fertilizers.

PubMed

Zhao, Zhiyong; Zhang, Yanmei; Xuan, Yanfang; Song, Wei; Si, Wenshuai; Zhao, Zhihui; Rao, Qinxiong

2016-06-01

The analysis of veterinary drugs in organic fertilizers is crucial for an assessment of potential risks to soil microbial communities and human health. We develop a robust and sensitive method to quantitatively determine 19 veterinary drugs (amantadine, sulfonamides and fluoroquinolones) in organic fertilizers. The method involved a simple solid-liquid extraction step using the combination of acetonitrile and McIlvaine buffer as extraction solvent, followed by cleanup with a solid-phase extraction cartridge containing polymeric mixed-mode anion-exchange sorbents. Ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was used to separate and detect target analytes. We particularly focused on the optimization of sample clean-up step: different diluents and dilution factors were tested. The developed method was validated in terms of linearity, recovery, precision, sensitivity and specificity. The recoveries of all the drugs ranged from 70.9% to 112.7% at three concentration levels, with the intra-day and inter-day relative standard deviation lower than 15.7%. The limits of quantification were between 1.0 and 10.0μg/kg for all the drugs. Matrix effect was minimized by matrix-matched calibration curves. The analytical method was successfully applied for the survey of veterinary drugs contamination in 20 compost samples. The results indicated that fluoroquinolones had higher incidence rate and mean concentration levels ranging from 31.9 to 308.7μg/kg compared with other drugs. We expect the method will provide the basis for risk assessment of veterinary drugs in organic fertilizers. Copyright © 2016 Elsevier B.V. All rights reserved.
Orifice plate for controlling solids flow, methods of use thereof and articles comprising the same

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

Jukkola, Glen D.; Teigen, Bard C.

Disclosed herein is an orifice plate comprising one or more plates having orifices disposed therein; the orifices being operative to permit the flow of solids from a moving bed heat exchanger to a solids flow control system; where the orifice plate is downstream of a tube bundle of the moving bed heat exchanger and upstream of the solids flow control system and wherein the orifice plate is operative to evenly distribute the flow of solids in the solids flow control system.
Stable and metastable nanowires displaying locally controllable properties

DOEpatents

Sutter, Eli Anguelova; Sutter, Peter Werner

2014-11-18

Vapor-liquid-solid growth of nanowires is tailored to achieve complex one-dimensional material geometries using phase diagrams determined for nanoscale materials. Segmented one-dimensional nanowires having constant composition display locally variable electronic band structures that are determined by the diameter of the nanowires. The unique electrical and optical properties of the segmented nanowires are exploited to form electronic and optoelectronic devices. Using gold-germanium as a model system, in situ transmission electron microscopy establishes, for nanometer-sized Au--Ge alloy drops at the tips of Ge nanowires (NWs), the parts of the phase diagram that determine their temperature-dependent equilibrium composition. The nanoscale phase diagram is then used to determine the exchange of material between the NW and the drop. The phase diagram for the nanoscale drop deviates significantly from that of the bulk alloy.
A discrete model of Ostwald ripening based on multiple pairwise interactions

NASA Astrophysics Data System (ADS)

Di Nunzio, Paolo Emilio

2018-06-01

A discrete multi-particle model of Ostwald ripening based on direct pairwise interactions is developed for particles with incoherent interfaces as an alternative to the classical LSW mean field theory. The rate of matter exchange depends on the average surface-to-surface interparticle distance, a characteristic feature of the system which naturally incorporates the effect of volume fraction of second phase. The multi-particle diffusion is described through the definition of an interaction volume containing all the particles involved in the exchange of solute. At small volume fractions this is proportional to the size of the central particle, at higher volume fractions it gradually reduces as a consequence of diffusion screening described on a geometrical basis. The topological noise present in real systems is also included. For volume fractions below about 0.1 the model predicts broad and right-skewed stationary size distributions resembling a lognormal function. Above this value, a transition to sharper, more symmetrical but still right-skewed shapes occurs. An excellent agreement with experiments is obtained for 3D particle size distributions of solid-solid and solid-liquid systems with volume fraction 0.07, 0.30, 0.52 and 0.74. The kinetic constant of the model depends on the cube root of volume fraction up to about 0.1, then increases rapidly with an upward concavity. It is in good agreement with the available literature data on solid-liquid mixtures in the volume fraction range from 0.20 to about 0.75.
Metastable nanobubbles at the solid-liquid interface due to contact angle hysteresis.

PubMed

Nishiyama, Takashi; Yamada, Yutaka; Ikuta, Tatsuya; Takahashi, Koji; Takata, Yasuyuki

2015-01-27

Nanobubbles exist at solid-liquid interfaces between pure water and hydrophobic surfaces with very high stability, lasting in certain cases up to several days. Not only semispherical but also other shapes, such as micropancakes, are known to exist at such interfaces. However, doubt has been raised as to whether or not the nanobubbles are gas-phase entities. In this study, surface nanobubbles at a pure water-highly ordered pyrolytic graphite (HOPG) interface were investigated by peak force quantitative nanomechanics (PF-QNM). Multiple isolated nanobubbles generated by the solvent-exchange method were present on the terraced areas, avoiding the steps of the HOPG surface. Adjacent nanobubbles coalesced and formed metastable nanobubbles. Coalescence was enhanced by the PF-QNM measurement. We determined that nanobubbles can exist for a long time because of nanoscale contact angle hysteresis at the water-HOPG interface. Moreover, the hydrophilic steps of HOPG were avoided during coalescence, providing evidence that the nanobubbles are truly gas phase.
Self-assembly of large-scale crack-free gold nanoparticle films using a ‘drain-to-deposit’ strategy

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

Yang, Guang; Hallinan, Daniel T.

2016-04-26

Gold nanoparticles are widely studied due to the ease of controlled synthesis, facile surface modification, and interesting physical properties. However, a technique for depositing large-area, crack-free monolayers on solid substrates is lacking. Herein is presented a method for accomplishing this. Spherical gold nanoparticles were synthesized as an aqueous dispersion. Assembly into monolayers and ligand exchange occurred simultaneously at an organic/aqueous interface. Then the monolayer film was deposited onto arbitrary solid substrates by slowly pumping out the lower, aqueous phase. This allowed the monolayer film (and liquid–liquid interface) to descend without significant disturbance, eventually reaching substrates contained in the aqueous phase.more » The resulting macroscopic quality of the films was found to be superior to films transferred by Langmuir techniques. The surface plasmon resonance and Raman enhancement of the films were evaluated and found to be uniform across the surface of each film.« less
Modeling of gun barrel surface erosion: Historic perspective

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

Buckingham, A.C.

1996-08-01

Results and interpretations of numerical simulations of some dominant processes influencing gun barrel propellant combustion and flow-induced erosion are presented. Results include modeled influences of erosion reduction techniques such as solid additives, vapor phase chemical modifications, and alteration of surface solid composition through use of thin coatings. Precedents and historical perspective are provided with predictions from traditional interior ballistics compared to computer simulations. Accelerating reactive combustion flow, multiphase and multicomponent transport, flow-to-surface thermal/momentum/phase change/gas-surface chemical exchanges, surface and micro-depth subsurface heating/stress/composition evolution and their roles in inducing surface cracking, spall, ablation, melting, and vaporization are considered. Recognition is given tomore » cyclic effects of previous firing history on material preconditioning. Current perspective and outlook for future are based on results of a US Army-LLNL erosion research program covering 7 y in late 1970s. This is supplemented by more recent research on hypervelocity electromagnetic projectile launchers.« less
Fabrication and characterization of Cu/sub 2/S-CdZnS solar cells. Final report. Realisation et caracterisation de cellules solaires Cu/sub 2/S-CdZnS

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

Cadene, M.

Thin films of Cd sub(1-y)Zn sub y S (0 < y < 0.2) have been prepared either by thermal evaporation of the powdered solids from a single crucible, or by rapid evaporation from two crucibles. Different methods were used to characterise the films according to their structural, electrical and electron-optical properties as a function of the amount of Zn in the film. Both liquid-phase and solid-phase ion exchange processes have been used to deposit a thin film of Cu/sub 2/S on the Cd sub(1-y)Zn sub y S film to produce a p-n hetero-junction. A study of the growth of themore » Cd/sub 2/S layer has been carried out. Photocurrents and voltages have been determined for these Cu/sub 2/S-CdZnS cells.« less
Inorganic Halogen Oxidizer Research.

DTIC Science & Technology

1978-01-25

depend on the rate of exchange. Finally, in our experiments we were dealing RI/RD78-125 B-4 -5- with polymeric solid AsF 5 or BF3 phases which on...well be a heterogeneous diffusion controlled reaction and step (5) might be the rate determining step in the above mechanism. It was shown that at...temperatures above -196*C, where a given NF+ salt is still stable in the absence of light, uv irradiation causes a rapid decay RI/RD78-125 B-5 -6- decay of

Physical Laws for Mechanobiology

NASA Technical Reports Server (NTRS)

Freed, Alan D.

2007-01-01

Higher-level physical laws applicable to biological tissues are presented that will permit the modeling of metabolic activity at the cellular level, including variations in the mass of a tissue. Here the tissue is represented as a fluid/solid mixture, wherein molecular solutes transport within the fluid, and cells can migrate throughout the porous solid. Variations in mass can arise via exchanges in mass between the constituent phases within a control volume such that mass is conserved in the tissue overall. The governing balance laws for mass, momentum, energy, and entropy are a special case of those describing a chemically reacting mixture with diffusion. Thermodynamic constraints on the constitutive structure are addressed. Biophysics; Biomechanics; Brownian motion; Cell migration; Mixture theory; Thermodynamic laws; Tissue mechanics
Sound velocity measurement of nuclear-ordered U2D2 solid 3He along the melting curve

NASA Astrophysics Data System (ADS)

Nomura, R.; Suzuki, M.; Yamaguchi, M.; Sasaki, Y.; Mizusaki, T.

2000-05-01

The sound velocity of a single-domain 3He crystal was measured in the nuclear-ordered low-field phase and the paramagnetic phase along the melting curve, using 10.98 MHz longitudinal sound. The temperature dependence of the sound velocity along the melting curve was explained by a nuclear spin contribution and the molar volume change along the melting curve. By comparing the measured velocity with thermodynamic quantities, we extracted the Grüneizen constant for the exchange energy. The anisotropy of the velocity in the ordered phase was investigated for three samples and was found to be smaller than 2×10 -5 in Δ v/ v. The attenuation coefficient of the sound was much smaller than 0.2 cm-1.
Geochemical processes in ground water resulting from surface mining of coal at the Big Sky and West Decker Mine areas, southeastern Montana

USGS Publications Warehouse

Clark, D.W.

1995-01-01

A potential hydrologic effect of surface mining of coal in southeastern Montana is a change in the quality of ground water. Dissolved-solids concen- trations in water in spoils aquifers generally are larger than concentrations in water in the coal aquifers they replaced; however, laboratory experiments have indicated that concentrations can decrease if ground water flows from coal-mine spoils to coal. This study was conducted to determine if decreases in concentrations occur onsite and, if so, which geochemical processes caused the decreases. Solid-phase core samples of spoils, unmined over- burden, and coal, and ground-water samples were collected from 16 observation wells at two mine areas. In the Big Sky Mine area, changes in ground- water chemistry along a flow path from an upgradient coal aquifer to a spoils aquifer probably were a result of dedolomitization. Dissolved-solids concentrations were unchanged as water flowed from a spoils aquifer to a downgradient coal aquifer. In the West Decker Mine area, dissolved-solids concentrations apparently decreased from about 4,100 to 2,100 milligrams per liter as water moved along an inferred flow path from a spoils aquifer to a downgradient coal aquifer. Geochemical models were used to analyze changes in water chemistry on the basis of results of solid-phase and aqueous geochemical characteristics. Geochemical processes postulated to result in the apparent decrease in dissolved-solids concentrations along this inferred flow path include bacterial reduction of sulfate, reverse cation exchange within the coal, and precipitation of carbonate and iron-sulfide minerals.
Ab initio molecular crystal structures, spectra, and phase diagrams.

PubMed

Hirata, So; Gilliard, Kandis; He, Xiao; Li, Jinjin; Sode, Olaseni

2014-09-16

Conspectus Molecular crystals are chemists' solids in the sense that their structures and properties can be understood in terms of those of the constituent molecules merely perturbed by a crystalline environment. They form a large and important class of solids including ices of atmospheric species, drugs, explosives, and even some organic optoelectronic materials and supramolecular assemblies. Recently, surprisingly simple yet extremely efficient, versatile, easily implemented, and systematically accurate electronic structure methods for molecular crystals have been developed. The methods, collectively referred to as the embedded-fragment scheme, divide a crystal into monomers and overlapping dimers and apply modern molecular electronic structure methods and software to these fragments of the crystal that are embedded in a self-consistently determined crystalline electrostatic field. They enable facile applications of accurate but otherwise prohibitively expensive ab initio molecular orbital theories such as Møller-Plesset perturbation and coupled-cluster theories to a broad range of properties of solids such as internal energies, enthalpies, structures, equation of state, phonon dispersion curves and density of states, infrared and Raman spectra (including band intensities and sometimes anharmonic effects), inelastic neutron scattering spectra, heat capacities, Gibbs energies, and phase diagrams, while accounting for many-body electrostatic (namely, induction or polarization) effects as well as two-body exchange and dispersion interactions from first principles. They can fundamentally alter the role of computing in the studies of molecular crystals in the same way ab initio molecular orbital theories have transformed research practices in gas-phase physical chemistry and synthetic chemistry in the last half century. In this Account, after a brief summary of formalisms and algorithms, we discuss applications of these methods performed in our group as compelling illustrations of their unprecedented power in addressing some of the outstanding problems of solid-state chemistry, high-pressure chemistry, or geochemistry. They are the structure and spectra of ice Ih, in particular, the origin of two peaks in the hydrogen-bond-stretching region of its inelastic neutron scattering spectra, a solid-solid phase transition from CO2-I to elusive, metastable CO2-III, pressure tuning of Fermi resonance in solid CO2, and the structure and spectra of solid formic acid, all at the level of second-order Møller-Plesset perturbation theory or higher.
In Situ Tracking Kinetic Pathways of Li + /Na + Substitution during Ion-Exchange Synthesis of Li xNa 1.5–x VOPO 4 F 0.5

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

Park, Young-Uk; Bai, Jianming; Wang, Liping

Ion exchange is a ubiquitous phenomenon central to wide industrial applications, ranging from traditional (bio)chemical separation to the emerging chimie douce synthesis of materials for batteries and other energy applications. The exchange process is complex, involving substitution and transport of different ions under non-equilibrium conditions, and thus difficult to probe, leaving a gap in mechanistic understanding of kinetic exchange pathways toward final products. Herein, we report in situ tracking kinetic pathways of Li +/Na + substitution during solvothermal ion-exchange synthesis of Li xNa 1.5-xVOPO 4F 0.5 (0 ≤ x ≤ 1.5), a promising multi-Li polyanionic cathode for batteries. The real-timemore » observation, corroborated by first-principles calculations, reveals a selective replacement of Na + by Li +, leading to peculiar Na +/Li +/vacancy orderings in the intermediates. Contradicting the traditional belief of facile topotactic substitution via solid solution reaction, an abrupt two-phase transformation occurs and predominantly governs the kinetics of ion exchange and transport in the 1D polyanionic framework, consequently leading to significant difference of Li stoichiometry and electrochemical properties in the exchanged products. The findings may help to pave the way for rational design of ion exchange synthesis for making new materials.« less
In Situ Tracking Kinetic Pathways of Li + /Na + Substitution during Ion-Exchange Synthesis of Li xNa 1.5–x VOPO 4 F 0.5

DOE PAGES

Park, Young-Uk; Bai, Jianming; Wang, Liping; ...

2017-08-29

Ion exchange is a ubiquitous phenomenon central to wide industrial applications, ranging from traditional (bio)chemical separation to the emerging chimie douce synthesis of materials for batteries and other energy applications. The exchange process is complex, involving substitution and transport of different ions under non-equilibrium conditions, and thus difficult to probe, leaving a gap in mechanistic understanding of kinetic exchange pathways toward final products. Herein, we report in situ tracking kinetic pathways of Li +/Na + substitution during solvothermal ion-exchange synthesis of Li xNa 1.5-xVOPO 4F 0.5 (0 ≤ x ≤ 1.5), a promising multi-Li polyanionic cathode for batteries. The real-timemore » observation, corroborated by first-principles calculations, reveals a selective replacement of Na + by Li +, leading to peculiar Na +/Li +/vacancy orderings in the intermediates. Contradicting the traditional belief of facile topotactic substitution via solid solution reaction, an abrupt two-phase transformation occurs and predominantly governs the kinetics of ion exchange and transport in the 1D polyanionic framework, consequently leading to significant difference of Li stoichiometry and electrochemical properties in the exchanged products. The findings may help to pave the way for rational design of ion exchange synthesis for making new materials.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)

Mathur, Anoop

A key technological issue facing the success of future Concentrating Solar Thermal Power (CSP) plants is creating an economical Thermal Energy Storage (TES) system. Current TES systems use either sensible heat in fluids such as oil, or molten salts, or use thermal stratification in a dual-media consisting of a solid and a heat-transfer fluid. However, utilizing the heat of fusion in inorganic molten salt mixtures in addition to sensible heat , as in a Phase change material (PCM)-based TES, can significantly increase the energy density of storage requiring less salt and smaller containers. A major issue that is preventing themore » commercial use of PCM-based TES is that it is difficult to discharge the latent heat stored in the PCM melt. This is because when heat is extracted, the melt solidifies onto the heat exchanger surface decreasing the heat transfer. Even a few millimeters of thickness of solid material on heat transfer surface results in a large drop in heat transfer due to the low thermal conductivity of solid PCM. Thus, to maintain the desired heat rate, the heat exchange area must be large which increases cost. This project demonstrated that the heat transfer coefficient can be increase ten-fold by using forced convection by pumping a hyper-eutectic salt mixture over specially coated heat exchanger tubes. However,only 15% of the latent heat is used against a goal of 40% resulting in a projected cost savings of only 17% against a goal of 30%. Based on the failure mode effect analysis and experience with pumping salt at near freezing point significant care must be used during operation which can increase the operating costs. Therefore, we conclude the savings are marginal to justify using this concept for PCM-TES over a two-tank TES. The report documents the specialty coatings, the composition and morphology of hypereutectic salt mixtures and the results from the experiment conducted with the active heat exchanger along with the lessons learnt during experimentation.« less
Mott transition in the π -flux S U (4 ) Hubbard model on a square lattice

NASA Astrophysics Data System (ADS)

Zhou, Zhichao; Wu, Congjun; Wang, Yu

2018-05-01

With increasing repulsive interaction, we show that a Mott transition occurs from the semimetal to the valence bond solid, accompanied by the Z4 discrete symmetry breaking. Our simulations demonstrate the existence of a second-order phase transition, which confirms the Ginzburg-Landau analysis. The phase transition point and the critical exponent η are also estimated. To account for the effect of a π flux on the ordering in the strong-coupling regime, we analytically derive by the perturbation theory the ring-exchange term, which is the leading-order term that can reflect the difference between the π -flux and zero-flux S U (4 ) Hubbard models.
The investigation of solid slag obtained by neutralization of sewage sludge.

PubMed

Kavaliauskas, Zydrunas; Valincius, Vitas; Stravinskas, Giedrius; Milieska, Mindaugas; Striugas, Nerijus

2015-11-01

The purpose of this research is to investigate the feasibility of utilizing the slag collected after gasification of organic fuel combined with sewage sludge. The residue left after gasification process is likely usable as raw material for production of supercondensers. The sewage sludge neutralization system consists of a dosing system (fuel tank), gasifier, plasma reactor, electrostatic filter, and heat exchangers. For the gasification process, dried solid sewage is supplied in proportion of 70% to biomass 30% by weight. The slag is collected in a specially designed chamber beneath the gasifier. A scanning electron microscope (SEM) was used to evaluate surface morphology of the samples. Elemental analysis of the sewage sludge slag was performed using the energy-dispersive spectroscopy (EDS) method, which showed different solid-state elements contained in the porous structure of the solid phase: carbon 29%, aluminum 26%, potassium 20%, chlorine 1%, and others. The specific surface area of the sewage sludge slag is 6.15 m(2)/g as the BET analysis shows. In order to use the slag as a secondary raw material, detailed analysis of the structure and properties is necessary for a decision on whether the slag left after gasification of sewage sludge is suitable for any further usages. Initial results indicate that the slag may be used for production of electrodes for supercapacitors. Every year thousands of tons of sewage sludge are formed in Lithuania. Sewage sludge consists of organic and inorganic compounds. Partial combustion, plasma decomposition, and other methods are used to neutralize the sewage sludge. The incineration of sewage sludge results in generation of solid-phase slag. In this paper the material structure and composition of a solid slag (formed during neutralization of sewage sludge) is considered. Also, the impact the ambient temperature on structure and composition of solid slag is analyzed.
System for exchange of hydrogen between liquid and solid phases

DOEpatents

Reilly, James J.; Grohse, Edward W.; Johnson, John R.; Winsche, deceased, Warren E.

1988-01-01

The reversible reaction M+x/2 H.sub.2 .rarw..fwdarw.MH.sub.x, wherein M is a reversible metal hydride former that forms a hydride MH.sub.x in the presence of H.sub.2, generally used to store and recall H.sub.2, is found to proceed under an inert liquid, thereby reducing contamination, providing better temperature control, providing in situ mobility of the reactants, and increasing flexibility in process design. Thus, a slurry of particles of a metal hydride former with an inert solvent is subjected to a temperature and pressure controlled atmosphere containing H.sub.2, to store hydrogen and to release previously stored hydrogen. The direction of the flow of the H.sub.2 through the liquid is dependent upon the H.sub.2 pressure in the gas phase at a given temperature. When the actual H.sub.2 pressure is above the equilibrium absorption pressure of the respective hydride the reaction proceeds to the right, i.e., the metal hydride is formed and hydrogen is stored in the solid particles. When the actual pressure in the gas phase is below the equilibrium dissociation pressure of the respective hydride the reaction proceeds to the left, the metal hydride is decomposed and hydrogen is released into the gas phase.
System for exchange of hydrogen between liquid and solid phases

DOEpatents

Reilly, J.J.; Grohse, E.W.; Johnson, J.R.; Winsche, W.E.

1985-02-22

The reversible reaction M + x/2 H/sub 2/ reversible MH/sub x/, wherein M is a reversible metal hydride former that forms a hydride MH/sub x/ in the presence of H/sub 2/, generally used to store and recall H/sub 2/, is found to proceed under an inert liquid, thereby reducing contamination, providing better temperature control, providing in situ mobility of the reactants, and increasing flexibility in process design. Thus, a slurry of particles of a metal hydride former with an inert solvent is subjected to a temperature and pressure controlled atmosphere containing H/sub 2/, to store hydrogen and to release previously stored hydrogen. The direction of the flow of the H/sub 2/ through the liquid is dependent upon the H/sub 2/ pressure in the gas phase at a given temperature. When the actual H/sub 2/ pressure is above the equilibrium absorption pressure of the respective hydride the reaction proceeds to the right, i.e., the metal hydride is formed and hydrogen is stored in the solid particle. When the actual pressure in the gas phase is below the equilibrium dissociation pressure of the respective hydride the reaction proceeds to the left, the metal hydride is decomposed and hydrogen is released into the gas phase.
High Chloride Doping Levels Stabilize the Perovskite Phase of Cesium Lead Iodide.

PubMed

Dastidar, Subham; Egger, David A; Tan, Liang Z; Cromer, Samuel B; Dillon, Andrew D; Liu, Shi; Kronik, Leeor; Rappe, Andrew M; Fafarman, Aaron T

2016-06-08

Cesium lead iodide possesses an excellent combination of band gap and absorption coefficient for photovoltaic applications in its perovskite phase. However, this is not its equilibrium structure under ambient conditions. In air, at ambient temperature it rapidly transforms to a nonfunctional, so-called yellow phase. Here we show that chloride doping, particularly at levels near the solubility limit for chloride in a cesium lead iodide host, provides a new approach to stabilizing the functional perovskite phase. In order to achieve high doping levels, we first co-deposit colloidal nanocrystals of pure cesium lead chloride and cesium lead iodide, thereby ensuring nanometer-scale mixing even at compositions that potentially exceed the bulk miscibility of the two phases. The resulting nanocrystal solid is subsequently fused into a polycrystalline thin film by chemically induced, room-temperature sintering. Spectroscopy and X-ray diffraction indicate that the chloride is further dispersed during sintering and a polycrystalline mixed phase is formed. Using density functional theory (DFT) methods in conjunction with nudged elastic band techniques, low-energy pathways for interstitial chlorine diffusion into a majority-iodide lattice were identified, consistent with the facile diffusion and fast halide exchange reactions observed. By comparison to DFT-calculated values (with the PBE exchange-correlation functional), the relative change in band gap and the lattice contraction are shown to be consistent with a Cl/I ratio of a few percent in the mixed phase. At these incorporation levels, the half-life of the functional perovskite phase in a humid atmosphere increases by more than an order of magnitude.
Spin Bose-metal phase in a spin- (1)/(2) model with ring exchange on a two-leg triangular strip

NASA Astrophysics Data System (ADS)

Sheng, D. N.; Motrunich, Olexei I.; Fisher, Matthew P. A.

2009-05-01

Recent experiments on triangular lattice organic Mott insulators have found evidence for a two-dimensional (2D) spin liquid in close proximity to the metal-insulator transition. A Gutzwiller wave function study of the triangular lattice Heisenberg model with a four-spin ring exchange term appropriate in this regime has found that the projected spinon Fermi sea state has a low variational energy. This wave function, together with a slave particle-gauge theory analysis, suggests that this putative spin liquid possesses spin correlations that are singular along surfaces in momentum space, i.e., “Bose surfaces.” Signatures of this state, which we will refer to as a “spin Bose metal” (SBM), are expected to manifest in quasi-one-dimensional (quasi-1D) ladder systems: the discrete transverse momenta cut through the 2D Bose surface leading to a distinct pattern of 1D gapless modes. Here, we search for a quasi-1D descendant of the triangular lattice SBM state by exploring the Heisenberg plus ring model on a two-leg triangular strip (zigzag chain). Using density matrix renormalization group (DMRG) supplemented by variational wave functions and a bosonization analysis, we map out the full phase diagram. In the absence of ring exchange the model is equivalent to the J1-J2 Heisenberg chain, and we find the expected Bethe-chain and dimerized phases. Remarkably, moderate ring exchange reveals a new gapless phase over a large swath of the phase diagram. Spin and dimer correlations possess singular wave vectors at particular “Bose points” (remnants of the 2D Bose surface) and allow us to identify this phase as the hoped for quasi-1D descendant of the triangular lattice SBM state. We use bosonization to derive a low-energy effective theory for the zigzag spin Bose metal and find three gapless modes and one Luttinger parameter controlling all power law correlations. Potential instabilities out of the zigzag SBM give rise to other interesting phases such as a period-3 valence bond solid or a period-4 chirality order, which we discover in the DMRG. Another interesting instability is into a spin Bose-metal phase with partial ferromagnetism (spin polarization of one spinon band), which we also find numerically using the DMRG.
Computation material science of structural-phase transformation in casting aluminium alloys

NASA Astrophysics Data System (ADS)

Golod, V. M.; Dobosh, L. Yu

2017-04-01

Successive stages of computer simulation the formation of the casting microstructure under non-equilibrium conditions of crystallization of multicomponent aluminum alloys are presented. On the basis of computer thermodynamics and heat transfer during solidification of macroscale shaped castings are specified the boundary conditions of local heat exchange at mesoscale modeling of non-equilibrium formation the solid phase and of the component redistribution between phases during coalescence of secondary dendrite branches. Computer analysis of structural - phase transitions based on the principle of additive physico-chemical effect of the alloy components in the process of diffusional - capillary morphological evolution of the dendrite structure and the o of local dendrite heterogeneity which stochastic nature and extent are revealed under metallographic study and modeling by the Monte Carlo method. The integrated computational materials science tools at researches of alloys are focused and implemented on analysis the multiple-factor system of casting processes and prediction of casting microstructure.
The influence of precipitation kinetics on trace element partitioning between solid and liquid solutions: A coupled fluid dynamics/thermodynamics framework to predict distribution coefficients

NASA Astrophysics Data System (ADS)

Kavner, A.

2017-12-01

In a multicomponent multiphase geochemical system undergoing a chemical reaction such as precipitation and/or dissolution, the partitioning of species between phases is determined by a combination of thermodynamic properties and transport processes. The interpretation of the observed distribution of trace elements requires models integrating coupled chemistry and mechanical transport. Here, a framework is presented that predicts the kinetic effects on the distribution of species between two reacting phases. Based on a perturbation theory combining Navier-Stokes fluid flow and chemical reactivity, the framework predicts rate-dependent partition coefficients in a variety of different systems. We present the theoretical framework, with applications to two systems: 1. species- and isotope-dependent Soret diffusion of species in a multicomponent silicate melt subjected to a temperature gradient, and 2. Elemental partitioning and isotope fractionation during precipitation of a multicomponent solid from a multicomponent liquid phase. Predictions will be compared with results from experimental studies. The approach has applications for understanding chemical exchange in at boundary layers such as the Earth's surface magmatic systems and at the core/mantle boundary.
Modeling of Blast Furnace with Layered Cohesive Zone

NASA Astrophysics Data System (ADS)

Dong, X. F.; Yu, A. B.; Chew, S. J.; Zulli, P.

2010-04-01

An ironmaking blast furnace (BF) is a moving bed reactor involving counter-, co-, and cross-current flows of gas, powder, liquids, and solids, coupled with heat exchange and chemical reactions. The behavior of multiple phases directly affects the stability and productivity of the furnace. In the present study, a mathematical model is proposed to describe the behavior of fluid flow, heat and mass transfer, as well as chemical reactions in a BF, in which gas, solid, and liquid phases affect each other through interaction forces, and their flows are competing for the space available. Process variables that characterize the internal furnace state, such as reduction degree, reducing gas and burden concentrations, as well as gas and condensed phase temperatures, have been described quantitatively. In particular, different treatments of the cohesive zone (CZ), i.e., layered, isotropic, and anisotropic nonlayered, are discussed, and their influence on simulation results is compared. The results show that predicted fluid flow and thermochemical phenomena within and around the CZ and in the lower part of the BF are different for different treatments. The layered CZ treatment corresponds to the layered charging of burden and naturally can predict the CZ as a gas distributor and liquid generator.
A complete two-phase model of a porous cathode of a PEM fuel cell

NASA Astrophysics Data System (ADS)

Hwang, J. J.

This paper has developed a complete two-phase model of a proton exchange membrane (PEM) fuel cell by considering fluid flow, heat transfer and current simultaneously. In fluid flow, two momentum equations governing separately the gaseous-mixture velocity (u g) and the liquid-water velocity (u w) illustrate the behaviors of the two-phase flow in a porous electrode. Correlations for the capillary pressure and the saturation level connect the above two-fluid transports. In heat transfer, a local thermal non-equilibrium (LTNE) model accounting for intrinsic heat transfer between the reactant fluids and the solid matrices depicts the interactions between the reactant-fluid temperature (T f) and the solid-matrix temperature (T s). The irreversibility heating due to electrochemical reactions, Joule heating arising from Ohmic resistance, and latent heat of water condensation/evaporation are considered in the present non-isothermal model. In current, Ohm's law is applied to yield the conservations in ionic current (i m) and electronic current (i s) in the catalyst layer. The Butler-Volmer correlation describes the relation of the potential difference (overpotential) and the transfer current between the electrolyte (such as Nafion™) and the catalyst (such as Pt/C).
Fast chemical and isotopic exchange of nitrogen during reaction with hot molybdenum

NASA Astrophysics Data System (ADS)

Yokochi, Reika; Marty, Bernard

2006-07-01

Molybdenum crucibles are commonly used to extract nitrogen from geological samples by induction heating. Because nitrogen is known to be reactive with certain metals (e.g., Ti and Fe), we have tested the reactivity of gaseous nitrogen with a Mo crucible held at 1800°C. The consumption of nitrogen, determined by monitoring the N2/40Ar ratio of the gas phase, varied between 25 and 100%, depending on the reaction duration. Nitrogen of the reacted gas was found to be systematically enriched in 15N relative to 14N by 10‰ compared to the initial isotopic composition, without any correlation with nitrogen consumption. We propose that a rapid isotopic exchange occurs between nitrogen originally trapped in the crucible and nitrogen from the gas phase, which modifies the isotopic composition of the reacted gas. This process can significantly bias the isotopic determination of nitrogen in rocks and minerals when a Mo furnace is used for gas extraction. Meanwhile, the rate of N-Mo chemical bonding may be controlled by the formation of nitride (rather than solid solution), a process slower than the isotopic exchange. The use of a Mo furnace for the extraction of trace nitrogen from rocks and minerals should therefore be avoided.
Geochemical phase and particle size relationships of metals in urban road dust.

PubMed

Jayarathne, Ayomi; Egodawatta, Prasanna; Ayoko, Godwin A; Goonetilleke, Ashantha

2017-11-01

Detailed knowledge of the processes that metals undergo during dry weather periods whilst deposited on urban surfaces and their environmental significance is essential to predict the potential influence of metals on stormwater quality in order to develop appropriate stormwater pollution mitigation measures. However, very limited research has been undertaken in this area. Accordingly, this study investigated the geochemical phase and particle size relationships of seven metals which are commonly associated with urban road dust, using sequential extraction in order to assess their mobility characteristics. Metals in the sequentially extracted fractions of exchangeable, reducible, oxidisable and residual were found to follow a similar trend for different land uses even though they had variable accumulation loads. The high affinity of Cd and Zn for exchangeable reactions in both, bulk and size-fractionated solid samples confirmed their high mobility, while the significant enrichment of Ni and Cr in the stable residual fraction indicated a low risk of mobility. The study results also confirmed the availability of Cu, Pb and Mn in both, stable and mobile fractions. The fine fraction of solids (<150 μm) and antecedent dry days can be highlighted as important parameters when determining the fate of metals associated with urban road dust. The outcomes from this study are expected to contribute to the development of effective stormwater pollution mitigation strategies by taking into consideration the metal-particulate relationships. Copyright © 2017 Elsevier Ltd. All rights reserved.
A validated UPLC-MS/MS method coupled with protein precipitation and ion exchange solid phase extraction for the quantitation of porcine relaxin B29 in dog plasma and its application to a pharmacokinetic study.

PubMed

Su, Chong; Sun, Hui; Yang, Hong; Yin, Lei; Zhang, Jiwen; Fawcett, John Paul; Gu, Jingkai

2017-11-01

Porcine relaxin is a 6 kDa peptide hormone of pregnancy with important physiological and pharmacological effects. It contains a number of analogs of which porcine relaxin B29 is one of the most important. To support the development of porcine relaxin B29 as a new drug, we established an UPLC-MS/MS method for its quantitation in dog plasma. Sample preparation by protein precipitation and ion exchange solid phase extraction was followed by UPLC on an XBridge™ BEH300 C18 column at 40 °C in a run time of only 5.5 min. Detection was performed on a Qtrap 6500 mass spectrometer using ESI in the positive ion mode with MRM of the transitions at m/z 831.7 [M+7H] 7+ → 505.4 and m/z 1162.4 [M+5H] 5+ → 226 for pRLX B29 and internal standard (recombinant human insulin), respectively. The method was linear over the concentration range 30-2000 ng/mL with no matrix effects. Intra- and inter-day precisions were < 15% with accuracies in the range 98.8-100.6%. The method was successfully applied to a pharmacokinetic study in beagle dogs after administration of a 0.15 mg/kg intravenous dose. Graphical abstract Sample preparation and detection procedure.

Citropin 1.1 Trifluoroacetate to Chloride Counter-Ion Exchange in HCl-Saturated Organic Solutions: An Alternative Approach.

PubMed

Sikora, Karol; Neubauer, Damian; Jaśkiewicz, Maciej; Kamysz, Wojciech

2018-01-01

In view of the increasing interest in peptides in various market sectors, a stronger emphasis on topics related to their production has been seen. Fmoc-based solid phase peptide synthesis, although being fast and efficient, provides final products with significant amounts of trifluoroacetate ions in the form of either a counter-ion or an unbound impurity. Because of the proven toxicity towards cells and peptide activity inhibition, ion exchange to more biocompatible one is purposeful. Additionally, as most of the currently used counter-ion exchange techniques are time-consuming and burdened by peptide yield reduction risk, development of a new approach is still a sensible solution. In this study, we examined the potential of peptide counter-ion exchange using non-aqueous organic solvents saturated with HCl. Counter-ion exchange of a model peptide, citropin 1.1 (GLFDVIKKVASVIGGL-NH 2 ), for each solvent was conducted through incubation with subsequent evaporation under reduced pressure, dissolution in water and lyophilization. Each exchange was performed four times and compared to a reference method-lyophilization of the peptide from an 0.1 M HCl solution. The results showed superior counter-ion exchange efficiency for most of the organic solutions in relation to the reference method. Moreover, HCl-saturated acetonitrile and tert -butanol provided a satisfying exchange level after just one repetition. Thus, those two organic solvents can be potentially introduced into routine peptide counter-ion exchange.
Revision of Fontes & Garnier's model for the initial 14C content of dissolved inorganic carbon used in groundwater dating

USGS Publications Warehouse

Han, Liang-Feng; Plummer, Niel

2013-01-01

The widely applied model for groundwater dating using 14C proposed by Fontes and Garnier (F&G) (Fontes and Garnier, 1979) estimates the initial 14C content in waters from carbonate-rock aquifers affected by isotopic exchange. Usually, the model of F&G is applied in one of two ways: (1) using a single 13C fractionation factor of gaseous CO2 with respect to a solid carbonate mineral, εg/s, regardless of whether the carbon isotopic exchange is controlled by soil CO2 in the unsaturated zone, or by solid carbonate mineral in the saturated zone; or (2) using different fractionation factors if the exchange process is dominated by soil CO2 gas as opposed to solid carbonate mineral (typically calcite). An analysis of the F&G model shows an inadequate conceptualization, resulting in underestimation of the initial 14C values (14C0) for groundwater systems that have undergone isotopic exchange. The degree to which the 14C0 is underestimated increases with the extent of isotopic exchange. Examples show that in extreme cases, the error in calculated adjusted initial 14C values can be more than 20% modern carbon (pmc). A model is derived that revises the mass balance method of F&G by using a modified model conceptualization. The derivation yields a “global” model both for carbon isotopic exchange dominated by gaseous CO2 in the unsaturated zone, and for carbon isotopic exchange dominated by solid carbonate mineral in the saturated zone. However, the revised model requires different parameters for exchange dominated by gaseous CO2 as opposed to exchange dominated by solid carbonate minerals. The revised model for exchange dominated by gaseous CO2 is shown to be identical to the model of Mook (Mook, 1976). For groundwater systems where exchange occurs both in the unsaturated zone and saturated zone, the revised model can still be used; however, 14C0 will be slightly underestimated. Finally, in carbonate systems undergoing complex geochemical reactions, such as oxidation of organic carbon, radiocarbon ages are best estimated by inverse geochemical modeling techniques.
A critical review of three methods used for the measurement of mercury (Hg2+)-dissolved organic matter stability constants

USGS Publications Warehouse

Gasper, J.D.; Aiken, G.R.; Ryan, J.N.

2007-01-01

Three experimental techniques - ion exchange, liquid-liquid extraction with competitive ligand exchange, and solid-phase extraction with competitive ligand exchange (CLE-SPE) - were evaluated as methods for determining conditional stability constants (K) for the binding of mercury (Hg2+) to dissolved organic matter (DOM). To determine the utility of a given method to measure stability constants at environmentally relevant experimental conditions, experimental results should meet three criteria: (1) the data must be experimentally valid, in that they were acquired under conditions that meet all the requirements of the experimental method, (2) the Hg:DOM ratio should be determined and it should fall within levels that are consistent with environmental conditions, and (3) the stability constants must fall within the detection window of the method. The ion exchange method was found to be limited by its detection window, which constrains the method to stability constants with log K values less than about 14. The liquid-liquid extraction method was found to be complicated by the ability of Hg-DOM complexes to partition into the organic phase. The CLE-SPE method was found to be the most suitable of these methods for the measurement of Hg-DOM stability constants. Stability constants for DOM isolates measured using the CLE-SPE method at environmentally relevant Hg:DOM ratios were log K = 25-30 (M-1). These values are consistent with the strong Hg2+ binding expected for reduced S-containing binding sites. ?? 2007 Elsevier Ltd. All rights reserved.
A new method of efficient heat transfer and storage at very high temperatures

NASA Technical Reports Server (NTRS)

Shaw, D.; Bruckner, A. P.; Hertzberg, A.

1980-01-01

A unique, high temperature (1000-2000 K) continuously operating capacitive heat exchanger system is described. The system transfers heat from a combustion or solar furnace to a working gas by means of a circulating high temperature molten refractory. A uniform aggregate of beads of a glass-like refractory is injected into the furnace volume. The aggregate is melted and piped to a heat exchanger where it is sprayed through a counter-flowing, high pressure working gas. The refractory droplets transfer their heat to the gas, undergoing a phase change into the solid bead state. The resulting high temperature gas is used to drive a suitable high efficiency heat engine. The solidified refractory beads are delivered back to the furnace and melted to continue the cycle. This approach avoids the important temperature limitations of conventional tube-type heat exchangers, giving rise to the potential of converting heat energy into useful work at considerably higher efficiencies than currently attainable and of storing energy at high thermodynamic potential.
A new phosphate-selective sorbent for the Rem Nut process. Laboratory investigation and field experience at a medium size wastewater treatment plant.

PubMed

Petruzzelli, D; De Florio, L; Dell'Erba, A; Liberti, L; Notarnicola, M; Sengupta, A K

2003-01-01

P-control technologies for municipal wastewater are essentially based on "destructive" methods, that lead to formation of concentrated solid-phases (sludge), usually disposed-off in controlled landfills. Ion exchange, as a "non-destructive" technology, allows for selective removal and simultaneous recovery of pollutants, which can be recycled to the same and/or related productive lines. In this context, the REM NUT process removes nutrient species (HPO4 = , NH4+, K+) present in biologically oxidised municipal effluents and recovers them in the form of struvites (MgNH4PO4; MgKPO4), premium quality slow release fertilisers. The main limitation to the extensive application of this ion exchange based process is the non-availability of selective exchangers for specific removal of nutrient species. This paper illustrates laboratory investigation and pilot scale development of a so-called "P-driven" modified REM NUT scheme based on a new phosphate-selective sorbent developed at Lehigh University, PA, USA.
Generalized ensemble method applied to study systems with strong first order transitions

DOE PAGES

Malolepsza, E.; Kim, J.; Keyes, T.

2015-09-28

At strong first-order phase transitions, the entropy versus energy or, at constant pressure, enthalpy, exhibits convex behavior, and the statistical temperature curve correspondingly exhibits an S-loop or back-bending. In the canonical and isothermal-isobaric ensembles, with temperature as the control variable, the probability density functions become bimodal with peaks localized outside of the S-loop region. Inside, states are unstable, and as a result simulation of equilibrium phase coexistence becomes impossible. To overcome this problem, a method was proposed by Kim, Keyes and Straub, where optimally designed generalized ensemble sampling was combined with replica exchange, and denoted generalized replica exchange method (gREM).more » This new technique uses parametrized effective sampling weights that lead to a unimodal energy distribution, transforming unstable states into stable ones. In the present study, the gREM, originally developed as a Monte Carlo algorithm, was implemented to work with molecular dynamics in an isobaric ensemble and coded into LAMMPS, a highly optimized open source molecular simulation package. Lastly, the method is illustrated in a study of the very strong solid/liquid transition in water.« less
Generalized ensemble method applied to study systems with strong first order transitions

NASA Astrophysics Data System (ADS)

Małolepsza, E.; Kim, J.; Keyes, T.

2015-09-01

At strong first-order phase transitions, the entropy versus energy or, at constant pressure, enthalpy, exhibits convex behavior, and the statistical temperature curve correspondingly exhibits an S-loop or back-bending. In the canonical and isothermal-isobaric ensembles, with temperature as the control variable, the probability density functions become bimodal with peaks localized outside of the S-loop region. Inside, states are unstable, and as a result simulation of equilibrium phase coexistence becomes impossible. To overcome this problem, a method was proposed by Kim, Keyes and Straub [1], where optimally designed generalized ensemble sampling was combined with replica exchange, and denoted generalized replica exchange method (gREM). This new technique uses parametrized effective sampling weights that lead to a unimodal energy distribution, transforming unstable states into stable ones. In the present study, the gREM, originally developed as a Monte Carlo algorithm, was implemented to work with molecular dynamics in an isobaric ensemble and coded into LAMMPS, a highly optimized open source molecular simulation package. The method is illustrated in a study of the very strong solid/liquid transition in water.
Automated protein hydrolysis delivering sample to a solid acid catalyst for amino acid analysis.

PubMed

Masuda, Akiko; Dohmae, Naoshi

2010-11-01

In this study, we developed an automatic protein hydrolysis system using strong cation-exchange resins as solid acid catalysts. Examining several kinds of inorganic solid acids and cation-exchange resins, we found that a few cation-exchange resins worked as acid catalysts for protein hydrolysis when heated in the presence of water. The most efficient resin yielded amounts of amino acids that were over 70% of those recovered after conventional hydrolysis with hydrochloric acid and resulted in amino acid compositions matching the theoretical values. The solid-acid hydrolysis was automated by packing the resin into columns, combining the columns with a high-performance liquid chromatography system, and heating them. The amino acids that constitute a protein can thereby be determined, minimizing contamination from the environment.
Determination of the clean-up efficiency of the solid-phase extraction of rosemary extracts: Application of full-factorial design in hyphenation with Gaussian peak fit function.

PubMed

Meischl, Florian; Kirchler, Christian Günter; Jäger, Michael Andreas; Huck, Christian Wolfgang; Rainer, Matthias

2018-02-01

We present a novel method for the quantitative determination of the clean-up efficiency to provide a calculated parameter for peak purity through iterative fitting in conjunction with design of experiments. Rosemary extracts were used and analyzed before and after solid-phase extraction using a self-fabricated mixed-mode sorbent based on poly(N-vinylimidazole/ethylene glycol dimethacrylate). Optimization was performed by variation of washing steps using a full three-level factorial design and response surface methodology. Separation efficiency of rosmarinic acid from interfering compounds was calculated using an iterative fit of Gaussian-like signals and quantifications were performed by the separate integration of the two interfering peak areas. Results and recoveries were analyzed using Design-Expert® software and revealed significant differences between the washing steps. Optimized parameters were considered and used for all further experiments. Furthermore, the solid-phase extraction procedure was tested and compared with commercial available sorbents. In contrast to generic protocols of the manufacturers, the optimized procedure showed excellent recoveries and clean-up rates for the polymer with ion exchange properties. Finally, rosemary extracts from different manufacturing areas and application types were studied to verify the developed method for its applicability. The cleaned-up extracts were analyzed by liquid chromatography with tandem mass spectrometry for detailed compound evaluation to exclude any interference from coeluting molecules. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Impact of the volume of gaseous phase in closed reactors on ANC results and modelling

NASA Astrophysics Data System (ADS)

Drapeau, Clémentine; Delolme, Cécile; Lassabatere, Laurent; Blanc, Denise

2016-04-01

The understanding of the geochemical behavior of polluted solid materials is often challenging and requires huge expenses of time and money. Nevertheless, given the increasing amounts of polluted solid materials and related risks for the environment, it is more and more crucial to understand the leaching of majors and trace metals elements from these matrices. In the designs of methods to quantify pollutant solubilization, the combination of experimental procedures with modeling approaches has recently gained attention. Among usual methods, some rely on the association of ANC and geochemical modeling. ANC experiments - Acid Neutralization Capacity - consists in adding known quantities of acid or base to a mixture of water and contaminated solid materials at a given liquid / solid ratio in closed reactors. Reactors are agitated for 48h and then pH, conductivity, redox potential, carbon, majors and heavy metal solubilized are quantified. However, in most cases, the amounts of matrix and water do not reach the total volume of reactors, leaving some space for air (gaseous phase). Despite this fact, no clear indication is given in standard procedures about the effect of this gaseous phase. Even worse, the gaseous phase is never accounted for when exploiting or modeling ANC data. The gaseous phase may exchange CO2 with the solution, which may, in turn, impact both pH and element release. This study lies within the most general framework for the use of geochemical modeling for the prediction of ANC results for the case of pure phases to real phase assemblages. In this study, we focus on the effect of the gaseous phase on ANC experiments on different mineral phases through geochemical modeling. To do so, we use PHREEQC code to model the evolution of pH and element release (including majors and heavy metals) when several matrices are put in contact with acid or base. We model the following scenarios for the gaseous phase: no gas, contact with the atmosphere (open system) and real reactors conditions (semi-closed systems). The solid phases tested are pure phases (calcite, sulfides, etc.) and synthetic assemblages mimicking complex polluted matrices. The modeling clearly shows that the systems are sensitive to the opening to the atmosphere. If the open system and the system with no gas are entirely different, "real" reactors also differ significantly from the other systems. Apparently, the presence of the gaseous phase in reactors greatly impacts pH and element release. This parameter should be accounted for in ANC experimental procedures and modeling. In addition to this numerical study, experimental results, previously obtained for urban polluted sediments, are analyzed in lights of the findings of the numerical study. This step allows us to strengthen conclusions and to pinpoint at the necessity to account for the gaseous phase when performing and modeling ANC experiments.
Three-Dimensional Modeling of Flow and Thermochemical Behavior in a Blast Furnace

NASA Astrophysics Data System (ADS)

Shen, Yansong; Guo, Baoyu; Chew, Sheng; Austin, Peter; Yu, Aibing

2015-02-01

An ironmaking blast furnace (BF) is a complex high-temperature moving bed reactor involving counter-, co- and cross-current flows of gas, liquid and solid, coupled with heat and mass exchange and chemical reactions. Two-dimensional (2D) models were widely used for understanding its internal state in the past. In this paper, a three-dimensional (3D) CFX-based mathematical model is developed for describing the internal state of a BF in terms of multiphase flow and the related thermochemical behavior, as well as process indicators. This model considers the intense interactions between gas, solid and liquid phases, and also their competition for the space. The model is applied to a BF covering from the burden surface at the top to the liquid surface in the hearth, where the raceway cavity is considered explicitly. The results show that the key in-furnace phenomena such as flow/temperature patterns and component distributions of solid, gas and liquid phases can be described and characterized in different regions inside the BF, including the gas and liquids flow circumferentially over the 3D raceway surface. The in-furnace distributions of key performance indicators such as reduction degree and gas utilization can also be predicted. This model offers a cost-effective tool to understand and control the complex BF flow and performance.
Barium isotope fractionation during witherite (BaCO3) dissolution, precipitation and at equilibrium

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; van Zuilen, Kirsten; Purgstaller, Bettina; Baldermann, Andre; Nägler, Thomas F.; Dietzel, Martin

2016-10-01

This study examines the behavior of Ba isotope fractionation between witherite and fluid during mineral dissolution, precipitation and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 10-2 M NaCl solution where the pH was adjusted by continuous bubbling of a water saturated gas phase of CO2 or atmospheric air. During witherite dissolution no Ba isotope fractionation was observed between solid and fluid. In contrast, during witherite precipitation, caused by a pH increase, a preferential uptake of the lighter 134Ba isotopomer in the solid phase was observed. In this case, the isotope fractionation factor αwitherite-fluid is calculated to be 0.99993 ± 0.00004 (or Δ137/134Bawitherite-fluid ≈ -0.07 ± 0.04‰, 2 sd). The most interesting feature of this study, however, is that after the attainment of chemical equilibrium, the Ba isotope composition of the aqueous phase is progressively becoming lighter, indicating a continuous exchange of Ba2+ ions between witherite and fluid. Mass balance calculations indicate that the detachment of Ba from the solid is not only restricted to the outer surface layer of the solid, but affects several (∼7 unit cells) subsurface layers of the crystal. This observation comes in excellent agreement with the concept of a dynamic system at chemical equilibrium in a mineral-fluid system, denoting that the time required for the achievement of isotopic equilibrium in the witherite-fluid system is longer compared to that observed for chemical equilibrium. Overall, these results indicate that the isotopic composition of Ba bearing carbonates in natural environments may be altered due to changes in fluid composition without a net dissolution/precipitation to be observed.
Solid polymer electrolyte water electrolysis preprototype subsystem. [oxygen production for life support systems on space stations

NASA Technical Reports Server (NTRS)

1979-01-01

Hardware and controls developed for an electrolysis demonstration unit for use with the life sciences payload program and in NASA's regenerative life support evaluation program are described. Components discussed include: the electrolysis module; power conditioner; phase separator-pump and hydrogen differential regulator; pressure regulation of O2, He, and N2; air-cooled heat exchanger; water accumulator; fluid flow sight gage assembly; catalytic O2/H2 sensor; gas flow sensors; low voltage power supply; 100 Amp DC contactor assembly; and the water purifier design.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaur, Maninder; Dai, Qilin; Bowden, Mark E.

Chromium (Cr) forms a solid solution with iron (Fe) lattice when doped in core-shell iron -iron oxide nanocluster (NC) and shows a mixed phase of sigma (σ) FeCr and bcc Fe. The Cr dopant affects heavily the magnetization and magnetic reversal process, and causes the hysteresis loop to shrink near the zero field axis. Dramatic transformation happens from dipolar interaction (0 at. % Cr) to strong exchange interaction (8 at. % of Cr) is confirmed from the Henkel plot and delta M plot, and is explained by a water-melon model of core-shell NC system.
Feasible conversion of solid waste bauxite tailings into highly crystalline 4A zeolite with valuable application.

PubMed

Ma, Dongyang; Wang, Zhendong; Guo, Min; Zhang, Mei; Liu, Jingbo

2014-11-01

Bauxite tailings are a major type of solid wastes generated in the flotation process. The waste by-products caused significant environmental impact. To lessen this hazardous effect from poisonous mine tailings, a feasible and cost-effective solution was conceived and implemented. Our approach focused on reutilization of the bauxite tailings by converting it to 4A zeolite for reuse in diverse applications. Three steps were involved in the bauxite conversion: wet-chemistry, alkali fusion, and crystallization to remove impurities and to prepare porous 4A zeolite. It was found that the cubic 4A zeolite was single phase, in high purity, with high crystallinity and well-defined structure. Importantly, the 4A zeolite displayed maximum calcium ion exchange capacity averaged at 296 mg CaCO3/g, comparable to commercially-available zeolite (310 mg CaCO3/g) exchange capacity. Base on the optimal synthesis condition, the reaction yield of zeolite 4A from bauxite tailings achieved to about 38.43%, hence, this study will provide a new paradigm for remediation of bauxite tailings, further mitigating the environmental and health care concerns, particularly in the mainland of PR China. Copyright © 2014 Elsevier Ltd. All rights reserved.
Rapid Flow-Based Peptide Synthesis

PubMed Central

Simon, Mark D.; Heider, Patrick L.; Adamo, Andrea; Vinogradov, Alexander A.; Mong, Surin K.; Li, Xiyuan; Berger, Tatiana; Policarpo, Rocco L.; Zhang, Chi; Zou, Yekui; Liao, Xiaoli; Spokoyny, Alexander M.; Jensen, Klavs F.

2014-01-01

A flow-based solid phase peptide synthesis methodology that enables the incorporation of an amino acid residue every 1.8 minutes under automatic control, or every three minutes under manual control, is described. This is accomplished by passing a stream of reagent through a heat exchanger, into a low volume, low backpressure reaction vessel, and through a UV detector. These features enable the continuous delivery of heated solvents and reagents to the solid support at high flow rate, maintaining a maximal concentration of reagents in the reaction vessel, quickly exchanging reagents, and eliminating the need to rapidly heat reagents after they have been added to the vessel. The UV detector enables continuous monitoring of the process. To demonstrate the broad applicability and reliability of this method, it was employed in the total synthesis of a small protein, as well as dozens of peptides. The quality of the material obtained with this method is comparable to traditional batch methods, and, in all cases, the desired material was readily purifiable via RP-HPLC. The application of this method to the synthesis of the 113 residue B. amyloliquefaciens RNase and the 130 residue pE59 DARPin is described in the accompanying manuscript. PMID:24616230
Low temperature synthesis of highly oriented p-type Si1-xGex (x: 0-1) on an insulator by Al-induced layer exchange

NASA Astrophysics Data System (ADS)

Toko, K.; Kusano, K.; Nakata, M.; Suemasu, T.

2017-10-01

A composition tunable Si1-xGex alloy has a wide range of applications, including in electronic and photonic devices. We investigate the Al-induced layer exchange (ALILE) growth of amorphous Si1-xGex on an insulator. The ALILE allowed Si1-xGex to be large grained (> 50 μm) and highly (111)-oriented (> 95%) over the whole composition range by controlling the growth temperature (≤ 400 °C). From a comparison with conventional solid-phase crystallization, we determined that such characteristics of the ALILE arose from the low activation energy of nucleation and the high frequency factor of lateral growth. The Si1-xGex layers were highly p-type doped, whereas the process temperatures were low, thanks to the electrically activated Al atoms with the amount of solid solubility limit. The electrical conductivities approached those of bulk single crystals within one order of magnitude. The resulting Si1-xGex layer on an insulator is useful not only for advanced SiGe-based devices but also for virtual substrates, allowing other materials to be integrated on three-dimensional integrated circuits, glass, and even a plastic substrate.
Study of conduction behavior in Pr0.67Sr0.03Ag0.30MnO3

NASA Astrophysics Data System (ADS)

Bhat, Masroor Ahmad; Modi, Anchit; Pandey, Devendra K.; Gaur, N. K.

2018-05-01

In this paper, we report the conduction mechanism in Pr0.67Sr0.03Ag0.30MnO3 system synthesized via conventional solid state reaction route. The structural information was carried by X - Ray diffraction using Rietveld refinement which confirms the secondary phase of the sample. The SEM image shows the formation of double phase composite because of limited reaction of silver with parent compound. The resistivity behavior indicates the semiconducting behavior. The electronic nature can be estimated by means of variable range hopping (VRH) and small polaron hopping (SPH) model showing that the enhancement of double exchange interaction suppress the band gap and boost the carrier delocalization of charge carriers.
Determination of tylosin residues in pig tissues using high-performance liquid chromatography.

PubMed

De Liguoro, M; Anfossi, P; Angeletti, R; Montesissa, C

1998-06-01

In accordance with the maximum residue limit of 100 micrograms kg-1 established by EU legislation, a simple and sensitive high-performance liquid chromatographic (HPLC) method was developed for the measurement of tylosin residues in pig tissues (fat, kidney, liver and muscle). Tylosin, a macrolide antibiotic, is extracted with water-methanol and cleaned-up by solid-phase extraction (SPE) on cation-exchange cartridges using methanol elution. Tylosin was determined by reversed-phase HPLC with UV detection at 280 nm and the mean recovery from pig tissues fortified in the range 50-200 micrograms kg-1 was 70-85%, with intra- and inter-day RSDs in the ranges 3.4-9.1 and 3.9-10.1% respectively.
Hydrogen storage systems based on magnesium hydride: from laboratory tests to fuel cell integration

NASA Astrophysics Data System (ADS)

de Rango, P.; Marty, P.; Fruchart, D.

2016-02-01

The paper reviews the state of the art of hydrogen storage systems based on magnesium hydride, emphasizing the role of thermal management, whose effectiveness depends on the effective thermal conductivity of the hydride, but also depends of other limiting factors such as wall contact resistance and convective exchanges with the heat transfer fluid. For daily cycles, the use of phase change material to store the heat of reaction appears to be the most effective solution. The integration with fuel cells (1 kWe proton exchange membrane fuel cell and solid oxide fuel cell) highlights the dynamic behaviour of these systems, which is related to the thermodynamic properties of MgH2. This allows for "self-adaptive" systems that do not require control of the hydrogen flow rate at the inlet of the fuel cell.

Potentiometric Sensor for Real-Time Remote Surveillance of Actinides in Molten Salts

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

Natalie J. Gese; Jan-Fong Jue; Brenda E. Serrano

2012-07-01

A potentiometric sensor is being developed at the Idaho National Laboratory for real-time remote surveillance of actinides during electrorefining of spent nuclear fuel. During electrorefining, fuel in metallic form is oxidized at the anode while refined uranium metal is reduced at the cathode in a high temperature electrochemical cell containing LiCl-KCl-UCl3 electrolyte. Actinides present in the fuel chemically react with UCl3 and form stable metal chlorides that accumulate in the electrolyte. This sensor will be used for process control and safeguarding of activities in the electrorefiner by monitoring the concentrations of actinides in the electrolyte. The work presented focuses onmore » developing a solid-state cation conducting ceramic sensor for detecting varying concentrations of trivalent actinide metal cations in eutectic LiCl-KCl molten salt. To understand the basic mechanisms for actinide sensor applications in molten salts, gadolinium was used as a surrogate for actinides. The ß?-Al2O3 was selected as the solid-state electrolyte for sensor fabrication based on cationic conductivity and other factors. In the present work Gd3+-ß?-Al2O3 was prepared by ion exchange reactions between trivalent Gd3+ from GdCl3 and K+-, Na+-, and Sr2+-ß?-Al2O3 precursors. Scanning electron microscopy (SEM) was used for characterization of Gd3+-ß?-Al2O3 samples. Microfocus X-ray Diffraction (µ-XRD) was used in conjunction with SEM energy dispersive X-ray spectroscopy (EDS) to identify phase content and elemental composition. The Gd3+-ß?-Al2O3 materials were tested for mechanical and chemical stability by exposing them to molten LiCl-KCl based salts. The effect of annealing on the exchanged material was studied to determine improvements in material integrity post ion exchange. The stability of the ß?-Al2O3 phase after annealing was verified by µ-XRD. Preliminary sensor tests with different assembly designs will also be presented.« less
Microsphere zeolite materials derived from coal fly ash cenospheres as precursors to mineral-like aluminosilicate hosts for 135,137Cs and 90Sr

NASA Astrophysics Data System (ADS)

Vereshchagina, Tatiana A.; Vereshchagin, Sergei N.; Shishkina, Nina N.; Vasilieva, Nataly G.; Solovyov, Leonid A.; Anshits, Alexander G.

2013-06-01

Hollow microsphere zeolite materials with a bilayered zeolite/glass crystalline shell bearing NaP1 zeolite were synthesized by the hydrothermal treatment of coal fly ash cenospheres (Si/Al = 2.7) in an alkaline medium. Cs+ and/or Sr2+ forms of zeolitized cenospheres with the different Cs+ and/or Sr2+ loading were prepared by the ion exchange from nitrate solutions. The resulted (Cs,Na)P1, (Sr,Na)P1 and (Cs,Sr,Na)P1 bearing microsphere zeolites were converted to glass ceramics by heating at 900-1000 °C. The differential scanning calorimetry and quantitative phase analysis were used to monitor the solid-phase transformation of the initial and ion exchanged zeolite materials. It was established that the final solidified forms of Cs+ and/or Sr2+ are glass-crystalline ceramic materials based on pollucite-nepheline, Sr-feldspar-nepheline and Sr-feldspar-pollucite composites including ˜60 wt.% of the major host phases (pollucite, Sr-feldspar) and 10-20 wt.% of glass. The 137Cs leaching rate of 4.1 × 10-7 g cm-2 day-1 was determined for the pollucite glass-ceramic according to Russian State Standard (GOST) No. 52126 P-2003 (7 day, 25 °C, distilled water).
Shockwave Processing of Composite Boron and Titanium Nitride Powders

NASA Astrophysics Data System (ADS)

Beason, Matthew T.; Gunduz, I. Emre; Mukasyan, Alexander S.; Son, Steven F.

2015-06-01

Shockwave processing of powders has been shown to initiate reactions between condensed phase reactants. It has been observed that these reactions can occur at very short timescales, resulting in chemical reactions occurring at a high pressure state. These reactions have the potential to produce metastable phases. Kinetic limitations prevent gaseous reactants from being used in this type of synthesis reaction. To overcome this limitation, a solid source of gaseous reactants must be used. An example of this type of reaction is the nitrogen exchange reaction (e.g. B + TiN, B + Si3N4 etc.). In these reactions nitrogen is ``carried'' by a material that can be then reduced by the second reactant. This work explores the possibility of using nitrogen exchange reactions to synthesize the cubic phase of boron nitride (c-BN) through shockwave processing of ball milled mixtures of boron and titanium nitride. The heating from the passage of the shock wave (pore collapse, plastic work, etc.) combined with thermochemical energy from the reaction may provide a means to synthesize c-BN. This material is based upon work supported by the Department of Energy, National Nuclear Security Administration, under Award Number(s) DE-NA0002377. National Defense Science & Engineering Graduate Fellowship (NDSEG), 32 CFR 168a.
A new approach for downscaling of electromembrane extraction as a lab on-a-chip device followed by sensitive Red-Green-Blue detection.

PubMed

Baharfar, Mahroo; Yamini, Yadollah; Seidi, Shahram; Arain, Muhammad Balal

2018-05-30

A new design of electromembrane extraction (EME) as a lab on-a-chip device was proposed for the extraction and determination of phenazopyridine as the model analyte. The extraction procedure was accomplished by coupling of EME and the packing of a sorbent. The analyte was extracted under the applied electrical field across a membrane sheet impregnated by nitrophenyl octylether (NPOE) into an acceptor phase. It was followed by the absorption of the analyte on strong cation exchanger as a sorbent. The designed chip contained separate spiral channels for donor and acceptor phases featuring embedded platinum electrodes to enhance extraction efficiency. The selected donor and acceptor phases were 0 mM HCl and 100 mM HCl, respectively. The on-chip electromembrane extraction was carried out under the voltage level of 70 V for 50 min. The analysis was carried out by two modes of a simple Red-Green-Blue (RGB) image analysis tool and a conventional HPLC-UV system. After the absorption of the analyte on the solid phase, its color changed and a digital picture of the sorbent was taken for the RGB analysis. The effective parameters on the performance of the chip device, comprising the EME and solid phase microextraction steps, were distinguished and optimized. The accumulation of the analyte on the solid phase showed excellent sensitivity and a limit of detection (LOD) lower than 1.0 μg L-1 achieved by an image analysis using a smartphone. This device also offered acceptable intra- and inter-assay RSD% (<10%). The calibration curves were linear within the range of 10-1000 μg L-1 and 30-1000 μg L-1 (r2 > 0.9969) for HPLC-UV and RGB analysis, respectively. To investigate the applicability of the method in complicated matrices, urine samples of patients being treated with phenazopyridine were analyzed.
A Novel Solid-Phase Site-Specific PEGylation Enhances the In Vitro and In Vivo Biostabilty of Recombinant Human Keratinocyte Growth Factor 1

PubMed Central

Zhang, Jingui; Zhang, Yi; Zhang, Youting; Ye, Chaohui; Wang, Xiaojie; Ilghari, Dariush; Li, Xiaokun

2012-01-01

Keratinocyte growth factor 1 (KGF-1) has proven useful in the treatment of pathologies associated with dermal adnexae, liver, lung, and the gastrointestinal tract diseases. However, poor stability and short plasma half-life of the protein have restricted its therapeutic applications. While it is possible to improve the stability and extend the circulating half-life of recombinant human KGF-1 (rhKGF-1) using solution-phase PEGylation, such preparations have heterogeneous structures and often low specific activities due to multiple and/or uncontrolled PEGylation. In the present study, a novel solid-phase PEGylation strategy was employed to produce homogenous mono-PEGylated rhKGF-1. RhKGF-1 protein was immobilized on a Heparin-Sepharose column and then a site-selective PEGylation reaction was carried out by a reductive alkylation at the N-terminal amino acid of the protein. The mono-PEGylated rhKGF-1, which accounted for over 40% of the total rhKGF-1 used in the PEGylation reaction, was purified to homogeneity by SP Sepharose ion-exchange chromatography. Our biophysical and biochemical studies demonstrated that the solid-phase PEGylation significantly enhanced the in vitro and in vivo biostability without affecting the over all structure of the protein. Furthermore, pharmacokinetic analysis showed that modified rhKGF-1 had considerably longer plasma half-life than its intact counterpart. Our cell-based analysis showed that, similar to rhKGF-1, PEGylated rhKGF-1 induced proliferation in NIH 3T3 cells through the activation of MAPK/Erk pathway. Notably, PEGylated rhKGF-1 exhibited a greater hepatoprotection against CCl4-induced injury in rats compared to rhKGF-1. PMID:22574160
Waste isolation safety assessment program. Task 4. Collection and generation of transport data theoretical and experimental evaluation of waste transport in selected rocks. Annual progress report, October 1, 1978-September 30, 1979

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

Silva, R.J.; Benson, L.V.; Yee, A.W.

1979-09-30

The objective of the program is to establish a basis for the prediction of radionuclide sorption in geologic environments. In FY 79, experimental and theoretical efforts were concentrated on a study of the sorption of cesium on the solid substrates Min-u-sil (quartz) and Belle Fourche clay (montmorillonite). Cesium sorption isotherms were obtained for the two substrates at 26/sup 0/C as a function of initial Cs concentration in solution (10/sup -3/M to 10/sup -9/M), pH (5 to 10) and supporting electrolyte concentration (0.002M, 0.01M, 0.1M, and 1M) NaCl and a simulated basalt groundwater in batch-type experiments using crushed material. Characterization ofmore » the solid phases included measurements of chemical compositions, particle sizes, surface areas, and cation-exchange capacities. In addition, potentiometric acid/base titrations of the solid phases were conducted in order to determine the acid dissociation and electrolyte exchange constants of the surfaces. Preliminary analysis of the sorption data indicate that while the clay data could be explained by simple mass-action expressions, the quartz data could not. Theoretical efforts were aimed at developing and testing an electrolyte binding electrical double-layer model to predict sorption isotherms. A computerized version of the model, MINEQL, which simultaneously considers surface and solution chemical equilibria, was brought to operational status. Input parameters required by MINEQL were determined and sorption isotherms for Cs on the Belle Fourche clay were calculated over the same range of parameters as the experimental measurements. Comparisons showed that the model was able to simulate the isotherms quite well except at the lowest pH values for the 0.002M and 0.01M NaCl solutions.« less
Insights into the spurious long-range nature of local rs-dependent non-local exchange-correlation kernels

DOE PAGES

Lu, Deyu

2016-08-05

A systematic route to go beyond the exact exchange plus random phase approximation (RPA) is to include a physical exchange-correlation kernel in the adiabatic-connection fluctuation-dissipation theorem. Previously, [D. Lu, J. Chem. Phys. 140, 18A520 (2014)], we found that non-local kernels with a screening length depending on the local Wigner-Seitz radius, r s(r), suffer an error associated with a spurious long-range repulsion in van der Waals bounded systems, which deteriorates the binding energy curve as compared to RPA. Here, we analyze the source of the error and propose to replace r s(r) by a global, average r s in the kernel.more » Exemplary studies with the Corradini, del Sole, Onida, and Palummo kernel show that while this change does not affect the already outstanding performance in crystalline solids, using an average r s significantly reduces the spurious long-range tail in the exchange-correlation kernel in van der Waals bounded systems. Finally, when this method is combined with further corrections using local dielectric response theory, the binding energy of the Kr dimer is improved three times as compared to RPA.« less
Soil-modified carbon paste electrode: a useful tool in environmental assessment of heavy metal ion binding interactions.

PubMed

Svegl, I G; Ogorevc, B

2000-08-01

Carbon paste electrodes (CPEs) modified with different soils in their native form were prepared to create a soil-like solid phase suitable for application in studies of heavy metal ion uptake and binding interactions. The preparation of CPEs modified with five different soils was examined and their heavy metal ion uptake behavior investigated using a model Cu(II) aqueous solution. Metal ions were accumulated under open circuit conditions and were determined after a medium exchange using differential pulse anodic stripping voltammetry, applying preelectrolysis at -0.7 V. The soil-modified CPE accumulation behavior, including the linearity of the current response versus Cu(II) concentration, the influence of the pH on the solution, and the uptake kinetics, was thoroughly investigated. The correlation between the soil-modified CPE uptake capability and the standard soil parameters, such as ion exchange capacity, soil pH, organic matter and clay content, were evaluated for all five examined soils. The influence of selected endogenous cations (K(I), Ca(II), Fe(III)) on the transfer of Cu(II) ions from a solution to the simulated soil solid phase was examined and is discussed. Preliminary examinations of the soil-modified CPE uptake behavior with some exogenous heavy metal ions of strong environmental interest (Pb(II), Hg(II), Cd(II) and Ag(I)) are also presented. This work demonstrates some attractive possibilities for the application of a soil-modified CPE in studying soil-heavy metal ion binding interactions, with a further potential use as a new environmental sensor appropriate for fist on-site testing of polluted soils.
Fractionation analysis of oxyanion-forming metals and metalloids in leachates of cement-based materials using ion exchange solid phase extraction.

PubMed

Mulugeta, Mesay; Wibetoe, Grethe; Engelsen, Christian J; Lund, Walter

2009-05-15

A simple and versatile solid phase extraction (SPE) method has been developed to determine the anionic species of As, Cr, Mo, Sb, Se and V in leachates of cement mortar and concrete materials in the pH range 3-13. The anionic fractions of these elements were extracted using a strong anion exchanger (SAX) and their concentrations were determined as the difference in element concentration between the sample and the SAX effluent. Inductively coupled plasma mass spectrometry (ICP-MS) was used off-line to analyse solutions before and after passing through the SAX. The extraction method has been developed by optimizing sorbent type, sorbent conditioning and sample percolation rate. Breakthrough volumes and effect of matrix constituents were also studied. It was found that a polymer-based SAX conditioned with a buffer close to the sample pH or in some cases deionised water gave the best retention of the analytes. Optimal conditions were also determined for the quantitative elution of analytes retained on the SAX. Extraction of the cement mortar and concrete leachates showed that most of the elements had similar distribution of anions in both leachate types, and that the distribution was strongly pH dependent. Cr, Mo and V exist in anionic forms in strongly basic leachates (pH>12), and significant fractions of anionic Se were also detected in these solutions. Cr, Mo, Se and V were not determined as anions by the present method in the leachates of pH<12. Anionic As and Sb were found in small fractions in most of the leachates.
Direct measurement of the glucuronide conjugate of 1-hydroxypyrene in human urine by using liquid chromatography with tandem mass spectrometry.

PubMed

Kakimoto, Kensaku; Toriba, Akira; Ohno, Takanori; Ueno, Mariko; Kameda, Takayuki; Tang, Ning; Hayakawa, Kazuichi

2008-05-15

To evaluate human exposure to polycyclic aromatic hydrocarbons (PAHs), we developed a rapid, simple and sensitive method for determining 1-hydroxypyrene-glucuronide (1-OHP-G) in human urine. To improve precision, a deuterated glucuronide was used as an internal standard. The method requires only 1 mL of urine. The urine was treated with a mixed-mode anion-exchange and reversed-phase solid-phase extraction cartridge (Oasis MAX). The analytes were analyzed with a C(18) reversed-phase column with a gradient elution, followed by tandem mass spectrometry with electrospray ionization in negative ion mode. The detection limit of 1-OHP-G (corresponding to a signal-to-noise ratio of 3) was 0.13 fmol/injection. Urinary concentrations of 1-OHP-G determined by this method were strongly correlated (r(2)=0.961) with concentrations of 1-hydroxypyrene by conventional HPLC with fluorescence detection.
Non-invasive analysis of swelling in polymer dispersions by means of time-domain(TD)-NMR.

PubMed

Nestle, Nikolaus; Häberle, Karl

2009-11-03

In this contribution, we discuss the potential of low-field time-domain(TD)-NMR to study the swelling of (aqueous) polymer dispersions by a volatile solvent. Due to the sensitivity of transverse relaxation times (T2) to swelling-induced changes in the molecular dynamics of the polymer component, the effects of swelling can be measured without spectral resolution. The measurement is performed on polymer dispersions in native state with solids contents around 50% in a non-invasive way without separating the polymeric phase and the water phase from each other. Using acetone in two polyurethane (PU) dispersions with different hard phase contents, we explore the sensitivity of the method and present a data evaluation strategy based on multicomponent fitting and proton balancing. Furthermore, we report exchange continualization as a further effect that needs to be taken into account for correct interpretation of the data.
Screened hybrid density functionals for solid-state chemistry and physics.

PubMed

Janesko, Benjamin G; Henderson, Thomas M; Scuseria, Gustavo E

2009-01-21

Density functional theory incorporating hybrid exchange-correlation functionals has been extraordinarily successful in providing accurate, computationally tractable treatments of molecular properties. However, conventional hybrid functionals can be problematic for solids. Their nonlocal, Hartree-Fock-like exchange term decays slowly and incorporates unphysical features in metals and narrow-bandgap semiconductors. This article provides an overview of our group's work on designing hybrid functionals for solids. We focus on the Heyd-Scuseria-Ernzerhof screened hybrid functional [J. Chem. Phys. 2003, 118, 8207], its applications to the chemistry and physics of solids and surfaces, and our efforts to build upon its successes.
Simulation of reactive polydisperse sprays strongly coupled to unsteady flows in solid rocket motors: Efficient strategy using Eulerian Multi-Fluid methods

NASA Astrophysics Data System (ADS)

Sibra, A.; Dupays, J.; Murrone, A.; Laurent, F.; Massot, M.

2017-06-01

In this paper, we tackle the issue of the accurate simulation of evaporating and reactive polydisperse sprays strongly coupled to unsteady gaseous flows. In solid propulsion, aluminum particles are included in the propellant to improve the global performances but the distributed combustion of these droplets in the chamber is suspected to be a driving mechanism of hydrodynamic and acoustic instabilities. The faithful prediction of two-phase interactions is a determining step for future solid rocket motor optimization. When looking at saving computational ressources as required for industrial applications, performing reliable simulations of two-phase flow instabilities appears as a challenge for both modeling and scientific computing. The size polydispersity, which conditions the droplet dynamics, is a key parameter that has to be accounted for. For moderately dense sprays, a kinetic approach based on a statistical point of view is particularly appropriate. The spray is described by a number density function and its evolution follows a Williams-Boltzmann transport equation. To solve it, we use Eulerian Multi-Fluid methods, based on a continuous discretization of the size phase space into sections, which offer an accurate treatment of the polydispersion. The objective of this paper is threefold: first to derive a new Two Size Moment Multi-Fluid model that is able to tackle evaporating polydisperse sprays at low cost while accurately describing the main driving mechanisms, second to develop a dedicated evaporation scheme to treat simultaneously mass, moment and energy exchanges with the gas and between the sections. Finally, to design a time splitting operator strategy respecting both reactive two-phase flow physics and cost/accuracy ratio required for industrial computations. Using a research code, we provide 0D validations of the new scheme before assessing the splitting technique's ability on a reference two-phase flow acoustic case. Implemented in the industrial-oriented CEDRE code, all developments allow to simulate realistic solid rocket motor configurations featuring the first polydisperse reactive computations with a fully Eulerian method.
Liquid membrane coated ion-exchange column solids

DOEpatents

Barkey, Dale P.

1988-01-01

This invention relates to a method for improving the performance of liquid membrane separations by coating a liquid membrane onto solid ion-exchange resin beads in a fixed bed. Ion-exchange beads fabricated from an ion-exchange resin are swelled with water and are coated with a liquid membrane material that forms a film over the beads. The beads constitute a fixed bed ion-exchange column. Fluid being treated that contains the desired ion to be trapped by the ion-exchange particle is passed through the column. A carrier molecule, contained in the liquid membrane ion-exchange material, is selective for the desired ion in the fluid. The carrier molecule forms a complex with the desired ion, transporting it through the membrane and thus separating it from the other ions. The solution is fed continuously until breakthrough occurs at which time the ion is recovered, and the bed is regenerated.
Liquid membrane coated ion-exchange column solids

DOEpatents

Barkey, Dale P.

1989-01-01

This invention relates to a method for improving the performance of liquid embrane separations by coating a liquid membrane onto solid ion-exchange resin beads in a fixed bed. Ion-exchange beads fabricated from an ion-exchange resin are swelled with water and are coated with a liquid membrane material that forms a film over the beads. The beads constitute a fixed bed ion-exchange column. Fluid being treated that contains the desired ion to be trapped by the ion-exchange particle is passed through the column. A carrier molecule, contained in the liquid membrane ion-exchange material, is selected for the desired ion in the fluid. The carrier molecule forms a complex with the desired ion, transporting it through the membrane and thus separating it from the other ions. The solution is fed continuously until breakthrough occurs at which time the ion is recovered, and the bed is regenerated.
The exchange interactions and the state of manganese atoms in the solid solutions in Bi{sub 3}NbO{sub 7} of cubic and tetragonal modifications

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

Chezhina, N.V., E-mail: chezhina@nc2490.spb.edu; Zhuk, N.A.; Korolev, D.A.

2016-01-15

The comparative analysis of magnetic behavior of manganese-containing solid solutions Bi{sub 3}Nb{sub 1−x}Mn{sub x}O{sub 7−δ} (x=0.01−0.10) of cubic and tetragonal modifications was performed. Based on the results of magnetic susceptibility studies paramagnetic manganese atoms in solid solutions of cubic and tetragonal modifications were found to be in the form of Mn(III), Mn(IV) monomers and exchange-coupled dimers of Mn(III)–O–Mn(III), Mn(IV)–O–Mn(IV), Mn(III)–O–Mn(IV). The exchange parameters and the distribution of monomers and dimers in solid solutions as a function of the content of paramagnetic atoms were calculated. - Graphical abstract: Structural transition of cubic to tetragonal Bi{sub 3}NbO{sub 7−δ}.
Recent Progress in Studies of Nanostructured Impurity Helium Solids

NASA Astrophysics Data System (ADS)

Khmelenko, V. V.; Kunttu, H.; Lee, D. M.

2007-07-01

Impurity helium (Im He) solids are porous materials formed inside superfluid 4He by nanoclusters of impurities injected from the gas phase. The results of studies of these materials have relevance to soft condensed matter physics, matrix isolation of free radicals and low temperature chemistry. Recent studies by a variety of experimental techniques, including CW and pulse ESR, X-ray diffraction, ultrasound and Raman spectroscopy allow a better characterization of the properties of Im He solids. The structure of Im He solids, the trapping sites of stabilized atoms and the possible energy content of the samples are analyzed on the basis of experimental data. The kinetics of exchange tunneling reactions of hydrogen isotopes in nanoclusters and the changes of environment of the atoms during the course of these reactions are reviewed. Analysis of the ESR data shows that very large fraction of the stabilized atoms in Im He solids reside on the surfaces of impurity nanoclusters. The future directions for studying Im He solids are described. Among the most attractive are the studies of Im He solids with high concentrations of stabilized atoms at ultralow (10 20 mK) temperature for the observation of new collective quantum phenomena, the studies of practical application of Im He solids as a medium in neutron moderator for efficient production of ultracold (˜1 mK) neutrons, and the possibilities of obtaining high concentration of atomic nitrogen embedded in N2 clusters for energy storage.
Magnetic and electronic properties of SrMnO3 thin films

NASA Astrophysics Data System (ADS)

Mandal, Arup Kumar; Panchal, Gyanendra; Choudhary, R. J.; Phase, D. M.

2018-05-01

Single phase hexagonal bulk SrMnO3 (SMO) was prepared by solid state route and it was used for depositing thin films by pulsed laser deposition (PLD) technique on single crystalline (100) oriented SrTiO3 (STO) substrate. X-ray diffraction shows that the thin film is deposited in cubic SrMnO3 phase. From X-ray absorption at the Mn L edge we observed the mixed valency of Mn (Mn3+& Mn4+) due to strain induced by the lattice mismatching between SMO and STO. Due to this mixed valency of Mn ion in SMO film, the ferromagnetic nature is observed at lower temperature because of double exchange. After post annealing with very low oxygen partial pressure, magnetic and electronic property of SMO films are effectively modified.
Simultaneous spectrophotometric determination of trace copper, nickel, and cobalt ions in water samples using solid phase extraction coupled with partial least squares approaches

NASA Astrophysics Data System (ADS)

Guo, Yugao; Zhao, He; Han, Yelin; Liu, Xia; Guan, Shan; Zhang, Qingyin; Bian, Xihui

2017-02-01

A simultaneous spectrophotometric determination method for trace heavy metal ions based on solid-phase extraction coupled with partial least squares approaches was developed. In the proposed method, trace metal ions in aqueous samples were adsorbed by cation exchange fibers and desorbed by acidic solution from the fibers. After the ion preconcentration process, the enriched solution was detected by ultraviolet and visible spectrophotometer (UV-Vis). Then, the concentration of heavy metal ions were quantified by analyzing ultraviolet and visible spectrum with the help of partial least squares (PLS) approaches. Under the optimal conditions of operation time, flow rate and detection parameters, the overlapped absorption peaks of mixed ions were obtained. The experimental data showed that the concentration, which can be calculated through chemometrics method, of each metal ion increased significantly. The heavy metal ions can be enriched more than 80-fold. The limits of detection (LOD) for the target analytes of copper ions (Cu2 +), cobalt ions (Co2 +) and nickel ions (Ni2 +) mixture was 0.10 μg L- 1, 0.15 μg L- 1 and 0.13 μg L- 1, respectively. The relative standard deviations (RSD) were less than 5%. The performance of the solid-phase extraction can enrich the ions efficiently and the combined method of spectrophotometric detection and PLS can evaluate the ions concentration accurately. The work proposed here is an interesting and promising attempt for the trace ions determination in water samples and will have much more applied field.
Simultaneous spectrophotometric determination of trace copper, nickel, and cobalt ions in water samples using solid phase extraction coupled with partial least squares approaches.

PubMed

Guo, Yugao; Zhao, He; Han, Yelin; Liu, Xia; Guan, Shan; Zhang, Qingyin; Bian, Xihui

2017-02-15

A simultaneous spectrophotometric determination method for trace heavy metal ions based on solid-phase extraction coupled with partial least squares approaches was developed. In the proposed method, trace metal ions in aqueous samples were adsorbed by cation exchange fibers and desorbed by acidic solution from the fibers. After the ion preconcentration process, the enriched solution was detected by ultraviolet and visible spectrophotometer (UV-Vis). Then, the concentration of heavy metal ions were quantified by analyzing ultraviolet and visible spectrum with the help of partial least squares (PLS) approaches. Under the optimal conditions of operation time, flow rate and detection parameters, the overlapped absorption peaks of mixed ions were obtained. The experimental data showed that the concentration, which can be calculated through chemometrics method, of each metal ion increased significantly. The heavy metal ions can be enriched more than 80-fold. The limits of detection (LOD) for the target analytes of copper ions (Cu 2+ ), cobalt ions (Co 2+ ) and nickel ions (Ni 2+ ) mixture was 0.10μgL -1 , 0.15μgL -1 and 0.13μgL -1 , respectively. The relative standard deviations (RSD) were less than 5%. The performance of the solid-phase extraction can enrich the ions efficiently and the combined method of spectrophotometric detection and PLS can evaluate the ions concentration accurately. The work proposed here is an interesting and promising attempt for the trace ions determination in water samples and will have much more applied field. Copyright © 2016 Elsevier B.V. All rights reserved.

Behaviour of Fe4O5-Mg2Fe2O5 solid solutions and their relation to coexisting Mg-Fe silicates and oxide phases

NASA Astrophysics Data System (ADS)

Uenver-Thiele, Laura; Woodland, Alan B.; Miyajima, Nobuyoshi; Ballaran, Tiziana Boffa; Frost, Daniel J.

2018-03-01

Experiments at high pressures and temperatures were carried out (1) to investigate the crystal-chemical behaviour of Fe4O5-Mg2Fe2O5 solid solutions and (2) to explore the phase relations involving (Mg,Fe)2Fe2O5 (denoted as O5-phase) and Mg-Fe silicates. Multi-anvil experiments were performed at 11-20 GPa and 1100-1600 °C using different starting compositions including two that were Si-bearing. In Si-free experiments the O5-phase coexists with Fe2O3, hp-(Mg,Fe)Fe2O4, (Mg,Fe)3Fe4O9 or an unquenchable phase of different stoichiometry. Si-bearing experiments yielded phase assemblages consisting of the O5-phase together with olivine, wadsleyite or ringwoodite, majoritic garnet or Fe3+-bearing phase B. However, (Mg,Fe)2Fe2O5 does not incorporate Si. Electron microprobe analyses revealed that phase B incorporates significant amounts of Fe2+ and Fe3+ (at least 1.0 cations Fe per formula unit). Fe-L2,3-edge energy-loss near-edge structure spectra confirm the presence of ferric iron [Fe3+/Fetot = 0.41(4)] and indicate substitution according to the following charge-balanced exchange: [4]Si4+ + [6]Mg2+ = 2Fe3+. The ability to accommodate Fe2+ and Fe3+ makes this potential "water-storing" mineral interesting since such substitutions should enlarge its stability field. The thermodynamic properties of Mg2Fe2O5 have been refined, yielding H°1bar,298 = - 1981.5 kJ mol- 1. Solid solution is complete across the Fe4O5-Mg2Fe2O5 binary. Molar volume decreases essentially linearly with increasing Mg content, consistent with ideal mixing behaviour. The partitioning of Mg and Fe2+ with silicates indicates that (Mg,Fe)2Fe2O5 has a strong preference for Fe2+. Modelling of partitioning with olivine is consistent with the O5-phase exhibiting ideal mixing behaviour. Mg-Fe2+ partitioning between (Mg,Fe)2Fe2O5 and ringwoodite or wadsleyite is influenced by the presence of Fe3+ and OH incorporation in the silicate phases.
Measuring the equation of state for a 2D colloidal membrane: A microfluidic approach to buffer exchange

NASA Astrophysics Data System (ADS)

Balchunas, Andrew; Cabanas, Rafael; Fraden, Seth; Dogic, Zvonimir

Previous work has shown that monodisperse rod-like colloidal particles, such as a filamentous bacteriophage, self assemble into a 2D monolayer smectic in the presence of a non-adsorbing depleting polymer. These structures have the same functional form of bending rigidity and lateral compressibility as conventional lipid bi-layers, so we name the monolayer smectic a colloidal membrane. We have developed a microfluidic device such that the osmotic pressure acting on a colloidal membrane may be controlled via a full in situ buffer exchange. Rod density within individual colloidal membranes was measured as a function of osmotic pressure and a first order phase transition, from 2D fluid to 2D solid, was observed. kon and koff rates of rod to membrane binding were measured by lowering the osmotic pressure until membrane evaporation occurred.
Deorbitalization strategies for meta-generalized-gradient-approximation exchange-correlation functionals

NASA Astrophysics Data System (ADS)

Mejia-Rodriguez, Daniel; Trickey, S. B.

2017-11-01

We explore the simplification of widely used meta-generalized-gradient approximation (mGGA) exchange-correlation functionals to the Laplacian level of refinement by use of approximate kinetic-energy density functionals (KEDFs). Such deorbitalization is motivated by the prospect of reducing computational cost while recovering a strictly Kohn-Sham local potential framework (rather than the usual generalized Kohn-Sham treatment of mGGAs). A KEDF that has been rather successful in solid simulations proves to be inadequate for deorbitalization, but we produce other forms which, with parametrization to Kohn-Sham results (not experimental data) on a small training set, yield rather good results on standard molecular test sets when used to deorbitalize the meta-GGA made very simple, Tao-Perdew-Staroverov-Scuseria, and strongly constrained and appropriately normed functionals. We also study the difference between high-fidelity and best-performing deorbitalizations and discuss possible implications for use in ab initio molecular dynamics simulations of complicated condensed phase systems.
A Numerical Model of Exchange Chromatography Through 3D Lattice Structures

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

Salloum, Maher; Robinson, David B.

Rapid progress in the development of additive manufacturing technologies is opening new opportunities to fabricate structures that control mass transport in three dimensions across a broad range of length scales. We describe a structure that can be fabricated by newly available commercial 3D printers. It contains an array of regular three-dimensional flow paths that are in intimate contact with a solid phase, and thoroughly shuffle material among the paths. We implement a chemically reacting flow model to study its behavior as an exchange chromatography column, and compare it to an array of one-dimensional flow paths that resemble more traditional honeycombmore » monoliths. A reaction front moves through the columns and then elutes. Here, the front is sharper at all flow rates for the structure with three-dimensional flow paths, and this structure is more robust to channel width defects than the one-dimensional array.« less
The Solid-Phase Synthesis of an Fe-N-C Electrocatalyst for High-Power Proton-Exchange Membrane Fuel Cells.

PubMed

Liu, Qingtao; Liu, Xiaofang; Zheng, Lirong; Shui, Jianglan

2018-01-26

The environmentally friendly synthesis of highly active Fe-N-C electrocatalysts for proton-exchange membrane fuel cells (PEMFCs) is desirable but remains challenging. A simple and scalable method is presented to fabricate Fe II -doped ZIF-8, which can be further pyrolyzed into Fe-N-C with 3 wt % of Fe exclusively in Fe-N 4 active moieties. Significantly, this Fe-N-C derived acidic PEMFC exhibits an unprecedented current density of 1.65 A cm -2 at 0.6 V and the highest power density of 1.14 W cm -2 compared with previously reported NPMCs. The excellent PEMFC performance can be attributed to the densely and atomically dispersed Fe-N 4 active moieties on the small and uniform catalyst nanoparticles. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
A Numerical Model of Exchange Chromatography Through 3D Lattice Structures

DOE PAGES

Salloum, Maher; Robinson, David B.

2018-01-30

Rapid progress in the development of additive manufacturing technologies is opening new opportunities to fabricate structures that control mass transport in three dimensions across a broad range of length scales. We describe a structure that can be fabricated by newly available commercial 3D printers. It contains an array of regular three-dimensional flow paths that are in intimate contact with a solid phase, and thoroughly shuffle material among the paths. We implement a chemically reacting flow model to study its behavior as an exchange chromatography column, and compare it to an array of one-dimensional flow paths that resemble more traditional honeycombmore » monoliths. A reaction front moves through the columns and then elutes. Here, the front is sharper at all flow rates for the structure with three-dimensional flow paths, and this structure is more robust to channel width defects than the one-dimensional array.« less
A Tractable Disequilbrium Framework for Integrating Computational Thermodynamics and Geodynamics

NASA Astrophysics Data System (ADS)

Spiegelman, M. W.; Tweed, L. E. L.; Evans, O.; Kelemen, P. B.; Wilson, C. R.

2017-12-01

The consistent integration of computational thermodynamics and geodynamics is essential for exploring and understanding a wide range of processes from high-PT magma dynamics in the convecting mantle to low-PT reactive alteration of the brittle crust. Nevertheless, considerable challenges remain for coupling thermodynamics and fluid-solid mechanics within computationally tractable and insightful models. Here we report on a new effort, part of the ENKI project, that provides a roadmap for developing flexible geodynamic models of varying complexity that are thermodynamically consistent with established thermodynamic models. The basic theory is derived from the disequilibrium thermodynamics of De Groot and Mazur (1984), similar to Rudge et. al (2011, GJI), but extends that theory to include more general rheologies, multiple solid (and liquid) phases and explicit chemical reactions to describe interphase exchange. Specifying stoichiometric reactions clearly defines the compositions of reactants and products and allows the affinity of each reaction (A = -Δ/Gr) to be used as a scalar measure of disequilibrium. This approach only requires thermodynamic models to return chemical potentials of all components and phases (as well as thermodynamic quantities for each phase e.g. densities, heat capacity, entropies), but is not constrained to be in thermodynamic equilibrium. Allowing meta-stable phases mitigates some of the computational issues involved with the introduction and exhaustion of phases. Nevertheless, for closed systems, these problems are guaranteed to evolve to the same equilibria predicted by equilibrium thermodynamics. Here we illustrate the behavior of this theory for a range of simple problems (constructed with our open-source model builder TerraFERMA) that model poro-viscous behavior in the well understood Fo-Fa binary phase loop. Other contributions in this session will explore a range of models with more petrologically interesting phase diagrams as well as other rheologies.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Deyu

A systematic route to go beyond the exact exchange plus random phase approximation (RPA) is to include a physical exchange-correlation kernel in the adiabatic-connection fluctuation-dissipation theorem. Previously, [D. Lu, J. Chem. Phys. 140, 18A520 (2014)], we found that non-local kernels with a screening length depending on the local Wigner-Seitz radius, r s(r), suffer an error associated with a spurious long-range repulsion in van der Waals bounded systems, which deteriorates the binding energy curve as compared to RPA. Here, we analyze the source of the error and propose to replace r s(r) by a global, average r s in the kernel.more » Exemplary studies with the Corradini, del Sole, Onida, and Palummo kernel show that while this change does not affect the already outstanding performance in crystalline solids, using an average r s significantly reduces the spurious long-range tail in the exchange-correlation kernel in van der Waals bounded systems. Finally, when this method is combined with further corrections using local dielectric response theory, the binding energy of the Kr dimer is improved three times as compared to RPA.« less
Determination of ethephon residues in water by gas chromatography with cubic mass spectrometry after ion-exchange purification and derivatisation with N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide.

PubMed

Royer, A; Laporte, F; Bouchonnet, S; Communal, P-Y

2006-03-03

An analytical method has been developed for the determination of residues of ethephon (2-chloroethyl phosphonic acid) in drinking and surface water. The procedure is based on de-ionisation with an anion/cation-exchange resin, solid phase extraction by means of anion-exchange polystyrene-divinylbenzene extraction disks, elution with a mixture of methanol and 10 M hydrochloric acid (98/2, v/v), redisolution into acetonitrile after evaporation and silylation with N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide (MTBSTFA). Quantification is performed by gas chromatography with ion-trap cubic mass spectrometric detection in the electron impact mode (GC-EI-MS3). Method validation was conducted using samples of mineral, tap, and river water that were fortified with ethephon at concentration levels ranging from 0.1 to 1.0 microg/L. The mean recovery from all the fortified samples (n = 36) amounted to 88% with a relative standard deviation of 17%. The method, therefore, was shown to allow accurate determination of ethephon residues in drinking and surface water with a limit of quantification of 0.1 microg/L.
Si substrates texturing and vapor-solid-solid Si nanowhiskers growth using pure hydrogen as source gas

NASA Astrophysics Data System (ADS)

Nordmark, H.; Nagayoshi, H.; Matsumoto, N.; Nishimura, S.; Terashima, K.; Marioara, C. D.; Walmsley, J. C.; Holmestad, R.; Ulyashin, A.

2009-02-01

Scanning and transmission electron microscopies have been used to study silicon substrate texturing and whisker growth on Si substrates using pure hydrogen source gas in a tungsten hot filament reactor. Substrate texturing, in the nanometer to micrometer range of mono- and as-cut multicrystalline silicon, was observed after deposition of WSi2 particles that acted as a mask for subsequent hydrogen radical etching. Simultaneous Si whisker growth was observed for long residence time of the source gas and low H2 flow rate with high pressure. The whiskers formed via vapor-solid-solid growth, in which the deposited WSi2 particles acted as catalysts for a subsequent metal-induced layer exchange process well below the eutectic temperature. In this process, SiHx species, formed by substrate etching by the H radicals, diffuse through the metal particles. This leads to growth of crystalline Si whiskers via metal-induced solid-phase crystallization. Transmission electron microscopy, electron diffraction, and x-ray energy dispersive spectroscopy were used to study the WSi2 particles and the structure of the Si substrates in detail. It has been established that the whiskers are partly crystalline and partly amorphous, consisting of pure Si with WSi2 particles on their tips as well as sometimes being incorporated into their structure.
Dispersive micro solid phase extraction (DMSPE) using polymer anion exchange (PAX) as the sorbent followed by UPLC-MS/MS for the rapid determination of four bisphenols in commercial edible oils.

PubMed

Xian, Yanping; Wu, Yuluan; Dong, Hao; Guo, Xindong; Wang, Bin; Wang, Li

2017-09-29

The present work presents a novel and rapid analytical method for the simultaneous analysis of bisphenol A (BPA), bisphenol B (BPB), bisphenol F (BPF) and bisphenol S (BPS) in edible oil based on dispersive micro solid phase extraction (DMSPE) for the first time followed by isotope dilution-ultra high performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS). The edible oil sample was dispersed by n-hexane and extracted with ammoniated methanol-water solution. Then the target analytes were dispersedly absorbed using the polymer anion exchange (PAX) as the sorbent and eluted by acidic methanol. After that, four bisphenols were separated on a C18 column by gradient elution with methanol and 0.05% ammonium hydroxide in water as mobile phase, detected by MS/MS under multiple reactions monitoring (MRM) mode and quantified by internal standard method. The PAX amounts, adsorption time, concentrations of formic acid in the elution solvent and volume of elution solvent for the DMSPE technique were optimized. The limit of detection and quantitation (LOD and LOQ), matrix effect, recovery and precision of the developed method were investigated. Results indicated that BPS and the rest three bisphenols displayed excellent linearity in the concentration ranges of 0.1-50μg/L and 0.5-250μg/L, respectively, with correlation coefficients (R 2 ) all larger than 0.998. Achieved MLODs (S/N=3) varied between 0.1-0.4μg/kg for all bisphenols. The mean recoveries at three spiked levels in edible oil were in the range of 87.3-108%. Intra-day precision (n=6) and inter-day precision (n=5) were <9% and <11%, respectively. This method is of rapid-and-simple pretreatment, accurate and sensitive, and suitable for the simultaneous determination of bisphenols in edible oil. Copyright © 2017. Published by Elsevier B.V.
A two-qubit logic gate in silicon.

PubMed

Veldhorst, M; Yang, C H; Hwang, J C C; Huang, W; Dehollain, J P; Muhonen, J T; Simmons, S; Laucht, A; Hudson, F E; Itoh, K M; Morello, A; Dzurak, A S

2015-10-15

Quantum computation requires qubits that can be coupled in a scalable manner, together with universal and high-fidelity one- and two-qubit logic gates. Many physical realizations of qubits exist, including single photons, trapped ions, superconducting circuits, single defects or atoms in diamond and silicon, and semiconductor quantum dots, with single-qubit fidelities that exceed the stringent thresholds required for fault-tolerant quantum computing. Despite this, high-fidelity two-qubit gates in the solid state that can be manufactured using standard lithographic techniques have so far been limited to superconducting qubits, owing to the difficulties of coupling qubits and dephasing in semiconductor systems. Here we present a two-qubit logic gate, which uses single spins in isotopically enriched silicon and is realized by performing single- and two-qubit operations in a quantum dot system using the exchange interaction, as envisaged in the Loss-DiVincenzo proposal. We realize CNOT gates via controlled-phase operations combined with single-qubit operations. Direct gate-voltage control provides single-qubit addressability, together with a switchable exchange interaction that is used in the two-qubit controlled-phase gate. By independently reading out both qubits, we measure clear anticorrelations in the two-spin probabilities of the CNOT gate.
Phosphopeptide Enrichment by Covalent Chromatography after Derivatization of Protein Digests Immobilized on Reversed-Phase Supports

PubMed Central

Nika, Heinz; Nieves, Edward; Hawke, David H.; Angeletti, Ruth Hogue

2013-01-01

A rugged sample-preparation method for comprehensive affinity enrichment of phosphopeptides from protein digests has been developed. The method uses a series of chemical reactions to incorporate efficiently and specifically a thiol-functionalized affinity tag into the analyte by barium hydroxide catalyzed β-elimination with Michael addition using 2-aminoethanethiol as nucleophile and subsequent thiolation of the resulting amino group with sulfosuccinimidyl-2-(biotinamido) ethyl-1,3-dithiopropionate. Gentle oxidation of cysteine residues, followed by acetylation of α- and ε-amino groups before these reactions, ensured selectivity of reversible capture of the modified phosphopeptides by covalent chromatography on activated thiol sepharose. The use of C18 reversed-phase supports as a miniaturized reaction bed facilitated optimization of the individual modification steps for throughput and completeness of derivatization. Reagents were exchanged directly on the supports, eliminating sample transfer between the reaction steps and thus, allowing the immobilized analyte to be carried through the multistep reaction scheme with minimal sample loss. The use of this sample-preparation method for phosphopeptide enrichment was demonstrated with low-level amounts of in-gel-digested protein. As applied to tryptic digests of α-S1- and β-casein, the method enabled the enrichment and detection of the phosphorylated peptides contained in the mixture, including the tetraphosphorylated species of β-casein, which has escaped chemical procedures reported previously. The isolates proved highly suitable for mapping the sites of phosphorylation by collisionally induced dissociation. β-Elimination, with consecutive Michael addition, expanded the use of the solid-phase-based enrichment strategy to phosphothreonyl peptides and to phosphoseryl/phosphothreonyl peptides derived from proline-directed kinase substrates and to their O-sulfono- and O-linked β-N-acetylglucosamine (O-GlcNAc)-modified counterparts. Solid-phase enzymatic dephosphorylation proved to be a viable tool to condition O-GlcNAcylated peptide in mixtures with phosphopeptides for selective affinity purification. Acetylation, as an integral step of the sample-preparation method, precluded reduction in recovery of the thiolation substrate caused by intrapeptide lysine-dehydroalanine cross-link formation. The solid-phase analytical platform provides robustness and simplicity of operation using equipment readily available in most biological laboratories and is expected to accommodate additional chemistries to expand the scope of solid-phase serial derivatization for protein structural characterization. PMID:23997662
Liquid uranium alloy-helium fission reactor

DOEpatents

Minkov, Vladimir

1986-01-01

This invention teaches a nuclear fission reactor having a core vessel and at least one tandem heat exchanger vessel coupled therewith across upper and lower passages to define a closed flow loop. Nuclear fuel such as a uranium alloy in its liquid phase fills these vessels and flow passages. Solid control elements in the reactor core vessel are adapted to be adjusted relative to one another to control fission reaction of the liquid fuel therein. Moderator elements in the other vessel and flow passages preclude fission reaction therein. An inert gas such as helium is bubbled upwardly through the heat exchanger vessel operable to move the liquid fuel upwardly therein and unidirectionally around the closed loop and downwardly through the core vessel. This helium gas is further directed to heat conversion means outside of the reactor vessels to utilize the heat from the fission reaction to generate useful output. The nuclear fuel operates in the 1200.degree.-1800.degree. C. range, and even higher to 2500.degree. C., limited only by the thermal effectiveness of the structural materials, increasing the efficiency of power generation from the normal 30-35% with 300.degree.-500.degree. C. upper limit temperature to 50-65%. Irradiation of the circulating liquid fuel, as contrasted to only localized irradiation of a solid fuel, provides improved fuel utilization.
Mechanical Stability Criterion, Triple-Phase Condition, and Pressure Differences of Matter Condensed in a Porous Matrix.

PubMed

Setzer, Max J.

2001-03-01

In contrast to the triple-point condition of bulk material, condensed matter in porous media can coexist stably as liquid, solid, and vapor over a wide temperature range. The necessary conditions are found by a thermodynamic approach starting with the potential which reflects the grand canonical distribution and is characterized by heat and matter exchange. The other parameters are volume and surface. Therefore, it is designated the free mechanical potential. General expressions for mechanical stability are given. On condensation and melting the nonwetting phases vanish. These are thermodynamically stable phase transitions. For the opposing effects evaporation and fusion, an energy barrier must be transgressed either by nucleation or by intrusion as discussed here. These are metastable states. Phase transitions are the conditions which limit the triple-phase region. Within this region high negative pressures are generated in the unfrozen liquid independent of the pore size where it exists. The findings are applied to water in the disperse matrix of hardened cement paste. They are the basis for "micro ice lens pumping". Copyright 2001 Academic Press.
Phase transition in lithium garnet oxide ionic conductors Li7La3Zr2O12: The role of Ta substitution and H2O/CO2 exposure

NASA Astrophysics Data System (ADS)

Wang, Yuxing; Lai, Wei

2015-02-01

High Li-content lithium garnet oxides are promising solid electrolyte materials for lithium batteries. Being the highest Li-content lithium garnet oxides, Li7La3Zr2O12 has been reported to crystallize in either the tetragonal or cubic phase with no consensus on the exact conditions under which these two phases are formed, which may be due to unintentional Al contamination and air exposure. In this work, the effects of Ta substitution and H2O/CO2 exposure have been studied under Al-contamination free conditions with minimal air exposure. We showed that 1) the Ta-substitution induced phase transition occurred through a two-phase mechanism and a minimum 0.6 mol of Ta substitution to Zr is needed to stabilize the cubic phase; 2) H2O and CO2 can individually induce the tetragonal-cubic phase transition in Li7La3Zr2O12 through proton exchange and Li extraction, respectively, which can have great influence on the transport properties of Li7La3Zr2O12.
Microchannel laminated mass exchanger and method of making

DOEpatents

Martin, Peter M [Kennewick, WA; Bennett, Wendy D [Kennewick, WA; Matson, Dean W [Kennewick, WA; Stewart, Donald C [Richland, WA; Drost, Monte K [Pasco, WA; Wegeng, Robert S [Richland, WA; Perez, Joseph M [Richland, WA; Feng, Xiangdong [West Richland, WA; Liu, Jun [West Richland, WA

2003-03-18

The present invention is a microchannel mass exchanger having a first plurality of inner thin sheets and a second plurality of outer thin sheets. The inner thin sheets each have a solid margin around a circumference, the solid margin defining a slot through the inner thin sheet thickness. The outer thin sheets each have at least two header holes on opposite ends and when sandwiching an inner thin sheet. The outer thin sheets further have a mass exchange medium. The assembly forms a closed flow channel assembly wherein fluid enters through one of the header holes into the slot and exits through another of the header holes after contacting the mass exchange medium.
Microchannel laminated mass exchanger and method of making

DOEpatents

Martin, Peter M.; Bennett, Wendy D.; Matson, Dean W.; Stewart, Donald C.; Drost, Monte K.; Wegeng, Robert S.; Perez, Joseph M.; Feng, Xiangdong; Liu, Jun

2000-01-01

The present invention is a microchannel mass exchanger having a first plurality of inner thin sheets and a second plurality of outer thin sheets. The inner thin sheets each have a solid margin around a circumference, the solid margin defining a slot through the inner thin sheet thickness. The outer thin sheets each have at least two header holes on opposite ends and when sandwiching an inner thin sheet. The outer thin sheets further have a mass exchange medium. The assembly forms a closed flow channel assembly wherein fluid enters through one of the header holes into the slot and exits through another of the header holes after contacting the mass exchange medium.
Microchannel laminated mass exchanger and method of making

DOEpatents

Martin, Peter M [Kennewick, WA; Bennett, Wendy D [Kennewick, WA; Matson, Dean W [Kennewick, WA; Stewart, Donald C [Richland, WA; Drost, Monte K [Pasco, WA; Wegeng, Robert S [Richland, WA; Perez, Joseph M [Richland, WA; Feng, Xiangdong [West Richland, WA; Liu, Jun [West Richland, WA

2002-03-05

The present invention is a microchannel mass exchanger having a first plurality of inner thin sheets and a second plurality of outer thin sheets. The inner thin sheets each have a solid margin around a circumference, the solid margin defining a slot through the inner thin sheet thickness. The outer thin sheets each have at least two header holes on opposite ends and when sandwiching an inner thin sheet. The outer thin sheets further have a mass exchange medium. The assembly forms a closed flow channel assembly wherein fluid enters through one of the header holes into the slot and exits through another of the header holes after contacting the mass exchange medium.
Structure of H2Ti3O7 and its evolution during sodium insertion as anode for Na ion batteries.

PubMed

Eguía-Barrio, Aitor; Castillo-Martínez, Elizabeth; Zarrabeitia, Maider; Muñoz-Márquez, Miguel A; Casas-Cabanas, Montse; Rojo, Teófilo

2015-03-14

H2Ti3O7 was prepared as a single phase material by ionic exchange from Na2Ti3O7. The complete ionic exchange was confirmed by (1)H and (23)Na solid state Nuclear Magnetic Resonance (NMR). The atomic positions of H2Ti3O7 were obtained from the Rietveld refinement of powder X-ray diffraction (PXRD) and neutron diffraction experimental data, the latter collected at two different wavelengths to precisely determine the hydrogen atomic positions in the structure. All H(+) cations are hydrogen bonded to two adjacent [Ti3O7](2-) layers leading to the gliding of the layers and lattice centring with respect to the parent Na2Ti3O7. In contrast with a previous report where protons were located in two different positions of H2Ti3O7, 3 types of proton positions were found. Two of the three types of proton are bonded to the only oxygen linked to a single titanium atom forming an H-O-H angle close to that of the water molecule. H2Ti3O7 is able to electrochemically insert Na(+). The electrochemical insertion of sodium into H2Ti3O7 starts with a solid solution regime of the C-centred phase. Then, between 0.6 and 1.2 inserted Na(+) the reaction proceeds through a two phase reaction and a plateau at 1.3 V vs. Na(+)/Na is observed in the voltage-composition curve. The second phase resembles the primitive Na2Ti3O7 cell as detected by in situ PXRD. Upon oxidation, from 0.9 to 2.2 V, the PXRD pattern remains mostly unchanged probably due to H(+) removal instead of Na(+), with the capacity quickly fading upon cycling. Conditioning H2Ti3O7 for two cycles at 0.9-2.2 V before cycling in the 0.05-1.6 V range yields similar specific capacity and better retention than the original Na2Ti3O7 in the same voltage range.

STS-79 Space Shuttle Mission Report

NASA Technical Reports Server (NTRS)

Fricke, Robert W., Jr.

1996-01-01

STS-79 was the fourth of nine planned missions to the Russian Mir Space Station. This report summarizes the activities such as rendezvous and docking and spaceborne experiment operations. The report also discusses the Orbiter, External Tank (ET), Solid Rocket Boosters (SRB), Reusable Solid Rocket Motor (RSRM) and the space shuttle main engine (SSME) systems performance during the flight. The primary objectives of this flight were to rendezvous and dock with the Mir Space Station and exchange a Mir Astronaut. A double Spacehab module carried science experiments and hardware, risk mitigation experiments (RME's) and Russian logistics in support of program requirements. Additionally, phase 1 program science experiments were carried in the middeck. Spacehab-05 operations were performed. The secondary objectives of the flight were to perform the operations necessary for the Shuttle Amateur Radio Experiment-2 (SAREX-2). Also, as a payload of opportunity, the requirements of Midcourse Space Experiment (MSX) were completed.
Cryogenic Heat Exchanger with Turbulent Flows

ERIC Educational Resources Information Center

Amrit, Jay; Douay, Christelle; Dubois, Francis; Defresne, Gerard

2012-01-01

An evaporator-type cryogenic heat exchanger is designed and built for introducing fluid-solid heat exchange phenomena to undergraduates in a practical and efficient way. The heat exchanger functions at liquid nitrogen temperature and enables cooling of N[subscript 2] and He gases from room temperatures. We present first the experimental results of…
Determining solid-fluid interface temperature distribution during phase change of cryogenic propellants using transient thermal modeling

NASA Astrophysics Data System (ADS)

Bellur, K.; Médici, E. F.; Hermanson, J. C.; Choi, C. K.; Allen, J. S.

2018-04-01

Control of boil-off of cryogenic propellants is a continuing technical challenge for long duration space missions. Predicting phase change rates of cryogenic liquids requires an accurate estimation of solid-fluid interface temperature distributions in regions where a contact line or a thin liquid film exists. This paper described a methodology to predict inner wall temperature gradients with and without evaporation using discrete temperature measurements on the outer wall of a container. Phase change experiments with liquid hydrogen and methane in cylindrical test cells of various materials and sizes were conducted at the Neutron Imaging Facility at the National Institute of Standards and Technology. Two types of tests were conducted. The first type of testing involved thermal cycling of an evacuated cell (dry) and the second involved controlled phase change with cryogenic liquids (wet). During both types of tests, temperatures were measured using Si-diode sensors mounted on the exterior surface of the test cells. Heat is transferred to the test cell by conduction through a helium exchange gas and through the cryostat sample holder. Thermal conduction through the sample holder is shown to be the dominant mode with the rate of heat transfer limited by six independent contact resistances. An iterative methodology is employed to determine contact resistances between the various components of the cryostat stick insert, test cell and lid using the dry test data. After the contact resistances are established, inner wall temperature distributions during wet tests are calculated.
Feasible conversion of solid waste bauxite tailings into highly crystalline 4A zeolite with valuable application

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

Ma, Dongyang; Wang, Zhendong; Guo, Min

2014-11-15

Highlights: • Concept to convert waste to valuable product is carried out in this study. • An industrially feasible and cost-effective approach was developed and optimized. • Highly crystalline and well-defined zeolite was produced under moderate conditions. • The zeolite derived from the bauxite tailings displayed high ion exchange capacity. • Bauxite tailings have potential application in heavy metal ions adsorbent. - Abstract: Bauxite tailings are a major type of solid wastes generated in the flotation process. The waste by-products caused significant environmental impact. To lessen this hazardous effect from poisonous mine tailings, a feasible and cost-effective solution was conceivedmore » and implemented. Our approach focused on reutilization of the bauxite tailings by converting it to 4A zeolite for reuse in diverse applications. Three steps were involved in the bauxite conversion: wet-chemistry, alkali fusion, and crystallization to remove impurities and to prepare porous 4A zeolite. It was found that the cubic 4A zeolite was single phase, in high purity, with high crystallinity and well-defined structure. Importantly, the 4A zeolite displayed maximum calcium ion exchange capacity averaged at 296 mg CaCO{sub 3}/g, comparable to commercially-available zeolite (310 mg CaCO{sub 3}/g) exchange capacity. Base on the optimal synthesis condition, the reaction yield of zeolite 4A from bauxite tailings achieved to about 38.43%, hence, this study will provide a new paradigm for remediation of bauxite tailings, further mitigating the environmental and health care concerns, particularly in the mainland of PR China.« less
User's guide to PHREEQC (Version 2) : a computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations

USGS Publications Warehouse

Parkhurst, David L.; Appelo, C.A.J.

1999-01-01

PHREEQC version 2 is a computer program written in the C programming language that is designed to perform a wide variety of low-temperature aqueous geochemical calculations. PHREEQC is based on an ion-association aqueous model and has capabilities for (1) speciation and saturation-index calculations; (2) batch-reaction and one-dimensional (1D) transport calculations involving reversible reactions, which include aqueous, mineral, gas, solid-solution, surface-complexation, and ion-exchange equilibria, and irreversible reactions, which include specified mole transfers of reactants, kinetically controlled reactions, mixing of solutions, and temperature changes; and (3) inverse modeling, which finds sets of mineral and gas mole transfers that account for differences in composition between waters, within specified compositional uncertainty limits.New features in PHREEQC version 2 relative to version 1 include capabilities to simulate dispersion (or diffusion) and stagnant zones in 1D-transport calculations, to model kinetic reactions with user-defined rate expressions, to model the formation or dissolution of ideal, multicomponent or nonideal, binary solid solutions, to model fixed-volume gas phases in addition to fixed-pressure gas phases, to allow the number of surface or exchange sites to vary with the dissolution or precipitation of minerals or kinetic reactants, to include isotope mole balances in inverse modeling calculations, to automatically use multiple sets of convergence parameters, to print user-defined quantities to the primary output file and (or) to a file suitable for importation into a spreadsheet, and to define solution compositions in a format more compatible with spreadsheet programs. This report presents the equations that are the basis for chemical equilibrium, kinetic, transport, and inverse-modeling calculations in PHREEQC; describes the input for the program; and presents examples that demonstrate most of the program's capabilities.
Polymeric ionic liquid modified graphene oxide-grafted silica for solid-phase extraction to analyze the excretion-dynamics of flavonoids in urine by Box-Behnken statistical design.

PubMed

Hou, Xiudan; Liu, Shujuan; Zhou, Panpan; Li, Jin; Liu, Xia; Wang, Licheng; Guo, Yong

2016-07-22

A solid-phase extraction method for the efficient analysis of the excretion-dynamics of flavonoids in urine was established and described. In this work, in situ surface radical chain-transfer polymerization and in situ anion exchange were utilized to tune the extraction performance of poly(1-vinyl-3-hexylimidazolium bromide)-graphene oxide-grafted silica (poly(VHIm(+)Br(-))@GO@Sil). Graphene oxide (GO) was first coated onto the silica using a layer-by-layer fabrication method, and then the anion of poly(VHIm(+)Br(-))@GO@Sil was changed into hexafluorophosphate (PF6(-)) by in situ anion exchange. The interaction energies between two PILs and four flavonoids were calculated with the Gaussian09 suite of programs. A Box-Behnken design was used for the optimization of four greatly influential parameters after single-factor experiments to obtain more accurate and precise results. Coupled to high performance liquid chromatography, the poly(VHIm(+)PF6(-))@GO@Sil method showed acceptable extraction recoveries for the four flavonoids, with limits of detection in the range of 0.1-0.5μgL(-1), and wide linear ranges with correlation coefficients (R) ranging from 0.9935 to 0.9987. Under the optimum conditions, the proposed method was applied to analyze the urines collected from a healthy volunteer. The excretion amount-time profiles revealed that 4-15h was the main excretion time for the detected flavonoids. The results indicated that the newly developed method offered the advantages of being feasible, green and cost-effective, and could be successfully applied to the extraction and enrichment of flavonoids in human body systems allowing the study of the metabolic kinetics. Copyright © 2016. Published by Elsevier B.V.
Chiral speciation and determination of selenomethionine enantiomers in selenized yeast by ligand-exchange micellar electrokinetic capillary chromatography after solid phase extraction.

PubMed

Duan, Jiankun; He, Man; Hu, Bin

2012-12-14

A new phenylalanine derivative (L-N-(2-hydroxy-propyl)-phenylalanine, L-HP-Phe) was synthesized and its chelate with Cu(II) (Cu(II)-(L-HP-Phe)(2)) was used as the chiral selector for the ligand-exchange (LE) chiral separation of D,L-selenomethionine (SeMet) in selenized yeast samples by micelle electrokinetic capillary chromatography (MEKC). In order to improve the sensitivity of MEKC-UV, two-step preconcentration strategy was employed, off-line solid phase extraction (SPE) and on-line large volume sample stacking (LVSS). D,L-SeMet was first retained on the Cu(II) loaded mesoporous TiO(2), then eluted by 0.1 mL of 5 mol L(-1) ammonia, and finally introduced for MEKC-UV analysis by LVSS injection after evaporation of NH(3). With the enrichment factors of 1400 and 1378, the LODs of 0.44 and 0.60 ng mL(-1) for L-SeMet and D-SeMet was obtained, respectively. The developed method was applied to the analysis of D,L-SeMet in a certified reference material of SELM-1 and a commercial nutrition yeast, and the results showed that most of SeMet in the SELM-1 selenized yeast was l isomer and the recovery for L and D isomers in the spiked commercial nutrition yeast was 96.3% and 103%, respectively. This method is featured with low running cost, high sensitivity and selectivity, and exhibits application potential in chiral analysis of seleno amino acids in real world samples. Copyright © 2012 Elsevier B.V. All rights reserved.
Chromium speciation in environmental samples using a solid phase spectrophotometric method

NASA Astrophysics Data System (ADS)

Amin, Alaa S.; Kassem, Mohammed A.

2012-10-01

A solid phase extraction technique is proposed for preconcentration and speciation of chromium in natural waters using spectrophotometric analysis. The procedure is based on sorption of chromium(III) as 4-(2-benzothiazolylazo)2,2'-biphenyldiol complex on dextran-type anion-exchange gel (Sephadex DEAE A-25). After reduction of Cr(VI) by 0.5 ml of 96% concentrated H2SO4 and ethanol, the system was applied to the total chromium. The concentration of Cr(VI) was calculated as the difference between the total Cr and the Cr(III) content. The influences of some analytical parameters such as: pH of the aqueous solution, amounts of 4-(2-benzothiazolylazo)2,2'-biphenyldiol (BTABD), and sample volumes were investigated. The absorbance of the gel, at 628 and 750 nm, packed in a 1.0 mm cell, is measured directly. The molar absorptivities were found to be 2.11 × 107 and 3.90 × 107 L mol-1 cm-1 for 500 and 1000 ml, respectively. Calibration is linear over the range 0.05-1.45 μg L-1 with RSD of <1.85% (n = 8.0). Using 35 mg exchanger, the detection and quantification limits were 13 and 44 ng L-1 for 500 ml sample, whereas for 1000 ml sample were 8.0 and 27 ng L-1, respectively. Increasing the sample volume can enhance the sensitivity. No considerable interferences have been observed from other investigated anions and cations on the chromium speciation. The proposed method was applied to the speciation of chromium in natural waters and total chromium preconcentration in microwave digested tobacco, coffee, tea, and soil samples. The results were simultaneously compared with those obtained using an ET AAS method, whereby the validity of the method has been tested.
The magnetic properties of BaCo0.5Ni0.5F4

NASA Astrophysics Data System (ADS)

Xu, Qingyu; Dai, Chuanjun; Han, Zhida; Li, Qi

2018-05-01

The family of BaMF4 with M of magnetic 3d transition metal ions is the typical multiferroic material. Pure phase solid solution of BaCoF4 and BaNiF4 with molar ratio of 1:1 (BaCo0.5Ni0.5F4) is prepared by solid state reaction, which has been confirmed by X ray diffraction patterns. Field dependent magnetization measurements only show the linear curve with temperature down to 5 K, indicating the antiferromagnetic nature. Compared with BaCoF4 and BaNiF4, no significant enhancement of magnetization is observed, indicating the absence of ferrimagnetism and the random distribution of Co and Ni ions. The low temperature magnetic anomalies are studied by zero field cooled (ZFC) and field cooled (FC) temperature dependent magnetization (M-T) measurements. A bifurcation between FC and ZFC M-T curves happens at 118 K, indicating the onset of 2-dimensional antiferromagnetism. The magnetization maximum at 87 K is attributed to the 2-dimensional antiferromagnetic clusters, followed by the drastic decrease of magnetization, which is due to the onset of 3-dimensional antiferromagnetism. A dip is observed in FC M-T curve at 40 K, which is attributed to the 3-dimensional antiferromagnetic clusters. A drastic increase of magnetization is observed at 9 K, which is due to the uncompensated isolated spins. Exchange bias is clearly observed, with blocking temperature of 90 K. The contribution from surface spin glass has been excluded by the AC magnetization measurements, and the mechanism has been explained by the exchange coupling between the two antiferromagnetic phases.
Morphological Control of In x Ga 1–x P Nanocrystals Synthesized in a Nonthermal Plasma

DOE PAGES

Bronstein, Noah D.; Wheeler, Lance M.; Anderson, Nicholas C.; ...

2018-04-09

We explore the growth of InxGa1-xP nanocrystals (x = 1, InP; x = 0, GaP; and 1 > x > 0, alloys) in a nonthermal plasma. By tuning the reactor conditions, we gain control over the morphology of the final product, producing either 10 nm diameter hollow nanocrystals or smaller 3 nm solid nanocrystals. We observe the gas-phase chemistry in the plasma reactor using plasma emission spectroscopy to understand the growth mechanism of the hollow versus solid morphology. We also connect this plasma chemistry to the subsequent native surface chemistry of the nanocrystals, which is dominated by the presence ofmore » both dative- and lattice-bound phosphine species. The dative phosphines react readily with oleylamine in an L-type ligand exchange reaction, evolving phosphines and allowing the particles to be dispersed in nonpolar solvents. Subsequent treatment by HF causes the solid InP1.5 and In0.5Ga0.5P1.3 to become photoluminescent, whereas the hollow particles remain nonemissive.« less
Morphological Control of In xGa 1–xP Nanocrystals Synthesized in a Nonthermal Plasma

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

Bronstein, Noah D.; Wheeler, Lance M.; Anderson, Nicholas C.

Here, we explore the growth of In xGa 1–xP nanocrystals (x = 1, InP; x = 0, GaP; and 1 > x > 0, alloys) in a nonthermal plasma. By tuning the reactor conditions, we gain control over the morphology of the final product, producing either 10 nm diameter hollow nanocrystals or smaller 3 nm solid nanocrystals. We observe the gas-phase chemistry in the plasma reactor using plasma emission spectroscopy to understand the growth mechanism of the hollow versus solid morphology. We also connect this plasma chemistry to the subsequent native surface chemistry of the nanocrystals, which is dominated bymore » the presence of both dative- and lattice-bound phosphine species. The dative phosphines react readily with oleylamine in an L-type ligand exchange reaction, evolving phosphines and allowing the particles to be dispersed in nonpolar solvents. Subsequent treatment by HF causes the solid InP 1.5 and In 0.5Ga 0.5P 1.3 to become photoluminescent, whereas the hollow particles remain nonemissive.« less
Morphological Control of In xGa 1–xP Nanocrystals Synthesized in a Nonthermal Plasma

DOE PAGES

Bronstein, Noah D.; Wheeler, Lance M.; Anderson, Nicholas C.; ...

2018-04-09

Here, we explore the growth of In xGa 1–xP nanocrystals (x = 1, InP; x = 0, GaP; and 1 > x > 0, alloys) in a nonthermal plasma. By tuning the reactor conditions, we gain control over the morphology of the final product, producing either 10 nm diameter hollow nanocrystals or smaller 3 nm solid nanocrystals. We observe the gas-phase chemistry in the plasma reactor using plasma emission spectroscopy to understand the growth mechanism of the hollow versus solid morphology. We also connect this plasma chemistry to the subsequent native surface chemistry of the nanocrystals, which is dominated bymore » the presence of both dative- and lattice-bound phosphine species. The dative phosphines react readily with oleylamine in an L-type ligand exchange reaction, evolving phosphines and allowing the particles to be dispersed in nonpolar solvents. Subsequent treatment by HF causes the solid InP 1.5 and In 0.5Ga 0.5P 1.3 to become photoluminescent, whereas the hollow particles remain nonemissive.« less
[Analysis of sulfonamids and their metabolites in drinking water by high Performance liquid chromatography tandem mass spectrometry].

PubMed

Wang, Shuo; Li, Shuming; Zhang, Xiangming; Wei, Yunfang; Zhang, Meiyun; Zhang, Jing

2015-07-01

To develop a comprehensive method for simultaneous analysis of sulfonamides and their metabolites in drinking water by high performance liquid chromatography tandem mass spectrometry (LC-MS/MS). Different solid-phase extraction columns were compared with respect to the recovery of target drugs from drinking water. The drinking water samples were adjusted to 3 by HCl and purified by a mix mode cation-ion exchange solid-phase extraction (SPE), following determination using LG-MS/MS. A total of 21 sulfonamides were separated by a C15 column (2.1 mm x 100 mm, 1.7 µm) and analyzed under positive ion mode with multi-reaction monitoring. The matrix-matched external standard calibration was used for quantification. The method quantification limits for 21 analytes were 0.03-0.63 ng/L with overall recoveries of 50.1%-114.9%, and the relative standard deviations less than 20%. The method was finally used to analyze sulfonamides in drinking water in Beijing, and 5 target compounds (sulfadiazine, sulfathiazole, sulfapyridine, trimethoprim and sulfamethazine) were detected at a concentration range of 0.08-32.54 ng/L. This method could be applied in simultaneous analysis of sulfonamides and their metabolites in drinking water samples.
Validated Method for the Quantification of Baclofen in Human Plasma Using Solid-Phase Extraction and Liquid Chromatography–Tandem Mass Spectrometry

PubMed Central

Nahar, Limon Khatun; Cordero, Rosa Elena; Nutt, David; Lingford-Hughes, Anne; Turton, Samuel; Durant, Claire; Wilson, Sue; Paterson, Sue

2016-01-01

Abstract A highly sensitive and fully validated method was developed for the quantification of baclofen in human plasma. After adjusting the pH of the plasma samples using a phosphate buffer solution (pH 4), baclofen was purified using mixed mode (C8/cation exchange) solid-phase extraction (SPE) cartridges. Endogenous water-soluble compounds and lipids were removed from the cartridges before the samples were eluted and concentrated. The samples were analyzed using triple-quadrupole liquid chromatography–tandem mass spectrometry (LC–MS-MS) with triggered dynamic multiple reaction monitoring mode for simultaneous quantification and confirmation. The assay was linear from 25 to 1,000 ng/mL (r2 > 0.999; n = 6). Intraday (n = 6) and interday (n = 15) imprecisions (% relative standard deviation) were <5%, and the average recovery was 30%. The limit of detection of the method was 5 ng/mL, and the limit of quantification was 25 ng/mL. Plasma samples from healthy male volunteers (n = 9, median age: 22) given two single oral doses of baclofen (10 and 60 mg) on nonconsecutive days were analyzed to demonstrate method applicability. PMID:26538544
Kinetic controls on the complexation between mercury and dissolved organic matter in a contaminated environment.

PubMed

Miller, Carrie L; Southworth, George; Brooks, Scott; Liang, Liyuan; Gu, Baohua

2009-11-15

The interaction of mercury (Hg) with dissolved natural organic matter (NOM) under equilibrium conditions is the focus of many studies but the kinetic controls on Hg-NOM complexation in aquatic systems have often been overlooked. We examined the rates of Hg-NOM complexation both in a contaminated Upper East Fork Poplar Creek (UEFPC) in Oak Ridge, Tennessee, and in controlled laboratory experiments using reducible Hg (Hg(R)) measurements and C(18) solid phase extraction techniques. Of the filterable Hg at the headwaters of UEFPC, >90% was present as Hg(R) and this fraction decreased downstream but remained >29% of the filterable Hg at all sites. The presence of higher Hg(R) concentrations than would be predicted under equilibrium conditions in UEFPC and in experiments with a NOM isolate suggests that kinetic reactions are controlling the complexation between Hg and NOM. The slow formation of Hg-NOM complexes is attributed to competitive ligand exchange among various moieties and functional groups in NOM with a range of binding strengths and configurations. This study demonstrates the need to consider the effects of Hg-NOM complexation kinetics on processes such as Hg methylation and solid phase partitioning.
Ultra-high performance liquid chromatography tandem mass spectrometry for the determination of five glycopeptide antibiotics in food and biological samples using solid-phase extraction.

PubMed

Deng, Fenfang; Yu, Hong; Pan, Xinhong; Hu, Guoyuan; Wang, Qiqin; Peng, Rongfei; Tan, Lei; Yang, Zhicong

2018-02-23

This paper demonstrated the development and validation of an ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) method for simultaneous determination of five glycopeptide antibiotics in food and biological samples. The target glycopeptide antibiotics were isolated from the samples by solvent extraction, and the extracts were cleaned with a tandem solid-phase extraction step using mixed strong cation exchange and hydrophilic/lipophilic balance cartridges. Subsequently, the analytes were eluted with different solvents, and then quantified by UHPLC-MS/MS in the positive ionization mode with multiple reaction monitoring. Under optimal conditions, good linear correlations were obtained for the five glycopeptide antibiotics in the concentration range of 1.0 μg/L to 20.0 μg/L, and with linear correlation coefficients >0.998. Employing this method, the target glycopeptide antibiotics in food and biological samples were identified with a recovery of 83.0-102%, and a low quantitation limit of 1.0 μg/kg in food and 2.0 μg/L in biological samples with low matrix effects. Copyright © 2018 Elsevier B.V. All rights reserved.
Incubation of air-pollution-control residues from secondary Pb smelter in deciduous and coniferous organic soil horizons: leachability of lead, cadmium and zinc.

PubMed

Chrastný, Vladislav; Vaněk, Aleš; Komárek, Michael; Farkaš, Juraj; Drábek, Ondřej; Vokurková, Petra; Němcová, Jana

2012-03-30

The leachability of air-pollution-control (APC) residues from a secondary lead smelter in organic soil horizons (F and H) from a deciduous and a coniferous forest during incubation periods of 0, 3 and 6 months were compared in this work. While the concentration of Pb, Zn and Cd associated with the exchangeable/acid extractable fraction in the horizon F from the coniferous forest was higher compared to the deciduous, significantly lower concentrations in the humified horizon H was found. It is suggested that lower pH and a higher share of fulvic acids fraction (FAs) of solid phase soil organic matter (SOM) in the humified soil horizon H from the coniferous compared to the deciduous forest is responsible for a higher metal association with solid phase SOM and therefore a lower metal leaching in a soil system. From this point of view, the humified soil horizon H from the deciduous forest represents a soil system more vulnerable to Pb, Zn and Cd leaching from APC residues. Copyright Â© 2012 Elsevier B.V. All rights reserved.
Poly(ionic liquids)-coated stainless-steel wires packed into a polyether ether ketone tube for in-tube solid-phase microextraction.

PubMed

Feng, Juanjuan; Wang, Xiuqin; Tian, Yu; Luo, Chuannan; Sun, Min

2017-12-01

An in-tube solid-phase microextraction device was developed by packing poly(ionic liquids)-coated stainless-steel wires into a polyether ether ketone tube. An anion-exchange process was performed to enhance the extraction performance. Surface properties of poly(ionic liquids)-coated stainless-steel wires were characterized by scanning electron microscopy and energy dispersive X-ray spectrometry. The extraction device was connected to high-performance liquid chromatography equipment to build an online enrichment and analysis system. Ten polycyclic aromatic hydrocarbons were used as model analytes, and important conditions including extraction time and desorption time were optimized. The enrichment factors from 268 to 2497, linear range of 0.03-20 μg/L, detection limits of 0.010-0.020 μg/L, extraction and preparation repeatability with relative standard deviation less than 1.8 and 19%, respectively were given by the established online analysis method. It has been used to detect polycyclic aromatic hydrocarbons in environmental samples, with the relative recovery (5, 10 μg/L) in the range of 85.1-118.9%. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Experimental investigation of the propagation of a planar shock wave through a two-phase gas-liquid medium

NASA Astrophysics Data System (ADS)

Chauvin, A.; Jourdan, G.; Daniel, E.; Houas, L.; Tosello, R.

2011-11-01

We conducted a series of shock tube experiments to study the influence of a cloud of water droplets on the propagation of a planar shock wave. In a vertically oriented shock tube, the cloud of droplets was released downwards into the air at atmospheric pressure while the shock wave propagated upwards. Two shock wave Mach numbers, 1.3 and 1.5, and three different heights of clouds, 150 mm, 400 mm, and 700 mm, were tested with an air-water volume fraction and a droplet diameter fixed at 1.2% and 500 μm, respectively. From high-speed visualization and pressure measurements, we analyzed the effect of water clouds on the propagation of the shock wave. It was shown that the pressure histories recorded in the two-phase gas-liquid mixture are different from those previously obtained in the gas-solid case. This different behavior is attributed to the process of atomization of the droplets, which is absent in the gas-solid medium. Finally, it was observed that the shock wave attenuation was dependent on the exchange surface crossed by the shock combined with the breakup criterion.
Mg-Al and Zn-Fe layered double hydroxides used for organic species storage and controlled release.

PubMed

Seftel, E M; Cool, P; Lutic, D

2013-12-01

Layered double hydroxides (LDH) containing (Mg and Al) or (Zn and Fe) were prepared by coprecipitation at constant pH, using NaOH and urea as precipitation agents. The most pure LDH phase in the Zn/Fe system was obtained with urea and in Mg/Al system when using NaOH. The incorporation of phenyl-alanine (Phe) anions in the interlayer of the LDH was performed by direct coprecipitation, ionic exchange and structure reconstruction of the mixed oxide obtained by the calcination of the coprecipitated product at 400°C. The reconstruction method and the direct coprecipitation in a medium containing Phe in the initial mixture were less successful in terms of high yields of organic-mineral composite than the ionic exchange method. A spectacular change in sample morphology and yield in exchanged solid was noticed for the Zn3Fe sample obtained by ionic exchange for 6h with Phe solution. A delivery test in PBS of pH=7.4 showed the release of the Phe in several steps up to 25 h indicating different host-guest interactions between the Phe and the LDH matrix. This behavior makes the preparation useful to obtain late delivery drugs, by the incorporation of the anion inside the LDH layer. © 2013.

On-line hyphenation of solid-phase extraction to chromatographic separation of sulfonamides with fused-core columns in sequential injection chromatography.

PubMed

Batista, Alex D; Chocholouš, Petr; Satínský, Dalibor; Solich, Petr; Rocha, Fábio R P

2015-02-01

On-line sample pretreatment (clean-up and analyte preconcentration) is for the first time coupled to sequential injection chromatography. The approach combines anion-exchange solid-phase extraction and the highly effective pentafluorophenylpropyl (F5) fused-core particle column for separation of eight sulfonamide antibiotics with similar structures (sulfathiazole, sulfanilamide, sulfacetamide, sulfadiazine, sulfamerazine, sulfadimidine, sulfamethoxazole and sulfadimethoxine). The stationary phase was selected after a critical comparison of the performance achieved by three fused-core reversed phase columns (Ascentis(®) Express RP-Amide, Phenyl-Hexyl, and F5) and two monolithic columns (Chromolith(®) High Resolution RP-18 and CN). Acetonitrile and acetate buffer pH 5.0 at 0.60 mL min(-1) were used as mobile phase to perform the separations before spectrophotometric detection. The first mobile phase was successfully used as eluent from SPE column ensuring transfer of a narrow zone to the chromatographic column. Enrichment factors up to 39.2 were achieved with a 500 µL sample volume. The developed procedure showed analysis time <10.5 min, resolutions >1.83 with peak symmetry ≤1.52, LODs between 4.9 and 27 µg L(-1), linear response ranges from 30.0 to 1000.0 µg L(-1) (r(2)>0.996) and RSDs of peak heights <2.9% (n=6) at a 100 µg L(-1) level and enabled the screening control of freshwater samples contaminated at the 100 µg L(-1) level. The proposed approach expanded the analytical potentiality of SIC and avoided the time-consuming batch sample pretreatment step, thus minimizing risks of sample contamination and analyte losses. Copyright © 2014 Elsevier B.V. All rights reserved.
A conjugate heat transfer procedure for gas turbine blades.

PubMed

Croce, G

2001-05-01

A conjugate heat transfer procedure, allowing for the use of different solvers on the solid and fluid domain(s), is presented. Information exchange between solid and fluid solution is limited to boundary condition values, and this exchange is carried out at any pseudo-time step. Global convergence rate of the procedure is, thus, of the same order of magnitude of stand-alone computations.
Modified sedimentation-dispersion model for solids in a three-phase slurry column

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

Smith, D.N.; Ruether, J.A.; Shah, Y.T.

1986-03-01

Solids distribution data for a three-phase, batch-fluidized slurry bubble column (SBC) are presented, using air as the gas phase, pure liquids and solutions as the liquid phase, and glass beads and carborundum catalyst powder as the solid phase. Solids distribution data for the three-phase SBC operated in a continuous mode of operation are also presented, using nitrogen as the gas phase, water as the liquid phase, and glass beads as the solid phase. A new model to provide a reasonable approach to predict solids concentration distributions for systems containing polydispersed solids is presented. The model is a modification of standardmore » sedimentation-dispersion model published earlier. Empirical correlations for prediction of hindered settling velocity and solids dispersion coefficient for systems containing polydispersed solids are presented. A new method of evaluating critical gas velocity (CGV) from concentrations of the sample withdrawn at the same port of the SBC is presented. Also presented is a new mapping for CGV which separates the two regimes in the SBC, namely, incomplete fluidization and complete fluidization.« less
Novel dispersive micro-solid-phase extraction combined with ultrahigh-performance liquid chromatography-high-resolution mass spectrometry to determine morpholine residues in citrus and apples.

PubMed

Chen, Dawei; Miao, Hong; Zou, Jianhong; Cao, Pei; Ma, Ning; Zhao, Yunfeng; Wu, Yongning

2015-01-21

This paper presents a new analytical method for the determination of morpholine residues in citrus and apples using a novel dispersive micro-solid-phase extraction (DMSPE), followed by ultrahigh-performance liquid chromatography-high-resolution mass spectrometry (UHPLC-HRMS). Samples were extracted with 1% formic acid in acetonitrile/water (1:1, v/v) and then cleaned up using the DMSPE procedure. Morpholine from the extract was adsorbed to a polymer cation exchange sorbent and eluted with ammonium hydroxide/acetonitrile (3:97, v/v) through a 1 mL syringe with a 0.22 μm nylon syringe filter. All of the samples were analyzed by UHPLC-HRMS/MS on a Waters Acquity BEH hydrophilic interaction chromatography column using 0.1% formic acid and 4 mM ammonium formate in water/acetonitrile as the mobile phase with gradient elution. The method showed good linearity (R(2) > 0.999) in the range of 1-100 μg/L for the analyte. The limit of detection and limit of quantitation values of morpholine were 2 and 5 μg/kg, respectively. The average recoveries of morpholine from the citrus and apple samples spiked at three different concentrations (5, 20, and 100 μg/kg) were in a range from 78.4 to 102.7%.
Navigating the Waters of Unconventional Crystalline Hydrates

PubMed Central

2015-01-01

Elucidating the crystal structures, transformations, and thermodynamics of the two zwitterionic hydrates (Hy2 and HyA) of 3-(4-dibenzo[b,f][1,4]oxepin-11-yl-piperazin-1-yl)-2,2-dimethylpropanoic acid (DB7) rationalizes the complex interplay of temperature, water activity, and pH on the solid form stability and transformation pathways to three neutral anhydrate polymorphs (Forms I, II°, and III). HyA contains 1.29 to 1.95 molecules of water per DB7 zwitterion (DB7z). Removal of the essential water stabilizing HyA causes it to collapse to an amorphous phase, frequently concomitantly nucleating the stable anhydrate Forms I and II°. Hy2 is a stoichiometric dihydrate and the only known precursor to Form III, a high energy disordered anhydrate, with the level of disorder depending on the drying conditions. X-ray crystallography, solid state NMR, and H/D exchange experiments on highly crystalline phase pure samples obtained by exquisite control over crystallization, filtration, and drying conditions, along with computational modeling, provided a molecular level understanding of this system. The slow rates of many transformations and sensitivity of equilibria to exact conditions, arising from its varying static and dynamic disorder and water mobility in different phases, meant that characterizing DB7 hydration in terms of simplified hydrate classifications was inappropriate for developing this pharmaceutical. PMID:26075319
Speciation of selenium in environmental samples by solid-phase spectrophotometry using 2,3-dichloro-6-(2,7-dihydroxy-naphthylazo)quinoxaline.

PubMed

Amin, Alaa S

2014-01-01

Solid-phase spectrophotometry was applied to determination of trace amounts of selenium (Se) in water, soil, plant materials, human hair, and a cosmetic preparation (lipstick). Se(IV) was sorbed in a dextran type lipophilic gel as a complex with 2,3-dichloro-6-(2,7-dihydroxy-naphthylazo)quinoxaline (DCDHNAQ), whereas Se(VI) was determined after boiling in HCI for 10 min to convert Se(VI) to Se(IV). Resin phase absorbances at 588 and 800 nm were measured directly, which allowed the determination of Se in the range of 0.2-3.3 microg/L with an RSD of 1.22%. The influences of analytical parameters including pH of the aqueous solution, amounts of DCDHNAQ, and sample volume were investigated. The molar absorptivities were found to be 1.09 x 10(6), 4.60 x 10(6), and 1.23 x 10(7) L/mol cm for 100, 500, and 1000 mL, respectively. The LOD and LOQ of the 500 mL sample method were 110 and 360 ng/L, respectively, when using 50 mg dextran type lipophilic gel. For a 1000 mL sample, the LOD and LOQ were 60 and 200 ng/L, respectively, using 50 mg of the exchanger. Increasing the sample volume enhanced the sensitivity. No considerable interferences were observed from other investigated anions and cations on the Se determination.
Amorphous surface layer versus transient amorphous precursor phase in bone - A case study investigated by solid-state NMR spectroscopy.

PubMed

Von Euw, Stanislas; Ajili, Widad; Chan-Chang, Tsou-Hsi-Camille; Delices, Annette; Laurent, Guillaume; Babonneau, Florence; Nassif, Nadine; Azaïs, Thierry

2017-09-01

The presence of an amorphous surface layer that coats a crystalline core has been proposed for many biominerals, including bone mineral. In parallel, transient amorphous precursor phases have been proposed in various biomineralization processes, including bone biomineralization. Here we propose a methodology to investigate the origin of these amorphous environments taking the bone tissue as a key example. This study relies on the investigation of a bone tissue sample and its comparison with synthetic calcium phosphate samples, including a stoichiometric apatite, an amorphous calcium phosphate sample, and two different biomimetic apatites. To reveal if the amorphous environments in bone originate from an amorphous surface layer or a transient amorphous precursor phase, a combined solid-state nuclear magnetic resonance (NMR) experiment has been used. The latter consists of a double cross polarization 1 H→ 31 P→ 1 H pulse sequence followed by a 1 H magnetization exchange pulse sequence. The presence of an amorphous surface layer has been investigated through the study of the biomimetic apatites; while the presence of a transient amorphous precursor phase in the form of amorphous calcium phosphate particles has been mimicked with the help of a physical mixture of stoichiometric apatite and amorphous calcium phosphate. The NMR results show that the amorphous and the crystalline environments detected in our bone tissue sample belong to the same particle. The presence of an amorphous surface layer that coats the apatitic core of bone apatite particles has been unambiguously confirmed, and it is certain that this amorphous surface layer has strong implication on bone tissue biogenesis and regeneration. Questions still persist on the structural organization of bone and biomimetic apatites. The existing model proposes a core/shell structure, with an amorphous surface layer coating a crystalline bulk. The accuracy of this model is still debated because amorphous calcium phosphate (ACP) environments could also arise from a transient amorphous precursor phase of apatite. Here, we provide an NMR spectroscopy methodology to reveal the origin of these ACP environments in bone mineral or in biomimetic apatite. The 1 H magnetization exchange between protons arising from amorphous and crystalline domains shows unambiguously that an ACP layer coats the apatitic crystalline core of bone et biomimetic apatite platelets. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Solid state phase change materials for thermal energy storage in passive solar heated buildings

NASA Astrophysics Data System (ADS)

Benson, D. K.; Christensen, C.

1983-11-01

A set of solid state phase change materials was evaluated for possible use in passive solar thermal energy storage systems. The most promising materials are organic solid solutions of pentaerythritol, pentaglycerine and neopentyl glycol. Solid solution mixtures of these compounds can be tailored so that they exhibit solid-to-solid phase transformations at any desired temperature within the range from less than 25 deg to 188 deg. Thermophysical properties such as thermal conductivity, density and volumetric expansion were measured. Computer simulations were used to predict the performance of various Trombe wall designs incorporating solid state phase change materials. Optimum performance was found to be sensitive to the choice of phase change temperatures and to the thermal conductivity of the phase change material. A molecular mechanism of the solid state phase transition is proposed and supported by infrared spectroscopic evidence.
Balancing Accuracy and Computational Efficiency for Ternary Gas Hydrate Systems

NASA Astrophysics Data System (ADS)

White, M. D.

2011-12-01

Geologic accumulations of natural gas hydrates hold vast organic carbon reserves, which have the potential of meeting global energy needs for decades. Estimates of vast amounts of global natural gas hydrate deposits make them an attractive unconventional energy resource. As with other unconventional energy resources, the challenge is to economically produce the natural gas fuel. The gas hydrate challenge is principally technical. Meeting that challenge will require innovation, but more importantly, scientific research to understand the resource and its characteristics in porous media. Producing natural gas from gas hydrate deposits requires releasing CH4 from solid gas hydrate. The conventional way to release CH4 is to dissociate the hydrate by changing the pressure and temperature conditions to those where the hydrate is unstable. The guest-molecule exchange technology releases CH4 by replacing it with a more thermodynamically stable molecule (e.g., CO2, N2). This technology has three advantageous: 1) it sequesters greenhouse gas, 2) it releases energy via an exothermic reaction, and 3) it retains the hydraulic and mechanical stability of the hydrate reservoir. Numerical simulation of the production of gas hydrates from geologic deposits requires accounting for coupled processes: multifluid flow, mobile and immobile phase appearances and disappearances, heat transfer, and multicomponent thermodynamics. The ternary gas hydrate system comprises five components (i.e., H2O, CH4, CO2, N2, and salt) and the potential for six phases (i.e., aqueous, liquid CO2, gas, hydrate, ice, and precipitated salt). The equation of state for ternary hydrate systems has three requirements: 1) phase occurrence, 2) phase composition, and 3) phase properties. Numerical simulation of the production of geologic accumulations of gas hydrates have historically suffered from relatively slow execution times, compared with other multifluid, porous media systems, due to strong nonlinearities and phase transitions. This paper describes and demonstrates a numerical solution scheme for ternary hydrate systems that seeks a balance between accuracy and computational efficiency. This scheme uses a generalize cubic equation of state, functional forms for the hydrate equilibria and cage occupancies, variable switching scheme for phase transitions, and kinetic exchange of hydrate formers (i.e., CH4, CO2, and N2) between the mobile phases (i.e., aqueous, liquid CO2, and gas) and hydrate phase. Accuracy of the scheme will be evaluated by comparing property values and phase equilibria against experimental data. Computational efficiency of the scheme will be evaluated by comparing the base scheme against variants. The application of interest will the production of a natural gas hydrate deposit from a geologic formation, using the guest molecule exchange process; where, a mixture of CO2 and N2 are injected into the formation. During the guest-molecule exchange, CO2 and N2 will predominately replace CH4 in the large and small cages of the sI structure, respectively.
Two-dimensional lattice gauge theories with superconducting quantum circuits

PubMed Central

Marcos, D.; Widmer, P.; Rico, E.; Hafezi, M.; Rabl, P.; Wiese, U.-J.; Zoller, P.

2014-01-01

A quantum simulator of U(1) lattice gauge theories can be implemented with superconducting circuits. This allows the investigation of confined and deconfined phases in quantum link models, and of valence bond solid and spin liquid phases in quantum dimer models. Fractionalized confining strings and the real-time dynamics of quantum phase transitions are accessible as well. Here we show how state-of-the-art superconducting technology allows us to simulate these phenomena in relatively small circuit lattices. By exploiting the strong non-linear couplings between quantized excitations emerging when superconducting qubits are coupled, we show how to engineer gauge invariant Hamiltonians, including ring-exchange and four-body Ising interactions. We demonstrate that, despite decoherence and disorder effects, minimal circuit instances allow us to investigate properties such as the dynamics of electric flux strings, signaling confinement in gauge invariant field theories. The experimental realization of these models in larger superconducting circuits could address open questions beyond current computational capability. PMID:25512676
Phase coherence and Andreev reflection in topological insulator devices

DOE PAGES

Finck, A. D. K.; Kurter, C.; Hor, Y. S.; ...

2014-11-04

Topological insulators (TIs) have attracted immense interest because they host helical surface states. Protected by time-reversal symmetry, they are robust to nonmagnetic disorder. When superconductivity is induced in these helical states, they are predicted to emulate p-wave pairing symmetry, with Majorana states bound to vortices. Majorana bound states possess non-Abelian exchange statistics that can be probed through interferometry. Here, we take a significant step towards Majorana interferometry by observing pronounced Fabry-Pérot oscillations in a TI sandwiched between a superconducting and a normal lead. For energies below the superconducting gap, we observe a doubling in the frequency of the oscillations, arisingmore » from an additional phase from Andreev reflection. When a magnetic field is applied perpendicular to the TI surface, a number of very sharp and gate-tunable conductance peaks appear at or near zero energy, which has consequences for interpreting spectroscopic probes of Majorana fermions. Our results show that TIs are a promising platform for exploring phase-coherent transport in a solid-state system.« less
Nature's engineering: Giant magnetic exchange bias > 1T in a natural mineral

NASA Astrophysics Data System (ADS)

McEnroe, S. A.; Carter-Stiglitz, B.; Harrison, R. J.; Robinson, P.; McCammon, C.

2006-12-01

Magnetic exchange bias is a phenomenon whereby the hysteresis loop of a "soft" magnetic phase is shifted along the applied field axis by an amount of exchange due to interaction with a "hard" magnetic phase. Exchange bias is the subject of intense experimental and theoretical investigation because of its widespread technological applications and recent advances in manipulating nanoscale materials. Understanding the physical origin of exchange bias has been hampered, by the general uncertainty in the crystal and magnetic structure of the interface between hard and soft phases. Here we discuss a natural sample that has one of the largest exchange biases ever reported, nearly 1 Tesla (T) in a 1.5 T field and is the first documented example of exchange bias of this magnitude in a natural mineral. We demonstrate that exchange bias in this system is due to the interaction between coherently intergrown magnetic phases, formed through a natural process of phase separation during slow cooling. These extreme properties are found in a sample of titanohematite (15- 19 percent Ti-substitution ) from the 1 Gyr metamorphic rocks of the Modum district, south Norway. Low temperature magnetic measurements demonstrate the nature of the giant exchange bias. Transmission electron microscopy, electron microprobe analyses combined with Mossbauer measurements, at room and low temperature, are used to identify the interacting phases. The titanohematite contain ilmenite lamellae which are mostly sub-unit cell size. Fe-rutile is also present as an intergrowth phase.
Determination of copper in tap water using solid-phase spectrophotometry

NASA Technical Reports Server (NTRS)

Hill, Carol M.; Street, Kenneth W.; Philipp, Warren H.; Tanner, Stephen P.

1994-01-01

A new application of ion exchange films is presented. The films are used in a simple analytical method of directly determining low concentrations of Cu(2+) in aqueous solutions, in particular, drinking water. The basis for this new test method is the color and absorption intensity of the ion when adsorbed onto the film. The film takes on the characteristic color of the adsorbed cation, which is concentrated on the film by many orders of magnitude. The linear relationship between absorbance (corrected for variations in film thickness) and solution concentration makes the determinations possible. These determinations agree well with flame atomic absorption determinations.
Thermodynamic model of a solid with RKKY interaction and magnetoelastic coupling

NASA Astrophysics Data System (ADS)

Balcerzak, T.; Szałowski, K.; Jaščur, M.

2018-04-01

Thermodynamic description of a model system with magnetoelastic coupling is presented. The elastic, vibrational, electronic and magnetic energy contributions are taken into account. The long-range RKKY interaction is considered together with the nearest-neighbour direct exchange. The generalized Gibbs potential and the set of equations of state are derived, from which all thermodynamic functions are self-consistently obtained. Thermodynamic properties are calculated numerically for FCC structure for arbitrary external pressure, magnetic field and temperature, and widely discussed. In particular, for some parameters of interaction potential and electron concentration corresponding to antiferromagnetic phase, the existence of negative thermal expansion coefficient is predicted.
Magnetic exchange bias of more than 1 Tesla in a natural mineral intergrowth.

PubMed

McEnroe, Suzanne A; Carter-Stiglitz, Brian; Harrison, Richard J; Robinson, Peter; Fabian, Karl; McCammon, Catherine

2007-10-01

Magnetic exchange bias is a phenomenon whereby the hysteresis loop of a 'soft' magnetic phase is shifted by an amount H(E) along the applied field axis owing to its interaction with a 'hard' magnetic phase. Since the discovery of exchange bias fifty years ago, the development of a general theory has been hampered by the uncertain nature of the interfaces between the hard and soft phases, commonly between an antiferromagnetic phase and a ferro- or ferrimagnetic phase. Exchange bias continues to be the subject of investigation because of its technological applications and because it is now possible to manipulate magnetic materials at the nanoscale. Here we present the first documented example of exchange bias of significant magnitude (>1 T) in a natural mineral. We demonstrate that exchange bias in this system is due to the interaction between coherently intergrown magnetic phases formed through a natural process of phase separation during slow cooling over millions of years. Transmission electron microscopy studies show that these intergrowths have a known crystallographic orientation with a known crystallographic structure and that the interfaces are coherent.
Condition of copper and organic matter in the soil contaminated with metal remediation of humic substances.

NASA Astrophysics Data System (ADS)

Kolchanova, Kseniia; Barsova, Natalia; Motuzova, Galina; Stepanov, Andrey; Karpukhin, Mikhail

2017-04-01

The aim of this study was to investigate the forms of copper and transformation of organic matter in the soil under the influence of humic substances (potassium humate, which was obtained from coal). The object of research was the top layer of soil model field experience. Field experiments were carried out in 10-liter plastic containers.The upper layers were constructed artificially as mixture of loam, sand and peat. Below it was a layer of loam, then gravel and under it we installed lysimeters. The experiment was conducted in 3 settings: 1) control, 2) control + Cu, and 3) control + Cu + potassium humate . Copper was deposited into upper layer at soil column construction as dry powder (CuSO4*5H2O), which is 1000mg per kg. Humic substance was introduced on surface as liquid form. The focus was the state of the copper and organic matter of solid and liquid phase. In the solid phase pH, carbon content, the molecular-mass distributions for the organic matter, total (HNO3 conc.+ H2O2; decomposition in a microwave oven) and acid-soluble (1H HNO3) copper content, sequential extraction of copper (1 M MgCl2, acetate buffer pH 4,8 (AAB), 1% EDTA) were determined. For liquid phase characteristics aqueous extract was obtained and identified therein: pH, total activity and copper content and water-soluble organic matter(WOM) amphiphilic properties. The introduction of copper is accompanied by a decrease in pH in soils from 7 to 6,3. The introduction of the humic substance softens this effect. Introducing humic preparation gives an increase in carbon at 0.5%. HS and copper has no significant effect on the molecular-mass distribution of solid organic matter. Only about 4% introduced copper accounted for the exchangeable form (MgCl2) for the variant only copper contaminated. Copper, mainly precipitated as hydroxides, moved in an AAB extract. And compared with the exchangeable forms its quantity increases by 10 times. Still more copper goes into an extract of EDTA, about half of the total. That is, the introduction of humic substances increases the amount of copper associated with organic matter in complexes with high stability constants. The total amount of copper of the results of extraction is 88-96% of the all total content. Water-soluble copper contains only 0.5% of the total. But the introduction of humic substances increases the amount of water-soluble copper is 3 times. This is due to the increase in the content of the WOM by 2.5-3 times, both due to the hydrophobic and hydrophilic factions of WOM. And this leads to a sharp reduction in the activity of copper in the liquid phase. Dual effect of introducing humic substances was obtained on the results of the work. On the one hand the introduction of humic substances contributes the immobilization of copper by increasing the fraction associated with organic matter in the solid phase. On the other hand the introduction of humic substances contributes the mobilization of copper in the liquid phase due to the increase of WOM.
MN15-L: A New Local Exchange-Correlation Functional for Kohn-Sham Density Functional Theory with Broad Accuracy for Atoms, Molecules, and Solids.

PubMed

Yu, Haoyu S; He, Xiao; Truhlar, Donald G

2016-03-08

Kohn-Sham density functional theory is widely used for applications of electronic structure theory in chemistry, materials science, and condensed-matter physics, but the accuracy depends on the quality of the exchange-correlation functional. Here, we present a new local exchange-correlation functional called MN15-L that predicts accurate results for a broad range of molecular and solid-state properties including main-group bond energies, transition metal bond energies, reaction barrier heights, noncovalent interactions, atomic excitation energies, ionization potentials, electron affinities, total atomic energies, hydrocarbon thermochemistry, and lattice constants of solids. The MN15-L functional has the same mathematical form as a previous meta-nonseparable gradient approximation exchange-correlation functional, MN12-L, but it is improved because we optimized it against a larger database, designated 2015A, and included smoothness restraints; the optimization has a much better representation of transition metals. The mean unsigned error on 422 chemical energies is 2.32 kcal/mol, which is the best among all tested functionals, with or without nonlocal exchange. The MN15-L functional also provides good results for test sets that are outside the training set. A key issue is that the functional is local (no nonlocal exchange or nonlocal correlation), which makes it relatively economical for treating large and complex systems and solids. Another key advantage is that medium-range correlation energy is built in so that one does not need to add damped dispersion by molecular mechanics in order to predict accurate noncovalent binding energies. We believe that the MN15-L functional should be useful for a wide variety of applications in chemistry, physics, materials science, and molecular biology.
High-performance liquid chromatography - Ultraviolet method for the determination of total specific migration of nine ultraviolet absorbers in food simulants based on 1,1,3,3-Tetramethylguanidine and organic phase anion exchange solid phase extraction to remove glyceride.

PubMed

Wang, Jianling; Xiao, Xiaofeng; Chen, Tong; Liu, Tingfei; Tao, Huaming; He, Jun

2016-06-17

The glyceride in oil food simulant usually causes serious interferences to target analytes and leads to failure of the normal function of the RP-HPLC column. In this work, a convenient HPLC-UV method for the determination of the total specific migration of nine ultraviolet (UV) absorbers in food simulants was developed based on 1,1,3,3-tetramethylguanidine (TMG) and organic phase anion exchange (OPAE) SPE to efficiently remove glyceride in olive oil simulant. In contrast to the normal ion exchange carried out in an aqueous solution or aqueous phase environment, the OPAE SPE was performed in the organic phase environments, and the time-consuming and challenging extraction of the nine UV absorbers from vegetable oil with aqueous solution could be readily omitted. The method was proved to have good linearity (r≥0.99992), precision (intra-day RSD≤3.3%), and accuracy(91.0%≤recoveries≤107%); furthermore, the lower limit of quantifications (0.05-0.2mg/kg) in five types of food simulants(10% ethanol, 3% acetic acid, 20% ethanol, 50% ethanol and olive oil) was observed. The method was found to be well suited for quantitative determination of the total specific migration of the nine UV absorbers both in aqueous and vegetable oil simulant according to Commission Regulation (EU) No. 10/2011. Migration levels of the nine UV absorbers were determined in 31 plastic samples, and UV-24, UV-531, HHBP and UV-326 were frequently detected, especially in olive oil simulant for UV-326 in PE samples. In addition, the OPAE SPE procedure was also been applied to efficiently enrich or purify seven antioxidants in olive oil simulant. Results indicate that this procedure will have more extensive applications in the enriching or purification of the extremely weak acidic compounds with phenol hydroxyl group that are relatively stable in TMG n-hexane solution and that can be barely extracted from vegetable oil. Copyright © 2016 Elsevier B.V. All rights reserved.
Matrix solid-phase dispersion followed by gas chromatography tandem mass spectrometry for the determination of benzotriazole UV absorbers in sediments.

PubMed

Carpinteiro, I; Abuín, B; Ramil, M; Rodríguez, I; Cela, R

2012-01-01

A cost-effective and low solvent consumption method, based on the matrix solid-phase dispersion (MSPD) technique, for the determination of six benzotriazole UV absorbers in sediments is presented. Sieved samples (0.5 g) were first mixed in a mortar with a solid sorbent and then transferred to a polypropylene syringe containing a layer of clean-up co-sorbent. Analytes were eluted with a suitable solvent and further determined by gas chromatography with tandem mass spectrometry (GC-MS/MS). Under final conditions, diatomaceous earth and silica, deactivated to 10%, were used as inert dispersant and clean-up co-sorbent, respectively. Analytes were recovered using just 5 mL of dichloromethane, and this extract was concentrated and exchanged to 1 mL of isooctane. Further removal of co-extracted sulphur was achieved adding activated copper powder to final extracts, which were stored overnight, before injection in the GC-MS/MS system. The accuracy of the method was assessed with river and marine sediment samples showing different carbon contents and spiked at different concentrations in the range from 40 to 500 ng g(-1). Recoveries varied between 78% and 110% with associated standard deviations below 14%. The limits of quantification of the method stayed between 3 and 15 ng g(-1). Levels of target compounds in sediment samples ranged from not detected up to a maximum of 56 ng g(-1) for Tinuvin 328.
Strontium isotope fractionation during strontianite (SrCO3) dissolution, precipitation and at equilibrium

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; Harrison, Anna L.; Eisenhauer, Anton; Dietzel, Martin

2017-12-01

In this study we examine the behavior of stable Sr isotopes between strontianite [SrCO3] and reactive fluid during mineral dissolution, precipitation, and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 0.01 M NaCl solutions wherein the pH was adjusted by bubbling of a water saturated gas phase of pure CO2 or atmospheric air. The equilibrium Sr isotope fractionation between strontianite and fluid after dissolution of the solid under 1 atm CO2 atmosphere was estimated as Δ88/86SrSrCO3-fluid = δ88/86Sr SrCO3 - δ88/86Srfluid = -0.05 ± 0.01‰. On the other hand, during strontianite precipitation, an enrichment of the fluid phase in 88Sr, the heavy isotopomer, was observed. The evolution of the δ88/86Srfluid during strontianite precipitation can be modeled using a Rayleigh distillation approach and the estimated, kinetically driven, fractionation factor αSrCO3-fluid between solid and fluid is calculated to be 0.99985 ± 0.00003 corresponding to Δ88/86SrSrCO3-fluid = -0.15‰. The obtained results further support that under chemical equilibrium conditions between solid and fluid a continuous exchange of isotopes occurs until the system approaches isotopic equilibrium. This isotopic exchange is not limited to the outer surface layer of the strontianite crystal, but extends to ∼7-8 unit cells below the crystal surface. The behavior of Sr isotopes in this study is in excellent agreement with the concept of dynamic equilibrium and it suggests that the time needed for achievement of chemical equilibrium is generally shorter compared to that for isotopic equilibrium. Thus it is suggested that in natural Sr-bearing carbonates an isotopic change may still occur close to thermodynamic equilibrium, despite no observable change in aqueous elemental concentrations. As such, a secondary and ongoing change of Sr isotope signals in carbonate minerals caused by isotopic re-equilibration with fluids has to be considered in order to use Sr isotopes as environmental proxies in aquatic environments.

A spin exchange model for singlet fission

NASA Astrophysics Data System (ADS)

Yago, Tomoaki; Wakasa, Masanobu

2018-03-01

Singlet fission has been analyzed with the Dexter model in which electron exchange occurs between chromophores, conserving the spin for each electron. In the present study, we propose a spin exchange model for singlet fission. In the spin exchange model, spins are exchanged by the exchange interaction between two electrons. Our analysis with simple spin functions demonstrates that singlet fission is possible by spin exchange. A necessary condition for spin exchange is a variation in exchange interactions. We also adapt the spin exchange model to triplet fusion and triplet energy transfer, which often occur after singlet fission in organic solids.
Bi2MoxW1-xO6 solid solutions with tunable band structure and enhanced visible-light photocatalytic activities

NASA Astrophysics Data System (ADS)

Li, Wenqi; Ding, Xingeng; Wu, Huating; Yang, Hui

2018-07-01

Semiconductor photocatalysis is an effective green way to combat water pollution. For the first time, this study reports a novel method to develop Bi2MoxW1-xO6 solid solution with microsphere structure through anion-exchange method. All Bi2MoxW1-xO6 samples exhibit an Aurivillius-type crystal structure without any secondary phase, confirming that in complete solid solutions as the value of x increases, the band gap energy of Bi2MoxW1-xO6 solid solutions decreases, while the optical absorption edge moves to longer wavelength. The Raman spectra research shows an increase in orthorhombic distortion with progressive replacement of W sites in Bi2WO6 with Mo6+ ions. Compared to Bi2MoO6 and Bi2WO6 samples, Bi2Mo0.4W0.6O6 sample displayed best photocatalytic activity and cycling stability for degradation of RhB dye. The enhanced photocatalytic activity of Bi2Mo0.4W0.6O6 sample can be synergetically linked to hierarchical hollow structure, enhanced light absorbance, and high carrier-separation efficiency. Additionally, the hollow Bi2MoxW1-xO6 microspheres formation can be attributed to the Kirkendall effect.
Micellar catalyzed degradation of fenitrothion, an organophosphorus pesticide, in solution and soils.

PubMed

Balakrishnan, Vimal K; Buncel, Erwin; Vanloon, Gary W

2005-08-01

We report on a study of the decomposition of fenitrothion (an organophosphorus pesticide that is a persistent contaminant in soils and groundwater) as catalyzed by cetyltrimethylammonium (CTA+) micelles. The CTA micelles were associated with two types of counterions: (1) inert counterions (e.g. CTABr) and (2) reactive counterions (e.g. CTAOH). The reactive counterion surfactants used were hydroxide anion (HO-) as a normal nucleophile and hydroperoxide anion (HOO-) and the anion of pyruvaldehyde oxime (MINA-) as two alpha-nucleophiles. The reactivity order followed: CTABr < CTAOH < CTAMINA < CTAOOH. Treatment of the rate data using the Pseudo-Phase Ion Exchange (PPIE) model of micellar catalysis showed the ratio k2M/k2w to be less than unity for all the surfactants employed. Rather than arising from a "true catalysis", we attributed the observed rate enhancements to a "concentration effect", where both pesticide and nucleophile were incorporated into the small micellar phase volume. Furthermore, the CTAOOH/CTAOH pair gave an alpha-effect of 57, showing that the alpha-effect can play an important role in micellar systems. We further investigated the effectiveness of reactive counterion surfactants in decontaminating selected environmental solids that were spiked with 27 ppb fenitrothion. The solids were as follows: the clay mineral montmorillonite and SO-1 and S0-2 soils (obtained from the Canadian Certified Reference Materials Project). The reactive counterion surfactant solutions significantly enhanced the rate of fenitrothion degradation in the spiked solids over that obtained when the spiked solid was placed in contact with either 0.02 M KOH or water. The rate enhancements followed the order CTAOOH > CTAMINA approximately CTAOH > KOH > water. We conclude that reactive counterion surfactants, especially with alpha-nucleophiles, hold great potential in terms of remediating soils contaminated by toxic organophosphorus esters.
High-quality multilayer graphene on an insulator formed by diffusion controlled Ni-induced layer exchange

NASA Astrophysics Data System (ADS)

Murata, H.; Saitoh, N.; Yoshizawa, N.; Suemasu, T.; Toko, K.

2017-12-01

The Ni-induced layer-exchange growth of amorphous carbon is a unique method used to fabricate uniform multilayer graphene (MLG) directly on an insulator. To improve the crystal quality of MLG, we prepare AlOx or SiO2 interlayers between amorphous C and Ni layers, which control the extent of diffusion of C atoms into the Ni layer. The growth morphology and Raman spectra observed from MLG formed by layer exchange strongly depend on the material type and thickness of the interlayers; a 1-nm-thick AlOx interlayer is found to be ideal for use in experiments. Transmission electron microscopy and electron energy-loss spectra reveal that the crystal quality of the resulting MLG is much higher than that of a sample without an interlayer. The grain size reaches a few μm, leading to an electrical conductivity of 1290 S/cm. The grain size and the electrical conductivity are the highest among MLG synthesized using a solid-phase reaction including metal-induced crystallization. The direct synthesis of uniform, high-quality MLG on arbitrary substrates will pave the way for advanced electronic devices integrated with carbon materials.
Extraction and derivatization of chemical weapons convention relevant aminoalcohols on magnetic cation-exchange resins.

PubMed

Singh, Varoon; Garg, Prabhat; Chinthakindi, Sridhar; Tak, Vijay; Dubey, Devendra Kumar

2014-02-14

Analysis and identification of nitrogen containing aminoalcohols is an integral part of the verification analysis of chemical weapons convention (CWC). This study was aimed to develop extraction and derivatization of aminoalcohols of CWC relevance by using magnetic dispersive solid-phase extraction (MDSPE) in combination with on-resin derivatization (ORD). For this purpose, sulfonated magnetic cation-exchange resins (SMRs) were prepared using magnetite nanoparticles as core, styrene and divinylbenzene as polymer coat and sulfonic acid as acidic cation exchanger. SMRs were successfully employed as extractant for targeted basic analytes. Adsorbed analytes were derivatized with hexamethyldisilazane (HMDS) on the surface of extractant. Derivatized (silylated) compounds were analyzed by GC-MS in SIM and full scan mode. The linearity of the method ranged from 5 to 200ngmL(-1). The LOD and LOQ ranged from 2 to 6ngmL(-1) and 5 to 19ngmL(-1) respectively. The relative standard deviation for intra-day repeatability and inter-day intermediate precision ranged from 5.1% to 6.6% and 0.2% to 7.6% respectively. Recoveries of analytes from spiked water samples from different sources varied from 28.4% to 89.3%. Copyright © 2014 Elsevier B.V. All rights reserved.
Extraction of acidic degradation products of organophosphorus chemical warfare agents. Comparison between silica and mixed-mode strong anion-exchange cartridges.

PubMed

Kanaujia, Pankaj K; Pardasani, Deepak; Gupta, A K; Kumar, Rajesh; Srivastava, R K; Dubey, D K

2007-08-17

The analysis of alkyl alkylphosphonic acids (AAPAs) and alkylphosphonic acids (APAs), the hydrolyzed products of nerve agents, constitutes an important aspect for verifying the compliance to the Chemical weapons convention (CWC). This work devotes on the development of solid-phase extraction method using polymeric mixed-mode strong anion-exchange (Oasis MAX) cartridges for extraction of AAPAs and APAs from water. The extracted analytes were analyzed by GC-MS under full scan and selected ion monitoring mode. The extraction efficiencies of MAX and silica-based anion-exchange cartridges were compared, and results revealed that MAX sorbents yielded better recoveries. Extraction parameters, such as loading capacity, extraction solvent, its volume, and washing solvent were optimized. Best recoveries were obtained using 1 mL of acidic methanol (0.1 M), and limits of detection could be achieved up to 5 x 10(-4) microg mL(-1) (in SIM) and 0.05 microg mL(-1) in full scan mode. The method was successfully employed for the detection and identification of alkylphosphonic acids present in soil sample sent by the Organization for Prohibition of Chemical Weapons (OPCW) in the official proficiency tests.
Improved ceramic heat exchange material

NASA Technical Reports Server (NTRS)

Mccollister, H. L.

1977-01-01

Improved corrosion resistant ceramic materials that are suitable for use as regenerative heat exchangers for vehicular gas turbines is reported. Two glass-ceramic materials, C-144 and C-145, have superior durability towards sulfuric acid and sodium sulfate compared to lithium aluminosilicate (LAS) Corning heat exchange material 9455. Material C-144 is a leached LAS material whose major crystalline phase is silica keatite plus mullite, and C-145 is a LAS keatite solid solution (S.S.) material. In comparison to material 9455, material C-144 is two orders of magnitude better in dimensional stability to sulfuric acid at 300 C, and one order of magnitude better in stability to sodium sulfate at 1000 C. Material C-145 is initially two times better in stability to sulfuric acid, and about one order of magnitude better in stability to sodium sulfate. Both C-144 and C-145 have less than 300 ppm delta L/L thermal expansion from ambient to 1000 C, and good dimensional stability of less than approximately 100 ppm delta L/L after exposure to 1000 C for 100 hours. The glass-ceramic fabrication process produced a hexagonal honeycomb matrix having an 85% open frontal area, 50 micrometer wall thickness, and less than 5% porosity.
40 CFR 227.32 - Liquid, suspended particulate, and solid phases of a material.

Code of Federal Regulations, 2010 CFR

2010-07-01

... solid phases of a material. 227.32 Section 227.32 Protection of Environment ENVIRONMENTAL PROTECTION... MATERIALS Definitions § 227.32 Liquid, suspended particulate, and solid phases of a material. (a) For the... obtained above prior to centrifugation and filtration. The solid phase includes all material settling to...
40 CFR 227.32 - Liquid, suspended particulate, and solid phases of a material.

Code of Federal Regulations, 2011 CFR

2011-07-01

... solid phases of a material. 227.32 Section 227.32 Protection of Environment ENVIRONMENTAL PROTECTION... MATERIALS Definitions § 227.32 Liquid, suspended particulate, and solid phases of a material. (a) For the... obtained above prior to centrifugation and filtration. The solid phase includes all material settling to...
Equilibrium lithium-ion transport between nanocrystalline lithium-inserted anatase TiO2 and the electrolyte.

PubMed

Ganapathy, Swapna; van Eck, Ernst R H; Kentgens, Arno P M; Mulder, Fokko M; Wagemaker, Marnix

2011-12-23

The power density of lithium-ion batteries requires the fast transfer of ions between the electrode and electrolyte. The achievable power density is directly related to the spontaneous equilibrium exchange of charged lithium ions across the electrolyte/electrode interface. Direct and unique characterization of this charge-transfer process is very difficult if not impossible, and consequently little is known about the solid/liquid ion transfer in lithium-ion-battery materials. Herein we report the direct observation by solid-state NMR spectroscopy of continuous lithium-ion exchange between the promising nanosized anatase TiO(2) electrode material and the electrolyte. Our results reveal that the energy barrier to charge transfer across the electrode/electrolyte interface is equal to or greater than the barrier to lithium-ion diffusion through the solid anatase matrix. The composition of the electrolyte and in turn the solid/electrolyte interface (SEI) has a significant effect on the electrolyte/electrode lithium-ion exchange; this suggests potential improvements in the power of batteries by optimizing the electrolyte composition. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Phase Space Exchange in Thick Wedge Absorbers

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

Neuffer, David

The problem of phase space exchange in wedge absorbers with ionization cooling is discussed. The wedge absorber exchanges transverse and longitudinal phase space by introducing a position-dependent energy loss. In this paper we note that the wedges used with ionization cooling are relatively thick, so that single wedges cause relatively large changes in beam phase space. Calculation methods adapted to such “thick wedge” cases are presented, and beam phase-space transformations through such wedges are discussed.
Biological treatment of soils contaminated with hydrophobic organics using slurry- and solid-phase techniques

NASA Astrophysics Data System (ADS)

Cassidy, Daniel H.; Irvine, Robert L.

1995-10-01

Both slurry-phase and solid-phase bioremediation are effective ex situ soil decontamination methods. Slurrying is energy intensive relative to solid-phase treatment, but provides homogenization and uniform nutrient distribution. Limited contaminant bioavailability at concentrations above the required cleanup level reduces biodegradation rates and renders solid phase bioremediation more cost effective than complete treatment in a bio-slurry reactor. Slurrying followed by solid-phase bioremediation combines the advantages and minimizes the weaknesses of each treatment method when used alone. A biological treatment system consisting of slurrying followed by aeration in solid phase bioreactors was developed and tested in the laboratory using a silty clay loam contaminated with diesel fuel. The first set of experiments was designed to determine the impact of the water content and mixing time during slurrying on the rate an extent of contaminant removal in continuously aerated solid phase bioreactors. The second set of experiments compared the volatile and total diesel fuel removal in solid phase bioreactors using periodic and continuous aeration strategies. Results showed that slurrying for 1.5 hours at a water content less than saturation markedly increased the rate and extent of contaminant biodegradation in the solid phase bioreactors compared with soil having no slurry pretreatment. Slurrying the soil at or above its saturation moisture content resulted in lengthy dewatering times which prohibited aeration, thereby delaying the onset of biological treatment in the solid phase bioreactors. Results also showed that properly operated periodic aeration can provide less volatile contaminant removal and a grater fraction of biological contaminant removal than continuous aeration.
[Effects of Low-Molecular-Weight Organic Acids on the Speciation of Pb in Purple Soil and Soil Solution].

PubMed

Liu, Jiang; Jiang, Tao; Huang, Rong; Zhang, Jin-zhong; Chen, Hong

2016-04-15

Lead (Pb) in purple soil was selected as the research target, using one-step extraction method with 0.01 mol · L⁻¹ sodium nitrate as the background electrolyte to study the release effect of citric acid (CA), tartaric acid (TA) and acetic acid (AC) with different concentrations. Sequential extraction and geochemical model (Visual Minteq v3.0) were applied to analyze and predict the speciation of Pb in soil solid phase and soil solution phase. Then the ebvironmental implications and risks of low-molecule weight organic acid (LMWOA) on soil Pb were analyzed. The results indicated that all three types of LMWOA increased the desorption capacity of Pb in purple soil, and the effect followed the descending order of CA > TA > AC. After the action of LMWOAs, the exchangeable Pb increased; the carbonate-bound Pb and Fe-Mn oxide bound Pb dropped in soil solid phase. Organic bound Pb was the main speciation in soil solution phase, accounting for 45.16%-75.05%. The following speciation of Pb in soil solution was free Pb, accounting for 22.71%-50.25%. For CA and TA treatments, free Pb ions and inorganic bound Pb in soil solution increased with increasing LMWOAs concentration, while organic bound Pb suffered a decrease in this process. An opposite trend for AC treatment was observed compared with CA and TA treatments. Overall, LMWOAs boosted the bioavailability of Pb in purple soil and had a potential risk to contaminate underground water. Among the three LMWOAs in this study, CA had the largest potential to activate soil Pb.
Insights on geochemical cycling of U, Re and Mo from seasonal sampling in Boston Harbor, Massachusetts, USA

USGS Publications Warehouse

Morford, J.L.; Martin, W. R.; Kalnejais, Linda H.; Francois, R.; Bothner, Michael H.; Karle, I.-M.

2007-01-01

This study examined the removal of U, Mo, and Re from seawater by sedimentary processes at a shallow-water site with near-saturation bottom water O2 levels (240–380 μmol O2/L), very high organic matter oxidation rates (annually averaged rate is 880 μmol C/cm2/y), and shallow oxygen penetration depths (4 mm or less throughout the year). Under these conditions, U, Mo, and Re were removed rapidly to asymptotic pore water concentrations of 2.2–3.3 nmol/kg (U), 7–13 nmol/kg (Mo), and 11–14 pmol/kg (Re). The depth order in which the three metals were removed, determined by fitting a diffusion-reaction model to measured profiles, was Re < U < Mo. Model fits also suggest that the Mo profiles clearly showed the presence of a near-interface layer in which Mo was added to pore waters by remineralization of a solid phase. The importance of this solid phase source of pore water Mo increased from January to October as the organic matter oxidation rate increased, bottom water O2 decreased, and the O2 penetration depth decreased. Experiments with in situ benthic flux chambers generally showed fluxes of U and Mo into the sediments. However, when the overlying water O2 concentration in the chambers was allowed to drop to very low levels, Mn and Fe were released to the overlying water along with the simultaneous release of Mo and U. These experiments suggest that remineralization of Mn and/or Fe oxides may be a source of Mo and perhaps U to pore waters, and may complicate the accumulation of U and Mo in bioturbated sediments with high organic matter oxidation rates and shallow O2 penetration depths.Benthic chamber experiments including the nonreactive solute tracer, Br−, indicated that sediment irrigation was very important to solute exchange at the study site. The enhancement of sediment–seawater exchange due to irrigation was determined for the nonreactive tracer (Br−), TCO2, NH4+">NH4+, U and Mo. The comparisons between these solutes showed that reactions within and around the burrows were very important for modulating the Mo flux, but less important for U. The effect of these reactions on Mo exchange was highly variable, enhancing Mo (and, to a lesser extent, U) uptake at times of relatively modest irrigation, but inhibiting exchange when irrigation rates were faster. These results reinforce the observation that Mo can be released to and removed from pore waters via sedimentary reactions.The removal rate of U and Mo from seawater by sedimentary reactions was found to agree with the rate of accumulation of authigenic U and Mo in the solid phase. The fluxes of U and Mo determined by in situ benthic flux chamber measurements were the largest that have been measured to date. These results confirm that removal of redox-sensitive metals from continental margin sediments underlying oxic bottom water is important, and suggest that continental margin sediments play a key role in the marine budgets of these metals.
78 FR 34687 - Self-Regulatory Organizations; NYSE MKT LLC; Notice of Filing and Immediate Effectiveness of...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-06-10

... To Amend Rule 1000-- Equities To Revise the Manner by Which the Exchange Will Phase Out the... Exchange will phase out the functionality associated with liquidity replenishment points (``LRPs'') in... Exchange filed to amend Rule 1000--Equities to provide that it would phase out the functionality associated...
Liquid uranium alloy-helium fission reactor

DOEpatents

Minkov, V.

1984-06-13

This invention describes a nuclear fission reactor which has a core vessel and at least one tandem heat exchanger vessel coupled therewith across upper and lower passages to define a closed flow loop. Nuclear fuel such as a uranium alloy in its liquid phase fills these vessels and flow passages. Solid control elements in the reactor core vessel are adapted to be adjusted relative to one another to control fission reaction of the liquid fuel therein. Moderator elements in the other vessel and flow passages preclude fission reaction therein. An inert gas such as helium is bubbled upwardly through the heat exchanger vessel operable to move the liquid fuel upwardly therein and unidirectionally around the closed loop and downwardly through the core vessel. This helium gas is further directed to heat conversion means outside of the reactor vessels to utilize the heat from the fission reaction to generate useful output. The nuclear fuel operates in the 1200 to 1800/sup 0/C range, and even higher to 2500/sup 0/C.
Fate of 90Sr and U(VI) in Dounreay sediments following saline inundation and erosion.

PubMed

Eagling, Jane; Worsfold, Paul J; Blake, William H; Keith-Roach, Miranda J

2013-08-01

There is concern that sea level rise associated with projected climate change will lead to the inundation, flooding and erosion of soils and sediments contaminated with radionuclides at coastal nuclear sites, such as Dounreay (UK), with seawater. Here batch and column experiments were designed to simulate these scenarios and sequential extractions were used to identify the key radionuclide solid phase associations. Strontium was exchangeable and was mobilised rapidly by ion exchange with seawater Mg(2+) in both batch and column experiments. In contrast, U was more strongly bound to the sediments and mobilisation was initially limited by the influence of the sediment on the pH of the water. Release was only observed when the pH increased above 6.9, suggesting that the formation of soluble U(VI)-carbonate species was important. Under dynamic flow conditions, long term release was significant (47%), but controlled by slow desorption kinetics from a range of binding sites. Copyright © 2013 Elsevier Ltd. All rights reserved.
Multilayer graphene on insulator formed by Co-induced layer exchange

NASA Astrophysics Data System (ADS)

Murata, Hiromasa; Toko, Kaoru; Suemasu, Takashi

2017-05-01

The direct synthesis of multilayer graphene (MLG) on arbitrary substrates is essential for incorporating carbon wirings and heat spreaders into electronic devices. Here, we applied the metal-induced layer exchange (MILE) technique, developed for group-IV semiconductors, to a sputtered amorphous carbon (a-C) thin film using Co as a catalyst. MLG was formed on a SiO2 substrate at 800 °C for 10 min; however, it disappeared during wet etching for removing Co. This behavior was attributed to the small contact area between MLG and SiO2 caused by the deformation of the Co layer during annealing. By preparing the Co layer at 200 °C, its thermal stability was improved, resulting in the synthesis of MLG on the substrate through MILE. Raman measurements indicated good crystal quality of the MLG compared with that obtained by conventional metal-induced solid-phase crystallization. MILE was thus proven to be useful not only for group-IV semiconductors but also for carbon materials on insulators.
Sorption characteristics of organic compounds on hexadecyltrimethylammonium-smectite

USGS Publications Warehouse

Boyd, Stephen A.; Mortland, Max M.; Chiou, Cary T.

1988-01-01

When hexadedyltrimethylammonium (HDTMA) ion is exchanged for metal cations like calcium in smectite, the sorptive properties of the clay are greatly modified. The resultant HDTMA-smectite complex behaves as a dual sorbent, in the sorption of organic compounds, in which the mineral fraction functions as a solid adsorbent and the organic (HDTMA) phase as a partition medium. Capacities of mineral adsorption and partition uptake by HDTMA in the HDTMA-smectites are illustrated by sorption of benzene, trichloroethene (TCE), and water as vapors on the dry sample and by sorption of benzene and TCE from water. The exchanged HDTMA in clay is found to be a much more powerful partition medium than ordinary soil organic matter in the uptake of benzene and TCE. Based on this finding, HDTMA-smectite appears to be an effective sorbent for removing organic contaminants from water. It is suggested that such sorptive organo-clay complexes could be used to enhance the containment capabilities of clay landfill liners and bentonite slurry walls.
Selective retention of basic compounds by metal aquo-ion affinity chromatography.

PubMed

Asakawa, Yoshiki; Yamamoto, Eiichi; Asakawa, Naoki

2014-10-01

A novel metal aquo-ion affinity chromatography has been developed for the analysis of basic compounds using heat-treated silica gel containing hydrated metal cations (metal aquo-ions) as the packing material. The packing materials of the metal aquo-ion affinity chromatography were prepared by the immobilization of a single metal component such as Fe(III), Al(III), Ag(I), and Ni(II) on silica gel followed by extensive heat treatment. The immobilized metals form aquo-ions to present cation-exchange ability for basic analytes and the cation-exchange ability for basic analytes depends on pKa of the immobilized metal species. In the present study, to evaluate the retention characteristics of metal aquo-ion affinity chromatography, the on-line solid-phase extraction of drugs was investigated. Obtained data clearly evidence the selective retention capability of metal aquo-ion affinity chromatography for basic analytes with sufficient capacity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of dual solid cryogens for high reliability refrigeration system

NASA Technical Reports Server (NTRS)

Caren, R. P.; Coston, R. M.

1967-01-01

High reliability solid cryogen refrigeration system consists of a container initially filled with a solid cryogen which is coupled thermally to an infrared detector by means of a link of high thermal conductivity extending from a heat exchanger within the cryogen container.
Accessing the bottleneck in all-solid state batteries, lithium-ion transport over the solid-electrolyte-electrode interface.

PubMed

Yu, Chuang; Ganapathy, Swapna; Eck, Ernst R H van; Wang, Heng; Basak, Shibabrata; Li, Zhaolong; Wagemaker, Marnix

2017-10-20

Solid-state batteries potentially offer increased lithium-ion battery energy density and safety as required for large-scale production of electrical vehicles. One of the key challenges toward high-performance solid-state batteries is the large impedance posed by the electrode-electrolyte interface. However, direct assessment of the lithium-ion transport across realistic electrode-electrolyte interfaces is tedious. Here we report two-dimensional lithium-ion exchange NMR accessing the spontaneous lithium-ion transport, providing insight on the influence of electrode preparation and battery cycling on the lithium-ion transport over the interface between an argyrodite solid-electrolyte and a sulfide electrode. Interfacial conductivity is shown to depend strongly on the preparation method and demonstrated to drop dramatically after a few electrochemical (dis)charge cycles due to both losses in interfacial contact and increased diffusional barriers. The reported exchange NMR facilitates non-invasive and selective measurement of lithium-ion interfacial transport, providing insight that can guide the electrolyte-electrode interface design for future all-solid-state batteries.
Versatile gas-phase reactions for surface to bulk esterification of cellulose microfibrils aerogels.

PubMed

Fumagalli, Matthieu; Ouhab, Djamila; Boisseau, Sonia Molina; Heux, Laurent

2013-09-09

Aqueous suspensions of microfibrillated cellulose obtained by a high pressure homogenization process were freeze-dried after solvent exchange into tert-butanol. The resulting aerogels, which displayed a remarkable open morphology with a surface area reaching 100 m(2)/g, were subjected to a gas-phase esterification with palmitoyl chloride. Under these conditions, variations of the reaction temperature from 100 to 200 °C, of the reaction time from 0.5 to 2 h, and of the initial quantity of reagent, led to the preparation of a library of cellulose palmitates with DS varying from zero to 2.36. These products were characterized by gravimetry, FTIR, and (13)C solid-state NMR spectroscopy. Of special interest were the cellulose palmitate samples of low DS in the range of 0.1-0.4, which corresponded to hydrophobic cellulose microfibrils exclusively esterified at their surface while keeping intact their inner structure.
Ab Initio Investigations of High-Pressure Melting of Dense Lithium

NASA Astrophysics Data System (ADS)

Clay, Raymond; Morales, Miguel; Bonev, Stanimir

Lithium at ambient conditions is the simplest alkali metal and exhibits textbook nearly-free electron behavior. As the density is increased, however, significant core/valence overlap leads to surprisingly complex chemistry. We have systematically investigated the phase diagram of lithium at pressures ranging between two and six million atmospheres. Through a combination of density functional theory based path-integral and classical molecular dynamics simulations, we have investigated the impact of both nuclear quantum effects and anharmonicity on the melting line and solid phase boundaries. We also investigate how the inclusion of nuclear quantum effects and approximations in the treatment of electronic exchange-correlation impact the robustness of previous predictions of tetrahedral clustering in dense liquid Li. Sandia National Laboratories is a multi-mission laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.
Determination of chlorinated acid herbicides in vegetation and soil by liquid chromatography/electrospray-tandem mass spectrometry.

PubMed

Schaner, Angela; Konecny, Jaclyn; Luckey, Laura; Hickes, Heidi

2007-01-01

The method presented uses reversed-phase liquid chromatography with negative electrospray ionization and tandem mass spectrometry to analyze 9 chlorinated acid herbicides in soil and vegetation matrixes: clopyralid, dicamba, MCPP, MCPA, 2,4-DP, 2,4-D, triclopyr, 2,4-DB, and picloram. A 20 g portion is extracted with a basic solution and an aliquot acidified and micropartitioned with 3 mL chloroform. Vegetation samples are subjected to an additional cleanup with a mixed-mode anion exchange solid-phase extraction cartridge. Two precursor product ion transitions per analyte are measured and evaluated to provide the maximum degree of confidence in results. Average recoveries for 3 different soil types tested ranged from 72 to 107% for all compounds with the exception of 2,4-DB at 56-99%. Average recoveries for the 3 different vegetation types studied were lower and ranged from 53 to 80% for all compounds.
Two-phase/two-phase heat exchanger analysis

NASA Technical Reports Server (NTRS)

Kim, Rhyn H.

1992-01-01

A capillary pumped loop (CPL) system with a condenser linked to a double two-phase heat exchanger is analyzed numerically to simulate the performance of the system from different starting conditions to a steady state condition based on a simplified model. Results of the investigation are compared with those of similar apparatus available in the Space Station applications of the CPL system with a double two-phase heat exchanger.
Polar Aprotic Modifiers for Chromatographic Separation and Back-Exchange Reduction for Protein Hydrogen/Deuterium Exchange Monitored by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

NASA Astrophysics Data System (ADS)

Valeja, Santosh G.; Emmett, Mark R.; Marshall, Alan G.

2012-04-01

Hydrogen/deuterium exchange monitored by mass spectrometry is an important non-perturbing tool to study protein structure and protein-protein interactions. However, water in the reversed-phase liquid chromatography mobile phase leads to back-exchange of D for H during chromatographic separation of proteolytic peptides following H/D exchange, resulting in incorrect identification of fast-exchanging hydrogens as unexchanged hydrogens. Previously, fast high-performance liquid chromatography (HPLC) and supercritical fluid chromatography have been shown to decrease back-exchange. Here, we show that replacement of up to 40% of the water in the LC mobile phase by the modifiers, dimethylformamide (DMF) and N-methylpyrrolidone (NMP) (i.e., polar organic modifiers that lack rapid exchanging hydrogens), significantly reduces back-exchange. On-line LC micro-ESI FT-ICR MS resolves overlapped proteolytic peptide isotopic distributions, allowing for quantitative determination of the extent of back-exchange. The DMF modified solvent composition also improves chromatographic separation while reducing back-exchange relative to conventional solvent.
A Geochemical Reaction Model for Titration of Contaminated Soil and Groundwater at the Oak Ridge Reservation

NASA Astrophysics Data System (ADS)

Zhang, F.; Parker, J. C.; Gu, B.; Luo, W.; Brooks, S. C.; Spalding, B. P.; Jardine, P. M.; Watson, D. B.

2007-12-01

This study investigates geochemical reactions during titration of contaminated soil and groundwater at the Oak Ridge Reservation in eastern Tennessee. The soils and groundwater exhibits low pH and high concentrations of aluminum, calcium, magnesium, manganese, various trace metals such as nickel and cobalt, and radionuclides such as uranium and technetium. The mobility of many of the contaminant species diminishes with increasing pH. However, base additions to increase pH are strongly buffered by various precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior and associated geochemical effects is thus critical to evaluate remediation performance of pH manipulation strategies. This study was undertaken to develop a practical but generally applicable geochemical model to predict aqueous and solid-phase speciation during soil and groundwater titration. To model titration in the presence of aquifer solids, an approach proposed by Spalding and Spalding (2001) was utilized, which treats aquifer solids as a polyprotic acid. Previous studies have shown that Fe and Al-oxyhydroxides strongly sorb dissolved Ni, U and Tc species. In this study, since the total Fe concentration is much smaller than that of Al, only ion exchange reactions associated with Al hydroxides are considered. An equilibrium reaction model that includes aqueous complexation, precipitation, ion exchange, and soil buffering reactions was developed and implemented in the code HydroGeoChem 5.0 (HGC5). Comparison of model results with experimental titration curves for contaminated groundwater alone and for soil- water systems indicated close agreement. This study is expected to facilitate field-scale modeling of geochemical processes under conditions with highly variable pH to develop practical methods to control contaminant mobility at geochemically complex sites.
Durability and Performance of Polystyrene-b-Poly(vinylbenzyl trimethylammonium) Diblock Copolymer and Equivalent Blend Anion Exchange Membranes

DTIC Science & Technology

2015-01-01

requiring circulation of the electrolyte to filter out the carbonate solids. The superior power density of proton exchange membrane fuel cells ( PEMFC ...without requir- ing a CO2 free oxidant stream, prevented commercial develop- ment of the liquid AFC, allowing PEMFCs to dominate low temperature fuel...cell research and development. PEMFCs employ a solid acidic polymer to transport protons from anode to cathode. PEMs have been researched heavily the
Coupling between crystal structure and magnetism in transition-metal oxides

NASA Astrophysics Data System (ADS)

Barton, Phillip Thomas

Transition-metal oxides exhibit a fascinating array of phenomena ranging from superconductivity to negative thermal expansion to catalysis. This dissertation focuses on magnetism, which is integral to engineering applications such as data storage, electric motors/generators, and transformers. The investigative approach follows structure-property relationships from materials science and draws on intuition from solid-state chemistry. The interplay between crystal structure and magnetic properties is studied experimentally in order to enhance the understanding of magnetostructural coupling mechanisms and provide insight into avenues for tuning behavior. A combination of diffraction and physical property measurements were used to study structural and magnetic phase transitions as a function of chemical composition, temperature, and magnetic field. The systems examined are of importance in Li-ion battery electrochemistry, condensed-matter physics, solid-state chemistry, and p-type transparent conducting oxides. The materials were prepared by solid-state reaction of powder reagents at high temperatures for periods lasting tens of hours. The first project discussed is of a solid solution between NiO, a correlated insulator, and LiNiO2, a layered battery cathode. Despite the deceptive structural and compositional simplicity of this system, a complete understanding of its complex magnetic properties has remained elusive. This study shows that nanoscale domains of chemical order form at intermediate compositions, creating interfaces between antiferromagnetism and ferrimagnetism that give rise to magnetic exchange bias. A simple model of the magnetism is presented along with a comprehensive phase diagram. The second set of investigations focus on the Ge-Co-O system where the spin-orbit coupling of Co(II) plays a significant role. GeCo2O 4 is reported to exhibit unusual magnetic behavior that arises from Ising spin in its spinel crystal structure. Studies by variable-temperature synchrotron X-ray diffraction reveal a magnetostructural transition and capacitance measurements show evidence for magnetodielectric behavior. The above work uncovered a Co10Ge3O16 phase that had a known structure but whose physical properties were largely uncharacterized. This project examined its metamagnetic properties using detailed magnetometry experiments. Upon the application of a magnetic field, this material goes through a first-order phase transition from a noncollinear antiferromagnet to an unknown ferrimagnetic state. Lastly, this thesis explored the chemical dilution of magnetism in some perovskite and delafossite solid solutions. In the perovskite structure, compositions intermediate to the endmembers SrRuO3, a ferromagnetic metal, and LaRhO3, a diamagnetic semiconductor, were investigated. While the magnetism of this system is poised between localized and itinerant behavior, a compositionally-driven metal to insulator transition, revealed by electrical resistivity measurements, did not strongly impact the magnetic properties. Instead, both octahedral tilting and magnetic dilution had strong effects, and comparison of this characterization to Sr1-- x CaxRuO3 reinforces the important role of structural distortions in determining magnetic ground state. The final materials studied were of composition CuAl1-- xCrxO2 (0 < x < 1) in the delafossite structure. The primary interest was the geometric frustration of antiferromagnetism in CuCrO 2 and significant short-range correlations were observed above TN. The analysis found that reducing the number of degenerate states through Al substitution did not enhance magnetic ordering because of the weakening of magnetic exchange.
Use of a novel cation-exchange restricted-access material for automated sample clean-up prior to the determination of basic drugs in plasma by liquid chromatography.

PubMed

Chiap, P; Rbeida, O; Christiaens, B; Hubert, Ph; Lubda, D; Boos, K S; Crommen, J

2002-10-25

A new kind of silica-based restricted-access material (RAM) has been tested in pre-columns for the on-line solid-phase extraction (SPE) of basic drugs from directly injected plasma samples before their quantitative analysis by reversed-phase liquid chromatography (LC), using the column switching technique. The outer surface of the porous RAM particlescontains hydrophilic diol groups while sulphonic acid groups are bound to the internal surface, which gives the sorbent the properties of a strong cation exchanger towards low molecular mass compounds. Macromolecules such as proteins have no access to the internal surface of the pre-column due to their exclusion from the pores and are then flushed directly out. The retention capability of this novel packing material has been tested for some hydrophilic basic drugs, such as atropine, fenoterol, ipratropium, procaine, sotalol and terbutaline, used as model compounds. The influence of the composition of the washing liquid on the retention of the analytes in the pre-column has been investigated. The elution profiles of the different compounds and the plasma matrix as well as the time needed for the transfer of the analytes from the pre-column to the analytical column were determined in order to deduce the most suitable conditions for the clean-up step and develop on-line methods for the LC determination of these compounds in plasma. The cationic exchange sorbent was also compared to another RAM, namely RP-18 ADS (alkyl diol silica) sorbent with respect to retention capability towards basic analytes.
High-Capacity Conductive Nanocellulose Paper Sheets for Electrochemically Controlled Extraction of DNA Oligomers

PubMed Central

Razaq, Aamir; Nyström, Gustav; Strømme, Maria; Mihranyan, Albert; Nyholm, Leif

2011-01-01

Highly porous polypyrrole (PPy)-nanocellulose paper sheets have been evaluated as inexpensive and disposable electrochemically controlled three-dimensional solid phase extraction materials. The composites, which had a total anion exchange capacity of about 1.1 mol kg−1, were used for extraction and subsequent release of negatively charged fluorophore tagged DNA oligomers via galvanostatic oxidation and reduction of a 30–50 nm conformal PPy layer on the cellulose substrate. The ion exchange capacity, which was, at least, two orders of magnitude higher than those previously reached in electrochemically controlled extraction, originated from the high surface area (i.e. 80 m2 g−1) of the porous composites and the thin PPy layer which ensured excellent access to the ion exchange material. This enabled the extractions to be carried out faster and with better control of the PPy charge than with previously employed approaches. Experiments in equimolar mixtures of (dT)6, (dT)20, and (dT)40 DNA oligomers showed that all oligomers could be extracted, and that the smallest oligomer was preferentially released with an efficiency of up to 40% during the reduction of the PPy layer. These results indicate that the present material is very promising for the development of inexpensive and efficient electrochemically controlled ion-exchange membranes for batch-wise extraction of biomolecules. PMID:22195031
Mixed-mode sorption of hydroxylated atrazine degradation products to sell: A mechanism for bound residue

USGS Publications Warehouse

Lerch, R.N.; Thurman, E.M.; Kruger, E.L.

1997-01-01

This study tested the hypothesis that sorption of hydroxylated atrazine degradation products (HADPs: hydroxyatrazine, HA; deethylhydroxyatrazine, DEHA; and deisopropylhydroxyatrazine, DIHA) to soils occurs by mixed-mode binding resulting from two simultaneous mechanisms: (1) cation exchange and (2) hydrophobic interaction. The objective was to use liquid chromatography and soil extraction experiments to show that mixed-mode binding is the mechanism controlling HADP sorption to soils and is also a mechanism for bound residue. Overall, HADP binding to solid-phase extraction (SPE) sorbents occurred in the order: cation exchange >> octadecyl (C18) >> cyanopropyl. Binding to cation exchange SPE and to a high-performance liquid chromatograph octyl (C8) column showed evidence for mixed-mode binding. Comparison of soil extracted by 0.5 M KH2P04, pH 7.5, or 25% aqueous CH3CN showed that, for HA and DIHA, cation exchange was a more important binding mechanism to soils than hydrophobic interaction. Based on differences between several extractants, the extent of HADP mixed-mode binding to soil occurred in the following order: HA > DIHA > DEHA. Mixed-mode extraction recovered 42.8% of bound atrazine residues from aged soil, and 88% of this fraction was identified as HADPs. Thus, a significant portion of bound atrazine residues in soils is sorbed by the mixed-mode binding mechanisms.
Seasonal multiphase equilibria in the atmospheres of Titan and Pluto

NASA Astrophysics Data System (ADS)

Tan, S. P.; Kargel, J. S.

2017-12-01

At the extremely low temperatures in Titan's upper troposphere and on Pluto's surface, the atmospheres as a whole are subject to freeze into solid solutions, not pure ices. The presence of the solid phases introduces conditions with rich phase equilibria upon seasonal changes, even if the temperature undergoes only small changes. For the first time, the profile of atmospheric methane in Titan's troposphere will be reproduced complete with the solid solutions. This means that the freezing point, i.e. the altitude where the first solid phase appears, is determined. The seasonal change will also be evaluated both at the equator and the northern polar region. For Pluto, also for the first time, the seasonal solid-vapor equilibria will be evaluated. The fate of the two solid phases, the methane-rich and carbon-monoxide-rich solid solutions, will be analyzed upon temperature and pressure changes. Such investigations are enabled by the development of a molecular-based thermodynamic model for cryogenic chemical systems, referred to as CRYOCHEM, which includes solid solutions in its phase-equilibria calculations. The atmospheres of Titan and Pluto are modeled as ternary gas mixtures: nitrogen-methane-ethane and nitrogen-methane-carbon monoxide, respectively. Calculations using CRYOCHEM can provide us with compositions not only in two-phase equilibria, but also that in three-phase equilibria. Densities of all phases involved will also be calculated. For Titan, density inversion between liquid and solid phases will be identified and presented. In the inversion, the density of solid phase is less than that in the liquid phase. The method and results of this work will be useful for further investigations and modeling on the atmospheres of Titan, Pluto, and other bodies with similar conditions in the Solar System and beyond.
Materials research for passive solar systems: Solid-state phase-change materials

NASA Astrophysics Data System (ADS)

Benson, D. K.; Webb, J. D.; Burrows, R. W.; McFadden, J. D. O.; Christensen, C.

1985-03-01

A set of solid-state phase-change materials is being evaluated for possible use in passive solar thermal energy storage systems. The most promising materials are organic solid solutions of pentaerythritol (C5H12O4), pentaglycerinve (C5H12O3), and neopentyl glycol (C5H12O2). Solid solution mixtures of these compounds can be tailored so that they exhibit solid-to-solid phase transformations at any desired temperature between 25 C and 188 C, and have latent heats of transformation etween 20 and 70 cal/g. Transformation temperatures, specific heats, and latent heats of transformation have been measured for a number of these materials. Limited cyclic experiments suggest that the solid solutions are stable. These phase-change materials exhibit large amounts of undercooling; however, the addition of certain nucleating agents as particulate dispersions in the solid phase-change material greatly reduces this effect. Computer simulations suggest that the use of an optimized solid-state phase-change material in a Trombe wall could provide better performance than a concrete Trombe wall four times thicker and nine times heavier.
Measurement of Intracellular Ribavirin Mono-, Di- and Triphosphate Using Solid Phase Extraction and LC-MS/MS Quantification

PubMed Central

Jimmerson, Leah C.; Ray, Michelle L.; Bushman, Lane R.; Anderson, Peter L.; Klein, Brandon; Rower, Joseph E.; Zheng, Jia-Hua; Kiser, Jennifer J.

2014-01-01

Ribavirin (RBV) is a nucleoside analog used to treat a variety of DNA and RNA viruses. RBV undergoes intracellular phosphorylation to a mono- (MP), di- (DP), and triphosphate (TP). The phosphorylated forms have been associated with the mechanisms of antiviral effect observed in vitro, but the intracellular pharmacology of the drug has not been well characterized in vivo. A highly sensitive LC-MS/MS method was developed and validated for the determination of intracellular RBV MP, DP, and TP in multiple cell matrix types. For this method, the individual MP, DP, and TP fractions were isolated from lysed intracellular matrix using strong anion exchange solid phase extraction, dephosphorylated to parent RBV, desalted and concentrated and quantified using LC-MS/MS. The method utilized a stable labeled internal standard (RBV-13C5) which facilitated accuracy (% deviation within ±15%) and precision (coefficient of variation of ≤15%). The quantifiable linear range for the assay was 0.50 to 200 pmol/sample. The method was applied to the measurement of RBV MP, DP, and TP in human peripheral blood mononuclear cells (PBMC), red blood cells (RBC), and dried blood spot (DBS) samples obtained from patients taking RBV for the treatment of chronic Hepatitis C virus infection. PMID:25555148
Validated Method for the Quantification of Baclofen in Human Plasma Using Solid-Phase Extraction and Liquid Chromatography-Tandem Mass Spectrometry.

PubMed

Nahar, Limon Khatun; Cordero, Rosa Elena; Nutt, David; Lingford-Hughes, Anne; Turton, Samuel; Durant, Claire; Wilson, Sue; Paterson, Sue

2016-03-01

A highly sensitive and fully validated method was developed for the quantification of baclofen in human plasma. After adjusting the pH of the plasma samples using a phosphate buffer solution (pH 4), baclofen was purified using mixed mode (C8/cation exchange) solid-phase extraction (SPE) cartridges. Endogenous water-soluble compounds and lipids were removed from the cartridges before the samples were eluted and concentrated. The samples were analyzed using triple-quadrupole liquid chromatography-tandem mass spectrometry (LC-MS-MS) with triggered dynamic multiple reaction monitoring mode for simultaneous quantification and confirmation. The assay was linear from 25 to 1,000 ng/mL (r(2) > 0.999; n = 6). Intraday (n = 6) and interday (n = 15) imprecisions (% relative standard deviation) were <5%, and the average recovery was 30%. The limit of detection of the method was 5 ng/mL, and the limit of quantification was 25 ng/mL. Plasma samples from healthy male volunteers (n = 9, median age: 22) given two single oral doses of baclofen (10 and 60 mg) on nonconsecutive days were analyzed to demonstrate method applicability. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.
Coupling solid-phase extraction and enzyme-linked immunosorbent assay for ultratrace determination of herbicides in pristine water

USGS Publications Warehouse

Aga, D.S.; Thurman, E.M.

1993-01-01

Solid-phase extraction (SPE) and enzyme-linked immunosorbent assay (ELISA) were coupled for automated trace analysis of pristine water samples containing 2-chloro-4-ethylamino-6-isopropylamine-s-triazine (atrazine) and 2-chloro-2???,6???-diethyl-N-(methoxymethyl)acetanilide (alachlor). The isolation of the two herbicides on a C18-resin involved the selection of an elution solvent that both removes interfering substances and is compatible with ELISA. Ethyl acetate was selected as the elution solvent followed by a solvent exchange with methanol/water (20/80, % v/v). The SPE-ELISA method has a detection limit of 5.0 ng/L (5 ppt), >90% recovery, and a relative standard deviation of ??10%. The performance of a microtiter plate-based ELISA and a magnetic particle-based ELISA coupled to SPE was also evaluated. Although the sensitivity of the two ELISA methods was comparable, the precision using magnetic particles was improved considerably (??10% versus ??20%) because of the faster reaction kinetics provided by the magnetic particles. Finally, SPE-ELISA and isotope dilution gas chromatography/ mass spectrometry correlated well (correlation coefficient of 0.96) for lake-water samples. The SPE-ELISA method is simple and may have broader applications for the inexpensive automated analysis of other contaminants in water at trace levels.
Acid transformation of bauxite residue: Conversion of its alkaline characteristics.

PubMed

Kong, Xiangfeng; Li, Meng; Xue, Shengguo; Hartley, William; Chen, Chengrong; Wu, Chuan; Li, Xiaofei; Li, Yiwei

2017-02-15

Bauxite residue (BR) is a highly alkaline solid hazardous waste produced from bauxite processing for alumina production. Alkaline transformation appears to reduce the environmental risk of bauxite residue disposal areas (BRDAs) whilst potentially providing opportunities for the sustainable reuse and on-going management of BR. Mineral acids, a novel citric acid and a hybrid combination of acid-gypsum treatments were investigated for their potential to reduce residue pH and total alkalinity and transform the alkaline mineral phase. XRD results revealed that with the exception of andradite, the primary alkaline solid phases of cancrinite, grossular and calcite were transformed into discriminative products based on the transformation used. Supernatants separated from BR and transformed bauxite residue (TBR) displayed distinct changes in soluble Na, Ca and Al, and a reduction in pH and total alkalinity. SEM images suggest that mineral acid transformations promote macro-aggregate formation, and the positive promotion of citric acid, confirming the removal or reduction in soluble and exchangeable Na. NEXAFS analysis of Na K-edge revealed that the chemical speciation of Na in TBRs was consistent with BR. Three acid treatments and gypsum combination had no effect on Na speciation, which affects the distribution of Na revealed by sodium STXM imaging. Copyright © 2016 Elsevier B.V. All rights reserved.
Rapid electron exchange between surface-exposed bacterial cytochromes and Fe(III) minerals

PubMed Central

White, Gaye F.; Shi, Zhi; Shi, Liang; Wang, Zheming; Dohnalkova, Alice C.; Marshall, Matthew J.; Fredrickson, James K.; Zachara, John M.; Butt, Julea N.; Richardson, David J.; Clarke, Thomas A.

2013-01-01

The mineral-respiring bacterium Shewanella oneidensis uses a protein complex, MtrCAB, composed of two decaheme cytochromes, MtrC and MtrA, brought together inside a transmembrane porin, MtrB, to transport electrons across the outer membrane to a variety of mineral-based electron acceptors. A proteoliposome system containing a pool of internalized electron carriers was used to investigate how the topology of the MtrCAB complex relates to its ability to transport electrons across a lipid bilayer to externally located Fe(III) oxides. With MtrA facing the interior and MtrC exposed on the outer surface of the phospholipid bilayer, the established in vivo orientation, electron transfer from the interior electron carrier pool through MtrCAB to solid-phase Fe(III) oxides was demonstrated. The rates were 103 times higher than those reported for reduction of goethite, hematite, and lepidocrocite by S. oneidensis, and the order of the reaction rates was consistent with those observed in S. oneidensis cultures. In contrast, established rates for single turnover reactions between purified MtrC and Fe(III) oxides were 103 times lower. By providing a continuous flow of electrons, the proteoliposome experiments demonstrate that conduction through MtrCAB directly to Fe(III) oxides is sufficient to support in vivo, anaerobic, solid-phase iron respiration. PMID:23538304

A simple and rapid in situ preconcentration method for the determination of phosphate in environmental waters by use of solid-phase extraction, and its applications to brackish lake waters.

PubMed

Okumura, M; Tong, L; Fujinaga, K; Seike, Y

2001-05-01

A simple and rapid in situ preconcentration method for the determination of phosphate in environmental waters has been developed for field analysis. This method is based on solid-phase extraction on a zirconium-loaded Sep-Pack Accell CM cartridge (Zr-SP) and is applicable to studies in which sampling is performed by use of a graduated syringe to prevent contamination and to ensure easy operation at sampling sites. The Zr-SP cartridge was prepared by passing 0.1 mol L(-1) zirconium solution through a Sep-Pak Accell CM cartridge, packed with cation exchange sorbent based on a silica matrix. The adsorption of phosphate and its desorption depend only on the pH of the solution. A water sample containing phosphate was adjusted to pH 2 and passed through the Zr-SP cartridge to collect it. The retained phosphate was quantitatively eluted with 0.5 mol L(-1) sodium hydroxide solution. The phosphate retained in the Zr-SP cartridge was stable for at least one month. The established preconcentration method was successfully applied to brackish lake waters to investigate seasonal changes in the distribution and behavior of phosphate in a brackish lake.
Rapid simultaneous determination of amphetamine, methamphetamine, 3,4-methylenedioxyamphetamine, 3,4-methylenedioxymethamphetamine, and 3,4-methylenedioxyethylamphetamine in urine by solid-phase extraction and GC-MS: a method optimized for high-volume laboratories.

PubMed

Stout, Peter R; Horn, Carl K; Klette, Kevin L

2002-01-01

To facilitate analysis of high sample volumes, an extraction, derivatization and gas chromatographic-mass spectrometric analysis method was developed to simultaneously determine amphetamine (AMP), methamphetamine (MAMP), 3,4-methylenedioxyamphetamine (MDA) 3,4-methylenedioxymethamphetamine (MDMA), and 3,4-methylenedioxyethylamphetamine (MDEA) in urine. This method utilized a positive-pressure manifold cation-exchange polymer-based solid-phase extraction followed by elution directly into automated liquid sampler (ALS) vials. Rapid derivatization was accomplished using heptafluorobutyric anhydride (HFBA). Recoveries averaged 90% or greater for each of the compounds. Limits of detection were 62.5 ng/mL (AMP and MDEA), 15.6 ng/mL (MAMP), and 31.3 ng/mL (MDA and MDMA) using a 2-mL sample volume. The method was linear to 5000 ng/mL for all compounds using MDMA-d5 and MAMP-d14 as internal standards. Over 200 human urine samples previously determined to contain the target analytes were analyzed using the method. Excellent agreement was seen with previous quantitations. The method was challenged with 75 potentially interfering compounds and no interferences were seen. These interfering compounds included ephedrine, pseudoephedrine, phenylpropanolamine, and phenethylamine. The method resulted in dramatic reductions in processing time and waste production.
Novel double-confined polymeric ionic liquids as sorbents for solid-phase microextraction with enhanced stability and durability in high-ionic-strength solution.

PubMed

Feng, Juanjuan; Sun, Min; Xu, Lili; Wang, Shuai; Liu, Xia; Jiang, Shengxiang

2012-12-14

Because of the occurrence of ion exchange between high-ionic-strength solution and anions of polymeric ionic liquids (PILs), PILs based solid-phase microextraction (SPME) fibers were rarely used in direct immersion mode to high-salt-added samples. In this work, a novel double-confined PIL sorbent was prepared by co-polymerization of cation and anion of 1-vinyl-3-octylimidzaolium p-styrenesulfonate (VOIm(+)SS(-)). The poly(VOIm(+)-SS(-)) was chemically bonded onto functionalized stainless steel wire via surface radical chain-transfer reaction. Stability of poly(VOIm(+)-SS(-)) in high-ionic-strength solution was investigated and compared with that of poly(1-vinyl-3-octylimidzaolium benzenesulfonate) (poly(VOIm(+)BS(-))) by elemental analysis of sulfur element, and results turned out that the poly(VOIm(+)-SS(-)) was more stable. Coupled to gas chromatography (GC), the poly(VOIm(+)-SS(-)) fiber was used to extract three sorts of compounds including anilines, phenols and phthalate esters in aqueous solution. The as-established method showed good linearity, low detection limits, and acceptable repeatability. The direct immersion SPME-GC method was applied to determine the model phthalate esters in bottled mineral water. The determination results were satisfactory. Copyright © 2012 Elsevier B.V. All rights reserved.
High temperature thermal energy storage, including a discussion of TES integrated into power plants

NASA Technical Reports Server (NTRS)

Turner, R. H.

1978-01-01

Storage temperatures of 260 C and above are considered. Basic considerations concerning energy thermal storage are discussed, taking into account general aspects of thermal energy storage, thermal energy storage integrated into power plants, thermal storage techniques and technical considerations, and economic considerations. A description of system concepts is provided, giving attention to a survey of proposed concepts, storage in unpressurized fluids, water storage in pressurized containers, the use of an underground lined cavern for water storage, a submerged thin insulated steel shell under the ocean containing pressurized water, gas passage through solid blocks, a rock bed with liquid heat transport fluid, hollow steel ingots, heat storage in concrete or sand, sand in a fluidized bed, sand poured over pipes, a thermal energy storage heat exchanger, pipes or spheres filled with phase change materials (PCM), macroencapsulated PCM with heat pipe concept for transport fluid, solid PCM removed from heat transfer pipes by moving scrapers, and the direct contact between PCM and transport fluid.
Benzocaine polymorphism: pressure-temperature phase diagram involving forms II and III.

PubMed

Gana, Inès; Barrio, Maria; Do, Bernard; Tamarit, Josep-Lluís; Céolin, René; Rietveld, Ivo B

2013-11-18

Understanding the phase behavior of an active pharmaceutical ingredient in a drug formulation is required to avoid the occurrence of sudden phase changes resulting in decrease of bioavailability in a marketed product. Benzocaine is known to possess three crystalline polymorphs, but their stability hierarchy has so far not been determined. A topological method and direct calorimetric measurements under pressure have been used to construct the topological pressure-temperature diagram of the phase relationships between the solid phases II and III, the liquid, and the vapor phase. In the process, the transition temperature between solid phases III and II and its enthalpy change have been determined. Solid phase II, which has the highest melting point, is the more stable phase under ambient conditions in this phase diagram. Surprisingly, solid phase I has not been observed during the study, even though the scarce literature data on its thermal behavior appear to indicate that it might be the most stable one of the three solid phases. Copyright © 2013 Elsevier B.V. All rights reserved.
Testing Relationships between Servant Leadership Dimensions and Leader Member Exchange (LMX)

ERIC Educational Resources Information Center

Barbuto, John E.; Hayden, Robert W.

2011-01-01

Leader member exchange has previously been found to be a solid predictor of positive organizational outcomes. Much research has tested a variety of possible antecedents to Leader Member Exchange (LMX), but only a limited number involving leadership styles. In this study servant leadership dimensions were tested for relationship to LMX quality.…
Preliminary Analysis of a Fully Solid State Magnetocaloric Refrigeration

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

Abdelaziz, Omar

Magnetocaloric refrigeration is an alternative refrigeration technology with significant potential energy savings compared to conventional vapor compression refrigeration technology. Most of the reported active magnetic regenerator (AMR) systems that operate based on the magnetocaloric effect use heat transfer fluid to exchange heat, which results in complicated mechanical subsystems and components such as rotating valves and hydraulic pumps. In this paper, we propose an alternative mechanism for heat transfer between the AMR and the heat source/sink. High-conductivity moving rods/sheets (e.g. copper, brass, iron, graphite, aluminum or composite structures from these) are utilized instead of heat transfer fluid significantly enhancing the heatmore » transfer rate hence cooling/heating capacity. A one-dimensional model is developed to study the solid state AMR. In this model, the heat exchange between the solid-solid interfaces is modeled via a contact conductance, which depends on the interface apparent pressure, material hardness, thermal conductivity, surface roughness, surface slope between the interfaces, and material filled in the gap between the interfaces. Due to the tremendous impact of the heat exchange on the AMR cycle performance, a sensitivity analysis is conducted employing a response surface method, in which the apparent pressure, effective surface roughness and grease thermal conductivity are the uncertainty factors. COP and refrigeration capacity are presented as the response in the sensitivity analysis to reveal the important factors influencing the fully solid state AMR and optimize the solid state AMR efficiency. The performances of fully solid state AMR and traditional AMR are also compared and discussed in present work. The results of this study will provide general guidelines for designing high performance solid state AMR systems.« less
The global phase diagram of the Gay-Berne model

NASA Astrophysics Data System (ADS)

de Miguel, Enrique; Vega, Carlos

2002-10-01

The phase diagram of the Gay-Berne model with anisotropy parameters κ=3, κ'=5 has been evaluated by means of computer simulations. For a number of temperatures, NPT simulations were performed for the solid phase leading to the determination of the free energy of the solid at a reference density. Using the equation of state and free energies of the isotropic and nematic phases available in the existing literature the fluid-solid equilibrium was calculated for the temperatures selected. Taking these fluid-solid equilibrium results as the starting points, the fluid-solid equilibrium curve was determined for a wide range of temperatures using Gibbs-Duhem integration. At high temperatures the sequence of phases encountered on compression is isotropic to nematic, and then nematic to solid. For reduced temperatures below T=0.85 the sequence is from the isotropic phase directly to the solid state. In view of this we locate the isotropic-nematic-solid triple point at TINS=0.85. The present results suggest that the high-density phase designated smectic B in previous simulations of the model is in fact a molecular solid and not a smectic liquid crystal. It seems that no thermodynamically stable smectic phase appears for the Gay-Berne model with the choice of parameters used in this work. We locate the vapor-isotropic liquid-solid triple point at a temperature TVIS=0.445. Considering that the critical temperatures is Tc=0.473, the Gay-Berne model used in this work presents vapor-liquid separation over a rather narrow range of temperatures. It is suggested that the strong lateral attractive interactions present in the Gay-Berne model stabilizes the layers found in the solid phase. The large stability of the solid phase, particularly at low temperatures, would explain the unexpectedly small liquid range observed in the vapor-liquid region.
Experimental constraints on reconstruction of Archean seawater Ni isotopic composition from banded iron formations

NASA Astrophysics Data System (ADS)

Wang, Shui-Jiong; Wasylenki, Laura E.

2017-06-01

The Ni isotopic systematics in banded iron formations (BIFs) potentially recorded the Ni isotopic composition of ancient seawater over Precambrian geological history. However, the utility of BIFs as proxies requires quantitative knowledge of how Ni isotopes fractionated as dissolved Ni was initially incorporated into iron-rich sediments and how diagenesis may have affected the Ni isotopic systematics. Here we report results of synthesis experiments to investigate the behavior of Ni isotopes during Ni coprecipitation with ferrihydrite and then transformation of ferrihydrite to hematite. Ferrihydrite coprecipitation experiments at neutral pH demonstrated that the dissolved Ni was variably heavier than coprecipitated Ni (likely a mixture of surface-adsorbed and structurally incorporated Ni), with the isotope fractionation becoming larger as the fraction of Ni associated with solid increased (Δ60/58Nisolution-solid = +0.08 to +0.50‰). Further experiments at lower pH (3.7-6.7), in which structurally incorporated Ni likely dominated in solids, documented a decrease in Δ60/58Nisolution-solid from +0.44‰ to -0.18‰ as the pH decreased. The negative value for Δ60/58Nisolution-solid at low pH indicates the enrichment of heavier isotopes in incorporated Ni relative to dissolved and adsorbed Ni, possibly as a result of the presence of a small amount of tetrahedral Ni2+ in addition to octahedral Ni2+ in the ferrihydrite structure. The results of the ferrihydrite experiments thus reflect equilibrium isotope fractionation between three pools of Ni, with δ60/58Ni values in the order of incorporated > dissolved > adsorbed. Hematite was synthesized by transformation of Ni-bearing ferrihydrite in aqueous solution at ∼100 °C. A significant amount of Ni (up to 60%) was released (desorbed) from solids into solutions as pH dropped from ∼7 to 4.5-5.5 upon phase transformation. Rinsing of the synthesized hematite in 2 M acetic acid released only very small amounts of Ni (<4% of total Ni, presumably surface-adsorbed) that were isotopically heavier (δ60/58Ni = +0.11 ± 0.06‰) than the residues (presumably dominated by incorporated Ni), which had δ60/58Ni of -0.26 ± 0.07‰. The preference of lighter isotopes for the incorporated Ni relative to the surface-adsorbed Ni after phase transformation (most had been released into solution) is probably due to distortion of Nisbnd O octahedra in the hematite structure, with weaker Nisbnd O bond strengths on average. Hence, the more variable Δ60/58Nisolution-solid values (-0.04 to +0.77‰) observed in hematite experiments most likely reflect thermodynamically driven Rayleigh fractionation, with incorporated Ni unavailable to exchange with dissolved Ni due to continuous reduction in size of the highly reactive surface pool of Ni, through which all solid-solution exchange must occur. Overall, the synthesized hematite was isotopically lighter than the ferrihydrite by ∼0.08‰ in δ60/58Ni, which is however within the current analytical uncertainties (±0.09‰). This implies that earliest diagenesis of BIFs results in very limited change in the isotopic composition of solid-associated Ni. Our experimental results, although conducted in a very simple system that differs from Archean seawater, represent an important step toward reconstruction of the Ni isotopic composition of ancient seawater from Ni isotopic signatures in BIFs.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Weaver, G.T.; Kanna, P.K.; Beese, F.

A shallow slightly acid Terra fusca (Rendolls) soil derived from triassic limestone contains substantial amounts of sulfate. Under high sulfate input, low pH and high salt input this soil can further retain sulfate. Soil chemical data indicate that this soil contains exchangeable Al and H. This finding and the analysis of the equilibrium soil solutions from batch and percolation studies indicate that the retention of sulfate can be described by an equilibrium solid/solution phase of the type Al(OH)SO4 (aluminum hydroxy sulfate). Under similar experimental conditions of solution composition and concentration, Freundlich type adsorption/desorption isotherms and the general solute transport equationmore » can describe the retention and transport of sulfate in this soil.« less
Analysis of organic acids and acylglycines for the diagnosis of related inborn errors of metabolism by GC- and HPLC-MS.

PubMed

la Marca, Giancarlo; Rizzo, Cristiano

2011-01-01

The analysis of organic acids in urine is commonly included in routine procedures for detecting many inborn errors of metabolism. Many analytical methods allow for both qualitative and quantitative determination of organic acids, mainly in urine but also in plasma, serum, whole blood, amniotic fluid, and cerebrospinal fluid. Liquid-liquid extraction and solid-phase extraction using anion exchange or silica columns are commonly employed approaches for sample treatment. Before analysis can be carried out using gas chromatography-mass spectrometry, organic acids must be converted into more thermally stable, volatile, and chemically inert forms, mainly trimethylsilyl ethers, esters, or methyl esters.
Method of producing gaseous products using a downflow reactor

DOEpatents

Cortright, Randy D; Rozmiarek, Robert T; Hornemann, Charles C

2014-09-16

Reactor systems and methods are provided for the catalytic conversion of liquid feedstocks to synthesis gases and other noncondensable gaseous products. The reactor systems include a heat exchange reactor configured to allow the liquid feedstock and gas product to flow concurrently in a downflow direction. The reactor systems and methods are particularly useful for producing hydrogen and light hydrocarbons from biomass-derived oxygenated hydrocarbons using aqueous phase reforming. The generated gases may find used as a fuel source for energy generation via PEM fuel cells, solid-oxide fuel cells, internal combustion engines, or gas turbine gensets, or used in other chemical processes to produce additional products. The gaseous products may also be collected for later use or distribution.
[Advances of poly (ionic liquid) materials in separation science].

PubMed

Liu, Cuicui; Guo, Ting; Su, Rina; Gu, Yuchen; Deng, Qiliang

2015-11-01

Ionic liquids, as novel ionization reagents, possess beneficial characteristics including good solubility, conductivity, thermal stability, biocompatibility, low volatility and non-flammability. Ionic liquids are attracting a mass of attention of analytical chemists. Poly (ionic liquid) materials have common performances of ionic liquids and polymers, and have been successfully applied in separation science area. In this paper, we discuss the interaction mechanisms between the poly(ionic liquid) materials and analytes including hydrophobic/hydrophilic interactions, hydrogen bond, ion exchange, π-π stacking and electrostatic interactions, and summarize the application advances of the poly(ionic liquid) materials in solid phase extraction, chromatographic separation and capillary electrophoresis. At last, we describe the future prospect of poly(ionic liquid) materials.
Determination of the phenoxyacid herbicides MCPA, mecoprop and 2,4-D in kidney tissue using liquid chromatography with electrospray tandem mass spectrometry.

PubMed

Charlton, Andrew J A; Stuckey, Vicki; Sykes, Mark D

2009-06-01

An analytical method was developed to determine the phenoxyacid herbicides 2,4-D, MCPA and mecoprop in kidney tissue from animals where poisoning is suspected. Samples were Soxhlet extracted using diethyl ether and the extracts cleaned-up using anion exchange solid phase extraction cartridges. Analysis was performed using liquid chromatography with negative-ion electrospray tandem mass spectrometry (LC-MS/MS). The method was evaluated by analysing control kidney samples fortified at 1 and 5 mg/kg. Mean recoveries ranged from 82 to 93% with relative standard deviations from 3.2 to 19%. The limit of detection was estimated to be 0.02 mg/kg.
Apparatus for silicon nitride precursor solids recovery

DOEpatents

Crosbie, Gary M.; Predmesky, Ronald L.; Nicholson, John M.

1995-04-04

Method and apparatus are provided for collecting reaction product solids entrained in a gaseous outflow from a reaction situs, wherein the gaseous outflow includes a condensable vapor. A condensate is formed of the condensable vapor on static mixer surfaces within a static mixer heat exchanger. The entrained reaction product solids are captured in the condensate which can be collected for further processing, such as return to the reaction situs. In production of silicon imide, optionally integrated into a production process for making silicon nitride caramic, wherein reactant feed gas comprising silicon halide and substantially inert carrier gas is reacted with liquid ammonia in a reaction vessel, silicon imide reaction product solids entrained in a gaseous outflow comprising residual carrier gas and vaporized ammonia can be captured by forming a condensate of the ammonia vapor on static mixer surfaces of a static mixer heat exchanger.
Method for silicon nitride precursor solids recovery

DOEpatents

Crosbie, Gary M.; Predmesky, Ronald L.; Nicholson, John M.

1992-12-15

Method and apparatus are provided for collecting reaction product solids entrained in a gaseous outflow from a reaction situs, wherein the gaseous outflow includes a condensable vapor. A condensate is formed of the condensable vapor on static mixer surfaces within a static mixer heat exchanger. The entrained reaction product solids are captured in the condensate which can be collected for further processing, such as return to the reaction situs. In production of silicon imide, optionally integrated into a production process for making silicon nitride caramic, wherein reactant feed gas comprising silicon halide and substantially inert carrier gas is reacted with liquid ammonia in a reaction vessel, silicon imide reaction product solids entrained in a gaseous outflow comprising residual carrier gas and vaporized ammonia can be captured by forming a condensate of the ammonia vapor on static mixer surfaces of a static mixer heat exchanger.
Measurement of bromate in bread by liquid chromatography with post-column flow reactor detection.

PubMed

Himata, K; Noda, M; Ando, S; Yamada, Y

2000-01-01

This method is suitable for the determination of bromate residues in a variety of baked goods. The peer-verified method trial was performed on white bread, multigrain bread, and coffee cake spiked with known levels of potassium bromate. The analytical portion is extracted with deionized water to remove bromate from the bulk of the baked product. The aqueous extract is carried through a series of steps to remove co-extractives that would interfere with the liquid chromatography (LC) in the determinative step or hasten the deterioration of the LC column. The extract is filtered before passing it through a reversed-phase solid-phase extraction (SPE) column and a cation-exchange column in the silver form to remove lipids and chloride, respectively. Ultrafiltration is then used to remove proteins with molecular weights of >30,000 daltons. Finally, a cation-exchange column in the sodium form is used to remove silver ions from the extract. The determinative step uses LC with a reversed-phase column and an ion-pairing agent in the mobile phase. Detection is based on the post-column reaction of bromate with o-dianisidine to form an oxidation product that is quantitated spectrophotometrically at 450 nm. Overall agreement between the submitting and peer laboratories was quite good. For bromate levels of 10-52 ppb, overall mean recoveries were 76.9 and 78.8% for the submitting and peer laboratories, respectively. The standard deviations were higher for the results of the peer laboratory, probably because of the generally higher level of baseline noise present in the chromatograms. The results demonstrate that the method provides adequate accuracy with low-fat as well as high-fat foods. Bromate at levels as low as 5 ppb (ng/g) can be detected with the method.
Separation and determination of polyurethane amine catalysts in polyether polyols by using UHPLC-Q-TOF-MS on a reversed-phase/cation-exchange mixed-mode column.

PubMed

Li, Jiaxiao; Zhu, Marcel

2018-02-01

A simple, selective, and accurate ultra-high performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry method was established and validated for the efficient separation and quantification of polyurethane amine catalysts in polyether polyols. Amine catalysts were primarily separated in polyether polyol-based sample by solid-phase extraction, and further baseline separated on a reversed-phase/cation-exchange mixed-mode column (SiELC Primesep™ 200) using 0.1% trifluoroacetic acid/acetonitrile as a mobile phase in gradient elution mode at a flow rate of 0.2 mL/min. High-resolution quadrupole time-of-flight mass spectrometry analysis in electrospray ionization positive mode allowed the identification as N,N'-bis[3-(dimethylamino)propyl]urea, N-[2-(2-dimethylaminoethoxy)ethyl]-N-methyl-1,3-propanediamine, and N,N,N',N'-tetramethyldipropylenetriamine. The method was validated and presented good linearity for all the analytes in blank matrices within the concentration range of 0.20-5.0 or 0.1-2.0 μg/mL with the correlation coefficients (R 2 ) ranging from 0.986 to 0.997. Method recovery ranged within 81-105% at all three levels (80, 100, and 120% of the original amount) with relative standard deviations of 1.0-6.2%. The limits of detection were in the range of 0.007-0.051 μg/mL. Good precision was obtained with relative standard deviation below 3.2 and 0.72% for peak area and retention time of three amines, respectively. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
The Effect of Metal Composition on Fe-Ni Partition Behavior between Olivine and FeNi-Metal, FeNi-Carbide, FeNi-Sulfide at Elevated Pressure

NASA Technical Reports Server (NTRS)

Holzheid, Astrid; Grove, Timothy L.

2005-01-01

Metal-olivine Fe-Ni exchange distribution coefficients were determined at 1500 C over the pressure range of 1 to 9 GPa for solid and liquid alloy compositions. The metal alloy composition was varied with respect to the Fe/Ni ratio and the amount of dissolved carbon and sulfur. The Fe/Ni ratio of the metal phase exercises an important control on the abundance of Ni in the olivine. The Ni abundance in the olivine decreases as the Fe/Ni ratio of the coexisting metal increases. The presence of carbon (up to approx. 3.5 wt.%) and sulfur (up to approx. 7.5 wt.%) in solution in the liquid Fe-Ni-metal phase has a minor effect on the partitioning of Fe and Ni between metal and olivine phases. No pressure dependence of the Fe-Ni-metal-olivine exchange behavior in carbon- and sulfur-free and carbon- and sulfur-containing systems was found within the investigated pressure range. To match the Ni abundance in terrestrial mantle olivine, assuming an equilibrium metal-olivine distribution, a sub-chondritic Fe/Ni-metal ratio that is a factor of 17 to 27 lower than the Fe/Ni ratios in estimated Earth core compositions would be required, implying higher Fe concentrations in the core forming metal phase. A simple metal-olivine equilibrium distribution does not seem to be feasible to explain the Ni abundances in the Earth's mantle. An equilibrium between metal and olivine does not exercise a control on the problem of Ni overabundance in the Earth's mantle. The experimental results do not contradict the presence of a magma ocean at the time of terrestrial core formation, if olivine was present in only minor amounts at the time of metal segregation.
Analysis of Mineral Assemblages Containing Unstable Hydrous Phases

NASA Astrophysics Data System (ADS)

Vaniman, D. T.; Wilson, S. A.; Bish, D. L.; Chipera, S.

2011-12-01

Minerals in many environments can be treated as durable phases that preserve a record of their formation. However many minerals, especially those with hydrogen-bonded H2O molecules as part of their structure, are ephemeral and are unlikely to survive disturbance let alone removal from their environment of formation. Minerals with exceptionally limited stability such as meridianiite (Mg-sulfate 11 hydrate), ikaite (Ca-carbonate 6 hydrate), and mirabilite (Na-sulfate 10 hydrate) are very susceptible to destabilization during analysis, and even modest changes in temperature or relative humidity can lead to change in hydration state or deliquescence. The result may be not only loss of the salt hydrate but dissolution of other salts present, precipitation of new phases, and ion exchange between the concentrated solution and otherwise unaffected phases. Exchange of H2O molecules can also occur in solid-vapor systems without any liquid involvement; moreover, recent work has shown that cation exchange between smectite and sulfate hydrates can occur without any liquid phase present other than a presumed thin film at the salt-silicate interface. Among hydrous silicates, clay minerals are susceptible to cation exchange and similar alteration can be expected for zeolites, palagonite, and possibly other hydrous silicate alteration products. Environmentally sensitive phases on Mars, such as meridianiite, may occur at higher latitudes or in the subsurface where permafrost may be present. Accurate determination of the presence and paragenesis of such minerals will be important for understanding the near-surface hydrogeology of Mars, and in situ analysis may be the only way to obtain this information. Access to the subsurface may be required, yet the act of exposure by excavation or drilling can itself lead to rapid degradation as the sample is exposed or brought to the surface for analysis. Mars is not the only body with which to be concerned, for similar concerns can be raised for sampling cold-environment deposits at the lunar poles, at the poles of Mercury, on icy satellites, and on many other bodies that may host hydrous minerals. The problem of adequate in situ analysis of such mutable assemblages extends to Earth as well, for example in the need for improved understanding of polar and permafrost regions, deep sea clathrates, cave minerals, and mine dump efflorescence. Advanced methods of in situ analysis are needed, including but not limited to contact instruments and instrumentation that can be inserted by probe or operated within a borehole that could be advanced with minimal thermal disturbance. One of the lessons of robotic analysis is that field instruments, which by necessity are less capable than laboratory equivalents, provide greatly improved interpretations if data from several different instruments can be compared.

Elaboration and characterization of solid materials of types zeolite NaA and faujasite NaY exchanged by zinc metallic ions Zn2+

NASA Astrophysics Data System (ADS)

Nibou, D.; Amokrane, S.; Mekatel, H.; Lebaili, N.

2009-11-01

The present work deals with the elaborated of NaA and faujasite NaY solid materials according to a hydrothermal crystallization of amorphous gels composed of solutions of silicon, aluminum and sodium. The process elaboration has been achieved in autoclaves made of steel lined in Teflon under different operating conditions of temperature of heating, time of contact and stirring. After crystallization, the samples were characterized by different techniques such as X ray diffraction, scanning electronic microscopy, infrared spectroscopy, thermal analysis, and chemical analysis. Pure solid materials NaA and NaY zeolites were obtained and were impregnated by (Zn2+) ions by ion exchange process. The effects of various parameters such as initial metal concentration, pH, solid-liquid ratio (R) and temperature on the exchange percentage are studied. The equilibrium isotherms of zinc ions sorption are also evaluated using Langmuir and Freundlich models. Thermodynamic parameters, i.e. enthalpy of adsorption ΔHads∘, entropy change ΔSads∘ and Gibbs free energy ΔGads∘ for the sorption of zinc ions on NaA and NaY zeolites were examined.
Precipitation in Al–Mg solid solution prepared by solidification under high pressure

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

Jie, J.C., E-mail: jiejc@dlut.edu.cn; School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001; Wang, H.W.

2014-01-15

The precipitation in Al–Mg solid solution containing 21.6 at.% Mg prepared by solidification under 2 GPa was investigated. The results show that the γ-Al{sub 12}Mg{sub 17} phase is formed and the β′ phase cannot be observed in the solid solution during ageing process. The precipitation of γ and β phases takes place in a non-uniform manner during heating process, i.e. the γ and β phases are first formed in the interdendritic region, which is caused by the inhomogeneous distribution of Mg atoms in the solid solution solidified under high pressure. Peak splitting of X-ray diffraction patterns of Al(Mg) solid solutionmore » appears, and then disappears when the samples are aged at 423 K for different times, due to the non-uniform precipitation in Al–Mg solid solution. The direct transformation from the γ to β phase is observed after ageing at 423 K for 24 h. It is considered that the β phase is formed through a peritectoid reaction of α + γ → β which needs the diffusion of Mg atoms across the interface of α/γ phases. - Highlights: • The γ phase is formed and the β′ phase is be observed in Al(Mg) solid solution. • Peak splitting of XRD pattern of Al(Mg) solid solution appears during aged at 150 °C. • The β phase is formed through a peritectoid reaction of α + γ → β.« less
Accurate Semilocal Density Functional for Condensed-Matter Physics and Quantum Chemistry.

PubMed

Tao, Jianmin; Mo, Yuxiang

2016-08-12

Most density functionals have been developed by imposing the known exact constraints on the exchange-correlation energy, or by a fit to a set of properties of selected systems, or by both. However, accurate modeling of the conventional exchange hole presents a great challenge, due to the delocalization of the hole. Making use of the property that the hole can be made localized under a general coordinate transformation, here we derive an exchange hole from the density matrix expansion, while the correlation part is obtained by imposing the low-density limit constraint. From the hole, a semilocal exchange-correlation functional is calculated. Our comprehensive test shows that this functional can achieve remarkable accuracy for diverse properties of molecules, solids, and solid surfaces, substantially improving upon the nonempirical functionals proposed in recent years. Accurate semilocal functionals based on their associated holes are physically appealing and practically useful for developing nonlocal functionals.
Heat Transfer in Metal Foam Heat Exchangers at High Temperature

NASA Astrophysics Data System (ADS)

Hafeez, Pakeeza

Heat transfer though open-cell metal foam is experimentally studied for heat exchanger and heat shield applications at high temperatures (˜750°C). Nickel foam sheets with pore densities of 10 and 40 pores per linear inch (PPI), have been used to make the heat exchangers and heat shields by using thermal spray coating to deposit an Inconel skin on a foam core. Heat transfer measurements were performed on a test rig capable of generating hot gas up to 1000°C. The heat exchangers were tested by exposing their outer surface to combustion gases at a temperature of 550°C and 750°C while being cooled by air flowing through them at room temperature at velocities up to 5 m/s. The temperature rise of the air, the surface temperature of the heat exchangers and the air temperature inside the heat exchanger were measured. The volumetric heat transfer coefficient and Nusselt number were calculated for different velocities. The heat transfer performance of the 40PPI sample brazed with the foil is found to be the most efficient. Pressure drop measurements were also performed for 10 and 40PPI metal foam. Thermographic measurements were done on 40PPI foam heat exchangers using a high temperature infrared camera. A high power electric heater was used to produce hot air at 300°C that passed over the foam heat exchanger while the cooling air was blown through it. Heat shields were made by depositing porous skins on metal foam and it was observed that a small amount of coolant leaking through the pores notably reduces the heat transfer from the hot gases. An analytical model was developed based assuming local thermal non-equilibrium that accounts for the temperature difference between solid and fluid phase. The experimental results are found to be in good agreement with the predicted values of the model.
Scalability, Scintillation Readout and Charge Drift in a Kilogram Scale Solid Xenon Particle Detector

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

Yoo, J.; Cease, H.; Jaskierny, W. F.

2014-10-23

We report a demonstration of the scalability of optically transparent xenon in the solid phase for use as a particle detector above a kilogram scale. We employ a liquid nitrogen cooled cryostat combined with a xenon purification and chiller system to measure the scintillation light output and electron drift speed from both the solid and liquid phases of xenon. Scintillation light output from sealed radioactive sources is measured by a set of high quantum efficiency photomultiplier tubes suitable for cryogenic applications. We observed a reduced amount of photons in solid phase compared to that in liquid phase. We used amore » conventional time projection chamber system to measure the electron drift time in a kilogram of solid xenon and observed faster electron drift speed in the solid phase xenon compared to that in the liquid phase.« less
Fuel spill identification using solid-phase extraction and solid-phase microextraction. 1. Aviation turbine fuels.

PubMed

Lavine, B K; Brzozowski, D M; Ritter, J; Moores, A J; Mayfield, H T

2001-12-01

The water-soluble fraction of aviation jet fuels is examined using solid-phase extraction and solid-phase microextraction. Gas chromatographic profiles of solid-phase extracts and solid-phase microextracts of the water-soluble fraction of kerosene- and nonkerosene-based jet fuels reveal that each jet fuel possesses a unique profile. Pattern recognition analysis reveals fingerprint patterns within the data characteristic of fuel type. By using a novel genetic algorithm (GA) that emulates human pattern recognition through machine learning, it is possible to identify features characteristic of the chromatographic profile of each fuel class. The pattern recognition GA identifies a set of features that optimize the separation of the fuel classes in a plot of the two largest principal components of the data. Because principal components maximize variance, the bulk of the information encoded by the selected features is primarily about the differences between the fuel classes.
Solid-solid phase change thermal storage application to space-suit battery pack

NASA Astrophysics Data System (ADS)

Son, Chang H.; Morehouse, Jeffrey H.

1989-01-01

High cell temperatures are seen as the primary safety problem in the Li-BCX space battery. The exothermic heat from the chemical reactions could raise the temperature of the lithium electrode above the melting temperature. Also, high temperature causes the cell efficiency to decrease. Solid-solid phase-change materials were used as a thermal storage medium to lower this battery cell temperature by utilizing their phase-change (latent heat storage) characteristics. Solid-solid phase-change materials focused on in this study are neopentyl glycol and pentaglycerine. Because of their favorable phase-change characteristics, these materials appear appropriate for space-suit battery pack use. The results of testing various materials are reported as thermophysical property values, and the space-suit battery operating temperature is discussed in terms of these property results.
Oxo-exchange of gas-phase uranyl, neptunyl, and plutonyl with water and methanol.

PubMed

Lucena, Ana F; Odoh, Samuel O; Zhao, Jing; Marçalo, Joaquim; Schreckenbach, Georg; Gibson, John K

2014-02-17

A challenge in actinide chemistry is activation of the strong bonds in the actinyl ions, AnO2(+) and AnO2(2+), where An = U, Np, or Pu. Actinyl activation in oxo-exchange with water in solution is well established, but the exchange mechanisms are unknown. Gas-phase actinyl oxo-exchange is a means to probe these processes in detail for simple systems, which are amenable to computational modeling. Gas-phase exchange reactions of UO2(+), NpO2(+), PuO2(+), and UO2(2+) with water and methanol were studied by experiment and density functional theory (DFT); reported for the first time are experimental results for UO2(2+) and for methanol exchange, as well as exchange rate constants. Key findings are faster exchange of UO2(2+) versus UO2(+) and faster exchange with methanol versus water; faster exchange of UO2(+) versus PuO2(+) was quantified. Computed potential energy profiles (PEPs) are in accord with the observed kinetics, validating the utility of DFT to model these exchange processes. The seemingly enigmatic result of faster exchange for uranyl, which has the strongest oxo-bonds, may reflect reduced covalency in uranyl as compared with plutonyl.
Dynamics of water droplets detached from porous surfaces of relevance to PEM fuel cells.

PubMed

Theodorakakos, A; Ous, T; Gavaises, M; Nouri, J M; Nikolopoulos, N; Yanagihara, H

2006-08-15

The detachment of liquid droplets from porous material surfaces used with proton exchange membrane (PEM) fuel cells under the influence of a cross-flowing air is investigated computationally and experimentally. CCD images taken on a purpose-built transparent fuel cell have revealed that the water produced within the PEM is forming droplets on the surface of the gas-diffusion layer. These droplets are swept away if the velocity of the flowing air is above a critical value for a given droplet size. Static and dynamic contact angle measurements for three different carbon gas-diffusion layer materials obtained inside a transparent air-channel test model have been used as input to the numerical model; the latter is based on a Navier-Stokes equations flow solver incorporating the volume of fluid (VOF) two-phase flow methodology. Variable contact angle values around the gas-liquid-solid contact-line as well as their dynamic change during the droplet shape deformation process, have allowed estimation of the adhesion force between the liquid droplet and the solid surface and successful prediction of the separation line at which droplets loose their contact from the solid surface under the influence of the air stream flowing around them. Parametric studies highlight the relevant importance of various factors affecting the detachment of the liquid droplets from the solid surface.
Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface

DOE PAGES

Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin; ...

2016-06-13

Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO 3 ) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H 2 O and CO 2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, Sr La ') by the positively charged oxygen vacancies (Vmore » $$••\\atop{o}$$) enriched at the surface. Here we show that reducing the surface V $$••\\atop{o}$$ concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O 2 molecules. We take La 0.8 Sr 0.2 CoO 3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of V $$••\\atop{o}$$ and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a 'volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss.« less
Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface

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

Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin

Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO 3 ) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H 2 O and CO 2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, Sr La ') by the positively charged oxygen vacancies (Vmore » $$••\\atop{o}$$) enriched at the surface. Here we show that reducing the surface V $$••\\atop{o}$$ concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O 2 molecules. We take La 0.8 Sr 0.2 CoO 3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of V $$••\\atop{o}$$ and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a 'volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss.« less
Rocksalt or cesium chloride: Investigating the relative stability of the cesium halide structures with random phase approximation based methods

NASA Astrophysics Data System (ADS)

Nepal, Niraj K.; Ruzsinszky, Adrienn; Bates, Jefferson E.

2018-03-01

The ground state structural and energetic properties for rocksalt and cesium chloride phases of the cesium halides were explored using the random phase approximation (RPA) and beyond-RPA methods to benchmark the nonempirical SCAN meta-GGA and its empirical dispersion corrections. The importance of nonadditivity and higher-order multipole moments of dispersion in these systems is discussed. RPA generally predicts the equilibrium volume for these halides within 2.4% of the experimental value, while beyond-RPA methods utilizing the renormalized adiabatic LDA (rALDA) exchange-correlation kernel are typically within 1.8%. The zero-point vibrational energy is small and shows that the stability of these halides is purely due to electronic correlation effects. The rAPBE kernel as a correction to RPA overestimates the equilibrium volume and could not predict the correct phase ordering in the case of cesium chloride, while the rALDA kernel consistently predicted results in agreement with the experiment for all of the halides. However, due to its reasonable accuracy with lower computational cost, SCAN+rVV10 proved to be a good alternative to the RPA-like methods for describing the properties of these ionic solids.
Cell dimensions and antiferromagnetism of lunar and terrestrial ilmenite single crystals

USGS Publications Warehouse

Thorpe, A.N.; Minkin, J.A.; Senftle, F.E.; Alexander, Corrine; Briggs, Charles; Evans, H.T.; Nord, G.L.

1977-01-01

X-Ray diffraction and anisotropic magnetic measurements have been made on single crystals of lunar ilmenite and on terrestrial ilmenite from Bancroft, Ontario, Canada and the Ilmen Mountains, U.S.S.R. The elongated c-axis of lunar ilmenite, previously reported, is confirmed by new measurements. The shorter c-axis found in terrestrial specimens is ascribed to Fe3+ substitution for Ti4+ in the titanium layer. Magnetic measurements on the same specimens show that, in agreement with the Ishikawa-Shirane et al. model, the initial shortening of the c-axis by the above substitution of small amounts of Fe3+ (<8%) causes an increase in Fe2+-Fe2+ exchange coupling through Fe3+ in the titanium layer that lowers the Ne??el transition temperature. The Weiss temperatures and other magnetic parameters confirm this model proposed by Ishikawa and Shirane et al. Additional transitions found in one of the terrestrial specimens (Bancroft) have been ascribed to a small amount of an exsolved spinel phase, possibly a solid solution phase of magnetite-u??lvospinel. The spinel phase is localized in hematite-rich blebs which exsolved from the host ilmenite-rich phase. ?? 1977.
Energy and Resource Saving of Steelmaking Process: Utilization of Innovative Multi-phase Flux During Dephosphorization Process

NASA Astrophysics Data System (ADS)

Matsuura, Hiroyuki; Hamano, Tasuku; Zhong, Ming; Gao, Xu; Yang, Xiao; Tsukihashi, Fumitaka

2014-09-01

An increase in the utilization efficiency of CaO, one of the major fluxing agents used in various steelmaking processes, is required to reduce the amount of discharged slag and energy consumption of the process. The authors have intensively focused on the development of innovative dephosphorization process by using so called "multi-phase flux" composed of solid and liquid phases. This article summarizes the research on the above topic done by the authors, in which the formation mechanisms of P2O5-containing phase during CaO or 2CaO·SiO2 dissolution into molten slag, the phase relationship between solid and liquid phases at equilibrium, and thermodynamic properties of P2O5-containing phase have been clarified. The reactions between solid CaO or 2CaO·SiO2 and molten CaO-FeO x -SiO2-P2O5 slag were observed by dipping solid specimen in the synthesized slag at 1573 K or 1673 K. The formation of the CaO-FeO layer and dual-phase layer of solid 2CaO·SiO2 and FeO x -rich liquid phase was observed around the interface from the solid CaO side toward the bulk slag phase side. Condensation of P2O5 into 2CaO·SiO2 phase as 2CaO·SiO2-3CaO·P2O5 solid solution was observed in both cases of CaO and 2CaO·SiO2 as solid specimens. Measurement of the phase relationship for the CaO-FeO x -SiO2-P2O5 system confirmed the condensation of P2O5 in solid phase at low oxygen partial pressure. The thermodynamics of 2CaO·SiO2-3CaO·P2O5 solid solution are to be clarified to quantitatively simulate the dephosphorization process, and the current results are also introduced. Based on the above results, the reduction of CaO consumption, the discharged slag curtailment, and energy-saving effects have been discussed.
A simple and selective method for determination of phthalate biomarkers in vegetable samples by high pressure liquid chromatography-electrospray ionization-tandem mass spectrometry.

PubMed

Zhou, Xi; Cui, Kunyan; Zeng, Feng; Li, Shoucong; Zeng, Zunxiang

2016-06-01

In the present study, solid-phase extraction cartridges including silica reversed-phase Isolute C18, polymeric reversed-phase Oasis HLB and mixed-mode anion-exchange Oasis MAX, and liquid-liquid extractions with ethyl acetate, n-hexane, dichloromethane and its mixtures were compared for clean-up of phthalate monoesters from vegetable samples. Best recoveries and minimised matrix effects were achieved using ethyl acetate/n-hexane liquid-liquid extraction for these target compounds. A simple and selective method, based on sample preparation by ultrasonic extraction and liquid-liquid extraction clean-up, for the determination of phthalate monoesters in vegetable samples by liquid chromatography/electrospray ionisation-tandem mass spectrometry was developed. The method detection limits for phthalate monoesters ranged from 0.013 to 0.120 ng g(-1). Good linearity (r(2)>0.991) between MQLs and 1000× MQLs was achieved. The intra- and inter-day relative standard deviation values were less than 11.8%. The method was successfully used to determine phthalate monoester metabolites in the vegetable samples. Copyright © 2016 Elsevier Ltd. All rights reserved.
A Laboratory Study of Natural Zeolite for Treatment of Fluorinated Water

NASA Astrophysics Data System (ADS)

Pandey, A.

2015-12-01

Fluoride contamination is mainly induced in ground water by chemical interaction between water and fluoride bearing rocks and natural fluoridation is further catalyzed by anthropogenic activities. Elevated fluoride concentrations in the water bodies above the permissible limits are not only degrading water for drinking purposes but also to the agricultural, industrial as well as daily household needs. Fluoride content in water has been constantly a subject of serious concern to the concerned authorities. It is significantly contributing in increasing tolls of arthritis, brain and kidney diseases, cancer, male fertility issues and cases of thyroid diseases. Hence, the present study has been conducted to investigate the possibility of treating fluorinated water using zeolites. The capabilities of natural zeolites are attributed to their catalytic, molecular sieve, adsorption and ion-exchange properties which have been utilized in our laboratory experiment. The experiment was carried out in two phases. In the first phase of the experiment, the properties of zeolites were tested in solid and liquid phases using ICP-OES, SEM, EDX and IC tests. Physio-chemical alterations induced by zeolites in the fluid chemistry were monitored by analyzing fluid sample regularly for pH, redox potential, electrical conductivity and total dissolved solids, and by conducting metal and anion tests. In second phase, zeolite was used for treatment of fluorinated water with known concentration of fluoride, and the geochemical processes associated with fluoride remediation were monitored by conducting non-invasive, invasive geochemical and physical measurements at regular time periods on the water samples collected from both control column and the experiment column. Results thus obtained in this study showed decrease in fluoride concentration over time, indicating the possibility of use of zeolites in treatment of fluorinated water.
Direction-dependent stability of skyrmion lattice in helimagnets induced by exchange anisotropy

NASA Astrophysics Data System (ADS)

Hu, Yangfan

2018-06-01

Exchange anisotropy provides a direction dependent mechanism for the stability of the skyrmion lattice phase in noncentrosymmetric bulk chiral magnets. Based on the Fourier representation of the skyrmion lattice, we explain the direction dependence of the temperature-magnetic field phase diagram for bulk MnSi through a phenomenological mean-field model incorporating exchange anisotropy. Through quantitative comparison with experimental results, we clarify that the stability of the skyrmion lattice phase in bulk MnSi is determined by a combined effect of negative exchange anisotropy and thermal fluctuation. The effect of exchange anisotropy and the order of Fourier representation on the equilibrium properties of the skyrmion lattice is discussed in detail.
Crystallization process

DOEpatents

Adler, Robert J.; Brown, William R.; Auyang, Lun; Liu, Yin-Chang; Cook, W. Jeffrey

1986-01-01

An improved crystallization process is disclosed for separating a crystallizable material and an excluded material which is at least partially excluded from the solid phase of the crystallizable material obtained upon freezing a liquid phase of the materials. The solid phase is more dense than the liquid phase, and it is separated therefrom by relative movement with the formation of a packed bed of solid phase. The packed bed is continuously formed adjacent its lower end and passed from the liquid phase into a countercurrent flow of backwash liquid. The packed bed extends through the level of the backwash liquid to provide a drained bed of solid phase adjacent its upper end which is melted by a condensing vapor.
Development and validation of a solid-phase extraction method using anion exchange sorbent for the analysis of cannabinoids in plasma and serum by gas chromatography-mass spectrometry.

PubMed

Gasse, Angela; Pfeiffer, Heidi; Köhler, Helga; Schürenkamp, Jennifer

2016-07-01

The aim of this work was to develop and validate a solid-phase extraction (SPE) method for the analysis of cannabinoids with emphasis on a very extensive and effective matrix reduction in order to ensure constant good results in selectivity and sensitivity regardless of the applied measuring technology. This was obtained by the use of an anion exchange sorbent (AXS) and the purposive ionic interaction between matrix components and this sorbent material. In a first step, the neutral cannabinoids ∆9-tetrahydrocannabinol (THC) and 11-hydroxy-∆9-tetrahydrocannabinol (11-OH-THC) were eluted, leaving 11-nor-9-carboxy-∆9-tetrahydrocannabinol (THC-COOH) and the main interfering matrix components bound to the AXS. In a second step, exploiting differences in pH and polarity, it was possible to separate matrix components and THC-COOH, thereby yielding a clean elution of THC-COOH into the same collecting tube as THC and 11-OH-THC. Even when using a simple measuring technology like gas chromatography with single quadrupole mass spectrometry, this two-step elution allows for an obvious decrease in number and intensity of matrix interference in the chromatogram. Hence, in both plasma and serum, the AXS extracts resulted in very good selectivity. Limits of detection and limits of quantification were below 0.25 and 0.35 ng/mL for the neutral cannabinoids in both matrices, 2.0 and 3.0 ng/mL in plasma and 1.6 and 3.3 ng/mL in serum for THC-COOH. The recoveries were ≥79.8 % for all analytes. Interday and intraday imprecisions ranged from 0.8 to 6.1 % relative standard deviation, and accuracy bias ranged from -12.6 to 3.6 %.
Chromium speciation in environmental samples using a solid phase spectrophotometric method.

PubMed

Amin, Alaa S; Kassem, Mohammed A

2012-10-01

A solid phase extraction technique is proposed for preconcentration and speciation of chromium in natural waters using spectrophotometric analysis. The procedure is based on sorption of chromium(III) as 4-(2-benzothiazolylazo)2,2'-biphenyldiol complex on dextran-type anion-exchange gel (Sephadex DEAE A-25). After reduction of Cr(VI) by 0.5 ml of 96% concentrated H(2)SO(4) and ethanol, the system was applied to the total chromium. The concentration of Cr(VI) was calculated as the difference between the total Cr and the Cr(III) content. The influences of some analytical parameters such as: pH of the aqueous solution, amounts of 4-(2-benzothiazolylazo)2,2'-biphenyldiol (BTABD), and sample volumes were investigated. The absorbance of the gel, at 628 and 750 nm, packed in a 1.0 mm cell, is measured directly. The molar absorptivities were found to be 2.11×10(7) and 3.90×10(7) L mol(-1)cm(-1) for 500 and 1000 ml, respectively. Calibration is linear over the range 0.05-1.45 μg L(-1) with RSD of <1.85% (n=8.0). Using 35 mg exchanger, the detection and quantification limits were 13 and 44 ng L(-1) for 500 ml sample, whereas for 1000 ml sample were 8.0 and 27 ng L(-1), respectively. Increasing the sample volume can enhance the sensitivity. No considerable interferences have been observed from other investigated anions and cations on the chromium speciation. The proposed method was applied to the speciation of chromium in natural waters and total chromium preconcentration in microwave digested tobacco, coffee, tea, and soil samples. The results were simultaneously compared with those obtained using an ET AAS method, whereby the validity of the method has been tested. Copyright © 2012 Elsevier B.V. All rights reserved.

Use of proteomics for validation of the isolation process of clotting factor IX from human plasma.

PubMed

Clifton, James; Huang, Feilei; Gaso-Sokac, Dajana; Brilliant, Kate; Hixson, Douglas; Josic, Djuro

2010-01-03

The use of proteomic techniques in the monitoring of different production steps of plasma-derived clotting factor IX (pd F IX) was demonstrated. The first step, solid-phase extraction with a weak anion-exchange resin, fractionates the bulk of human serum albumin (HSA), immunoglobulin G, and other non-binding proteins from F IX. The proteins that strongly bind to the anion-exchange resin are eluted by higher salt concentrations. In the second step, anion-exchange chromatography, residual HSA, some proteases and other contaminating proteins are separated. In the last chromatographic step, affinity chromatography with immobilized heparin, the majority of the residual impurities are removed. However, some contaminating proteins still remain in the eluate from the affinity column. The next step in the production process, virus filtration, is also an efficient step for the removal of residual impurities, mainly high molecular weight proteins, such as vitronectin and inter-alpha inhibitor proteins. In each production step, the active component, pd F IX and contaminating proteins are monitored by biochemical and immunochemical methods and by LC-MS/MS and their removal documented. Our methodology is very helpful for further process optimization, rapid identification of target proteins with relatively low abundance, and for the design of subsequent steps for their removal or purification.
Development of a Hypersensitive Periodate-Cleavable Amino Acid that is Methionine- and Disulfide-Compatible and its Application in MHC Exchange Reagents for T Cell Characterisation

PubMed Central

Amore, Alessia; Wals, Kim; Koekoek, Evelyn; Hoppes, Rieuwert; Toebes, Mireille; Schumacher, Ton N M; Rodenko, Boris; Ovaa, Huib

2013-01-01

Incorporation of cleavable linkers into peptides and proteins is of particular value in the study of biological processes. Here we describe the synthesis of a cleavable linker that is hypersensitive to oxidative cleavage as the result of the periodate reactivity of a vicinal amino alcohol moiety. Two strategies directed towards the synthesis of a building block suitable for solid-phase peptide synthesis were developed: a chemoenzymatic route, involving l-threonine aldolase, and an enantioselective chemical route; these led to α,γ-diamino-β-hydroxybutanoic acids in diastereoisomerically mixed and enantiopure forms, respectively. Incorporation of the 1,2-amino alcohol linker into the backbone of a peptide generated a conditional peptide that was rapidly cleaved at very low concentrations of sodium periodate. This cleavable peptide ligand was applied in the generation of MHC exchange reagents for the detection of antigen-specific T cells in peripheral blood cells. The extremely low concentration of periodate required to trigger MHC peptide exchange allowed the co-oxidation of methionine and disulfide residues to be avoided. Conditional MHC reagents hypersensitive to periodate can now be applied without limitations when UV irradiation is undesired or less practical. PMID:23280887
Dramatically different kinetics and mechanism at solid/liquid and solid/gas interfaces for catalytic isopropanol oxidation over size-controlled platinum nanoparticles.

PubMed

Wang, Hailiang; Sapi, Andras; Thompson, Christopher M; Liu, Fudong; Zherebetskyy, Danylo; Krier, James M; Carl, Lindsay M; Cai, Xiaojun; Wang, Lin-Wang; Somorjai, Gabor A

2014-07-23

We synthesize platinum nanoparticles with controlled average sizes of 2, 4, 6, and 8 nm and use them as model catalysts to study isopropanol oxidation to acetone in both the liquid and gas phases at 60 °C. The reaction at the solid/liquid interface is 2 orders of magnitude slower than that at the solid/gas interface, while catalytic activity increases with the size of platinum nanoparticles for both the liquid-phase and gas-phase reactions. The activation energy of the gas-phase reaction decreases with the platinum nanoparticle size and is in general much higher than that of the liquid-phase reaction which is largely insensitive to the size of catalyst nanoparticles. Water substantially promotes isopropanol oxidation in the liquid phase. However, it inhibits the reaction in the gas phase. The kinetic results suggest different mechanisms between the liquid-phase and gas-phase reactions, correlating well with different orientations of IPA species at the solid/liquid interface vs the solid/gas interface as probed by sum frequency generation vibrational spectroscopy under reaction conditions and simulated by computational calculations.
Jet fuel based high pressure solid oxide fuel cell system

NASA Technical Reports Server (NTRS)

Gummalla, Mallika (Inventor); Yamanis, Jean (Inventor); Olsommer, Benoit (Inventor); Dardas, Zissis (Inventor); Bayt, Robert (Inventor); Srinivasan, Hari (Inventor); Dasgupta, Arindam (Inventor); Hardin, Larry (Inventor)

2013-01-01

A power system for an aircraft includes a solid oxide fuel cell system which generates electric power for the aircraft and an exhaust stream; and a heat exchanger for transferring heat from the exhaust stream of the solid oxide fuel cell to a heat requiring system or component of the aircraft. The heat can be transferred to fuel for the primary engine of the aircraft. Further, the same fuel can be used to power both the primary engine and the SOFC. A heat exchanger is positioned to cool reformate before feeding to the fuel cell. SOFC exhaust is treated and used as inerting gas. Finally, oxidant to the SOFC can be obtained from the aircraft cabin, or exterior, or both.
Jet Fuel Based High Pressure Solid Oxide Fuel Cell System

NASA Technical Reports Server (NTRS)

Srinivasan, Hari (Inventor); Hardin, Larry (Inventor); Gummalla, Mallika (Inventor); Yamanis, Jean (Inventor); Olsommer, Benoit (Inventor); Dardas, Zissis (Inventor); Dasgupta, Arindam (Inventor); Bayt, Robert (Inventor)

2015-01-01

A power system for an aircraft includes a solid oxide fuel cell system which generates electric power for the aircraft and an exhaust stream; and a heat exchanger for transferring heat from the exhaust stream of the solid oxide fuel cell to a heat requiring system or component of the aircraft. The heat can be transferred to fuel for the primary engine of the aircraft. Further, the same fuel can be used to power both the primary engine and the SOFC. A heat exchanger is positioned to cool reformate before feeding to the fuel cell. SOFC exhaust is treated and used as inerting gas. Finally, oxidant to the SOFC can be obtained from the aircraft cabin, or exterior, or both.
Solidification and solid-state transformation sciences in metals additive manufacturing

DOE PAGES

Kirka, Michael M.; Nandwana, Peeyush; Lee, Yousub; ...

2017-02-11

Additive manufacturing (AM) of metals is rapidly emerging as an established manufacturing process for metal components. Unlike traditional metals fabrication processes, metals fabricated via AM undergo localized thermal cycles during fabrication. As a result, AM presents the opportunity to control the liquid-solid phase transformation, i.e. material texture. But, thermal cycling presents challenges from the standpoint of solid-solid phase transformations. We will discuss the opportunities and challenges in metals AM in the context of texture control and associated solid-solid phase transformations in Ti-6Al-4V and Inconel 718.
Microwave spectroscopic observation of distinct electron solid phases in wide quantum wells

NASA Astrophysics Data System (ADS)

Hatke, A. T.; Liu, Yang; Magill, B. A.; Moon, B. H.; Engel, L. W.; Shayegan, M.; Pfeiffer, L. N.; West, K. W.; Baldwin, K. W.

2014-06-01

In high magnetic fields, two-dimensional electron systems can form a number of phases in which interelectron repulsion plays the central role, since the kinetic energy is frozen out by Landau quantization. These phases include the well-known liquids of the fractional quantum Hall effect, as well as solid phases with broken spatial symmetry and crystalline order. Solids can occur at the low Landau-filling termination of the fractional quantum Hall effect series but also within integer quantum Hall effects. Here we present microwave spectroscopy studies of wide quantum wells that clearly reveal two distinct solid phases, hidden within what in d.c. transport would be the zero diagonal conductivity of an integer quantum-Hall-effect state. Explanation of these solids is not possible with the simple picture of a Wigner solid of ordinary (quasi) electrons or holes.
Extinguishment of a Diffusion Flame Over a PMMA Cylinder by Depressurization in Reduced-Gravity

NASA Technical Reports Server (NTRS)

Goldmeer, Jeffrey Scott

1996-01-01

Extinction of a diffusion flame burning over horizontal PMMA (Polymethyl methacrylate) cylinders in low-gravity was examined experimentally and via numerical simulations. Low-gravity conditions were obtained using the NASA Lewis Research Center's reduced-gravity aircraft. The effects of velocity and pressure on the visible flame were examined. The flammability of the burning solid was examined as a function of pressure and the solid-phase centerline temperature. As the solid temperature increased, the extinction pressure decreased, and with a centerline temperature of 525 K, the flame was sustained to 0.1 atmospheres before extinguishing. The numerical simulation iteratively coupled a two-dimensional quasi-steady, gas-phase model with a transient solid-phase model which included conductive heat transfer and surface regression. This model employed an energy balance at the gas/solid interface that included the energy conducted by the gas-phase to the gas/solid interface, Arrhenius pyrolysis kinetics, surface radiation, and the energy conducted into the solid. The ratio of the solid and gas-phase conductive fluxes Phi was a boundary condition for the gas-phase model at the solid-surface. Initial simulations modeled conditions similar to the low-gravity experiments and predicted low-pressure extinction limits consistent with the experimental limits. Other simulations examined the effects of velocity, depressurization rate and Phi on extinction.
Towards Organic Zeolites and Inclusion Catalysts: Heptazine Imide Salts Can Exchange Metal Cations in the Solid State.

PubMed

Savateev, Aleksandr; Pronkin, Sergey; Willinger, Marc Georg; Antonietti, Markus; Dontsova, Dariya

2017-07-04

Highly crystalline potassium (heptazine imides) were prepared by the thermal condensation of substituted 1,2,4-triazoles in eutectic salt melts. These semiconducting salts are already known to be highly active photocatalysts, for example, for the visible-light-driven generation of hydrogen from water. Herein, we show that within the solid-state structure, potassium ions can be exchanged to other metal ions while the crystal habitus is essentially preserved. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Effects of Drying Process on an IgG1 Monoclonal Antibody Using Solid-State Hydrogen Deuterium Exchange with Mass Spectrometric Analysis (ssHDX-MS).

PubMed

Moussa, Ehab M; Wilson, Nathan E; Zhou, Qi Tony; Singh, Satish K; Nema, Sandeep; Topp, Elizabeth M

2018-01-03

Lyophilization and spray drying are widely used to manufacture solid forms of therapeutic proteins. Lyophilization is used to stabilize proteins vulnerable to degradation in solution, whereas spray drying is mainly used to prepare inhalation powders or as an alternative to freezing for storing bulk drug substance. Both processes impose stresses that may adversely affect protein structure, stability and bioactivity. Here, we compared lyophilization with and without controlled ice nucleation, and spray drying for their effects on the solid-state conformation and matrix interactions of a model IgG1 monoclonal antibody (mAb). Solid-state conformation and matrix interactions of the mAb were probed using solid-state hydrogen-deuterium exchange with mass spectrometric analysis (ssHDX-MS), and solid-state Fourier transform infrared (ssFTIR) and solid-state fluorescence spectroscopies. mAb conformation and/or matrix interactions were most perturbed in mannitol-containing samples and the distribution of states was more heterogeneous in sucrose and trehalose samples that were spray dried. The findings demonstrate the sensitivity of ssHDX-MS to changes weakly indicated by spectroscopic methods, and support the broader use of ssHDX-MS to probe formulation and process effects on proteins in solid samples.
Inductively coupled plasma mass spectrometry study of the retention behavior of arsenic species on various solid phase extraction cartridges and its application in arsenic speciation

NASA Astrophysics Data System (ADS)

Yu, Chunhai; Cai, Qiantao; Guo, Zhong-Xian; Yang, Zhaoguang; Khoo, Soo Beng

2003-07-01

Inductively coupled plasma mass spectrometry (ICP-MS) was used to investigate the retention behavior of arsenite, arsenate, monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenobetaine (AsB), arsenocholine (AsC), trimethylarsine oxide (TMAO) and tetramethylarsonium ion (TMAI) on various silica-based solid phase extraction (SPE) cartridges. A method for arsenic speciation is then developed on the basis of selective SPE separation of arsenic species and highly sensitive ICP-MS detection. Factors affecting the retention and elution of arsenic species were examined. Results showed that the retention of arsenic species depended on the chemical characteristics of arsenic species and the types of sorbent materials. Change of pH in the range of 2.0-9.0 did not show significant effects on the retention of DMA, AsB, AsC, TMAI and TMAO on an ethylbenzene sulfonic acid-based strong cation exchange (SCX-3) cartridge. pH also did not influence the retention of AsB, AsC, TMAI and TMAO on a mixed-mode (M-M) cartridge containing non-polar, strong cation exchange and strong anion exchange (SAX) functional groups. However, the retentions of As(V) and MMA on the SAX and the M-M cartridge changed with pH. As(V) and MMA were completely retained on the SAX cartridge and sequentially selectively eluted with 1.0 mol l -1 acetic acid (for MMA). DMA, AsB, AsC, TMAI and TMAO were completely retained on the SCX-3 cartridge and sequentially selectively eluted with 1.0 mol l -1 HNO 3 (for DMA). As(V), MMA, AsB, AsC, TMAI and TMAO were completely retained on the M-M cartridge. As(III) was not retained on either cartridge and remained in solution. Arsenic species in solution and those eluted from the cartridges were subsequently determined by ICP-MS. A detection limit of 8 ng l -1 arsenic in water sample was obtained. This method was successfully applied to arsenic speciation in various sources of water samples (drinking water, waste water, raw water, etc.) and US National Institute of Standards and Technology standard reference materials with good precision and accuracy.
SOLID-LIQUID PHASE TRANSFER CATALYZED SYNTHESIS OF CINNAMYL ACETATE-KINETICS AND ANALYSIS OF FACTORS AFFECTING THE REACTION IN A BATCH REACTOR

EPA Science Inventory

The use of solid-liquid phase transfer catalysis has an advantage of carrying out reaction between two immiscible substrates, one in solid phase and the other in liquid phase, with high selectivity and at relatively low temperatures. In this study we investigated the synthesis ci...
Interparticle spacing and structural ordering in superlattice PbS nanocrystal solids undergoing ligand exchange

DOE PAGES

Weidman, Mark C.; Yager, Kevin G.; Tisdale, William A.

2014-12-12

Controlling the interparticle spacing in quantum dot (QD) thin films is the most readily accessible way to control transport rates between neighboring QDs and a critical component of device optimization. Here, we use X-ray scattering measurements to accurately measure the interparticle spacing in films of highly monodisperse lead sulfide (PbS) QDs that have undergone a variety of device-relevant ligand exchanges. We tabulate these values for use in simulations and data analysis. We find that monothiol and dithiol ligand species typically result in interparticle spacing values that are equal to the length of a single monothiol or dithiol ligand. Additionally, wemore » find that spin-coating a thick film of QDs followed by a long-duration ligand exchange results in a more complete ligand exchange than spin-coating many thin layers with short-duration ligand exchanges in between. The former method also preserves a remarkable degree of the long-range ordering that was present in the film prior to ligand exchange. These results shed light on ways to produce highly-ordered QD solids with compact and functional ligands, which could lead to enhanced interdot coupling and transport phenomena.« less
Identifying and Quantifying Chemical Forms of Sediment-Bound Ferrous Iron.

NASA Astrophysics Data System (ADS)

Kohler, M.; Kent, D. B.; Bekins, B. A.; Cozzarelli, I.; Ng, G. H. C.

2015-12-01

Aqueous Fe(II) produced by dissimilatory iron reduction comprises only a small fraction of total biogenic Fe(II) within an aquifer. Most biogenic Fe(II) is bound to sediments on ion exchange sites; as surface complexes and, possibly, surface precipitates; or incorporated into solid phases (e.g., siderite, magnetite). Different chemical forms of sediment-bound Fe(II) have different reactivities (e.g., with dissolved oxygen) and their formation or destruction by sorption/desorption and precipitation/dissolution is coupled to different solutes (e.g., major cations, H+, carbonate). We are quantifying chemical forms of sediment-bound Fe(II) using previously published extractions, novel extractions, and experimental studies (e.g., Fe isotopic exchange). Sediments are from Bemidji, Minnesota, where biodegradation of hydrocarbons from a burst oil pipeline has driven extensive dissimilatory Fe(III) reduction, and sites potentially impacted by unconventional oil and gas development. Generally, minimal Fe(II) was mobilized from ion exchange sites (batch desorption with MgCl2 and repeated desorption with NH4Cl). A < 2mm sediment fraction from the iron-reducing zone at Bemidji had 1.8umol/g Fe(II) as surface complexes or carbonate phases (sodium acetate at pH 5) of which ca. 13% was present as surface complexes (FerroZine extractions). Total bioavailable Fe(III) and biogenic Fe(II) (HCl extractions) was 40-50 umole/g on both background and iron-reducing zone sediments . Approximately half of the HCl-extractable Fe from Fe-reducing zone sediments was Fe(II) whereas 12 - 15% of Fe extracted from background sediments was present as Fe(II). One-third to one-half of the total biogenic Fe(II) extracted from sediments collected from a Montana prairie pothole located downgradient from a produced-water disposal pit was present as surface-complexed Fe(II).
Convergence behavior of the random phase approximation renormalized correlation energy

NASA Astrophysics Data System (ADS)

Bates, Jefferson E.; Sensenig, Jonathon; Ruzsinszky, Adrienn

2017-05-01

Based on the random phase approximation (RPA), RPA renormalization [J. E. Bates and F. Furche, J. Chem. Phys. 139, 171103 (2013), 10.1063/1.4827254] is a robust many-body perturbation theory that works for molecules and materials because it does not diverge as the Kohn-Sham gap approaches zero. Additionally, RPA renormalization enables the simultaneous calculation of RPA and beyond-RPA correlation energies since the total correlation energy is the sum of a series of independent contributions. The first-order approximation (RPAr1) yields the dominant beyond-RPA contribution to the correlation energy for a given exchange-correlation kernel, but systematically underestimates the total beyond-RPA correction. For both the homogeneous electron gas model and real systems, we demonstrate numerically that RPA renormalization beyond first order converges monotonically to the infinite-order beyond-RPA correlation energy for several model exchange-correlation kernels and that the rate of convergence is principally determined by the choice of the kernel and spin polarization of the ground state. The monotonic convergence is rationalized from an analysis of the RPA renormalized correlation energy corrections, assuming the exchange-correlation kernel and response functions satisfy some reasonable conditions. For spin-unpolarized atoms, molecules, and bulk solids, we find that RPA renormalization is typically converged to 1 meV error or less by fourth order regardless of the band gap or dimensionality. Most spin-polarized systems converge at a slightly slower rate, with errors on the order of 10 meV at fourth order and typically requiring up to sixth order to reach 1 meV error or less. Slowest to converge, however, open-shell atoms present the most challenging case and require many higher orders to converge.
40 CFR Table 2 to Subpart Mmm of... - Standards for New and Existing PAI Sources

Code of Federal Regulations, 2014 CFR

2014-07-01

... feedstock that is a solid and a HAP Particulate matter concentration not to exceed 0.01 gr/dscf. Heat exchange systems Each heat exchange system used to cool process equipment in PAI manufacturing operations...
40 CFR Table 2 to Subpart Mmm of... - Standards for New and Existing PAI Sources

Code of Federal Regulations, 2013 CFR

2013-07-01

... feedstock that is a solid and a HAP Particulate matter concentration not to exceed 0.01 gr/dscf. Heat exchange systems Each heat exchange system used to cool process equipment in PAI manufacturing operations...
MOF-5(Zn)-Fe2O4 nanocomposite based magnetic solid-phase microextraction followed by HPLC-UV for efficient enrichment of colchicine in root of colchicium extracts and plasma samples.

PubMed

Bahrani, Sonia; Ghaedi, Mehrorang; Dashtian, Kheibar; Ostovan, Abbas; Mansoorkhani, Mohammad Javad Khoshnood; Salehi, Amin

2017-11-01

In present work, facile method is developed for determination of colchicine in human plasma sample, autumn and spring root of colchicium extracts by ultrasound assisted dispersive magnetic solid phase microextraction followed by HPLC-UV method (UAD-MSPME-HPLC-UV). Magnetic (Fe 2 O 4 -nanoparticles) metal organic framework-5, (MOF-5(Zn)-Fe 2 O 4 NPs) was synthesized by dispersing MOF-5 and Fe(NO 3 ) 3 .9H 2 O in ethylene glycol (as capping agent) and NaOH (pH adjustment agent) by hydrothermal method. The prepared sorbent was characterized via XRD and SEM analysis and applied as magnetic solid phase in UAD-MSPME-HPLC-UV method. In this method, colchicine molecules were sorbed on MOF-5(Zn)-Fe 2 O 4 NPs sorbent by various mechanisms like ion exchange, hydrogen bonding and electrostatic, ᴨ-ᴨ, hard-hard and dipole-ion interaction followed by exposing sonication waves as incremental mass transfer agent and then the sorbent was separated from the sample matrix by an external magnetic fields. Subsequently, accumulated colchicine were eluted by small volume of desorption organic solvent. Influence of operational variables such as MOF-5(Zn)-Fe 2 O 4 NPs mass, volume of extracting solvent and sonication time on response property (recovery) were studied and optimized by central composite design (CCD) combined with desirability function (DF) approach. Under optimum condition, the method has wide linear calibration rang (0.5-1700ngmL -1 ) with reasonable detection limit (0.13ngmL -1 ) and R 2 =0.9971. Finally, the UAD-MSPME-HPLC-UV method was successfully applied for determination of colchicine autumn and spring root of colchicium extracts and plasma samples. Copyright © 2017 Elsevier B.V. All rights reserved.
Simulation study on exchange interaction and unique magnetization near ferromagnetic morphotropic phase boundary.

PubMed

Wei, Songrui; Liao, Xiaoqi; Gao, Yipeng; Yang, Sen; Wang, Dong; Song, Xiaoping

2017-11-08

Extensive efforts have been made in searching enhanced functionalities near the so-called morphotropic phase boundaries (MPBs) in both ferroelectric and ferromagnetic materials. Due to the exchange anti-symmetry of the wave function of fermions, it is widely recognized that the exchange interaction plays a critical role in ferromagnetism. As a quantum effect, the exchange interaction is magnitudes larger than electric interaction, leading to a fundamental difference between ferroelectricity and ferromagnetism. In this paper, we establish an energetic model capturing the interplay among the anisotropy energy, magnetostatic energy and the exchange energy to investigate systematically the effects of the exchange energy on the behavior of the ferromagnetic MPB. For the first time, it is found that the exchange energy can narrow the width of MPB region in the composition temperature phase diagram for ferromagnetic MPB systems. As temperature increases, MPB region becomes wider because of the weakening of the exchange interaction. Our simulation results suggest that the exchange energy play a critical role on the unique behavior of ferromagnetic MPB, which is in contrast different from that of ferroelectric MPB.
Numerical modelling of biomass combustion: Solid conversion processes in a fixed bed furnace

NASA Astrophysics Data System (ADS)

Karim, Md. Rezwanul; Naser, Jamal

2017-06-01

Increasing demand for energy and rising concerns over global warming has urged the use of renewable energy sources to carry a sustainable development of the world. Bio mass is a renewable energy which has become an important fuel to produce thermal energy or electricity. It is an eco-friendly source of energy as it reduces carbon dioxide emissions. Combustion of solid biomass is a complex phenomenon due to its large varieties and physical structures. Among various systems, fixed bed combustion is the most commonly used technique for thermal conversion of solid biomass. But inadequate knowledge on complex solid conversion processes has limited the development of such combustion system. Numerical modelling of this combustion system has some advantages over experimental analysis. Many important system parameters (e.g. temperature, density, solid fraction) can be estimated inside the entire domain under different working conditions. In this work, a complete numerical model is used for solid conversion processes of biomass combustion in a fixed bed furnace. The combustion system is divided in to solid and gas phase. This model includes several sub models to characterize the solid phase of the combustion with several variables. User defined subroutines are used to introduce solid phase variables in commercial CFD code. Gas phase of combustion is resolved using built-in module of CFD code. Heat transfer model is modified to predict the temperature of solid and gas phases with special radiation heat transfer solution for considering the high absorptivity of the medium. Considering all solid conversion processes the solid phase variables are evaluated. Results obtained are discussed with reference from an experimental burner.

Solvent-assisted lipid bilayer formation on silicon dioxide and gold.

PubMed

Tabaei, Seyed R; Choi, Jae-Hyeok; Haw Zan, Goh; Zhdanov, Vladimir P; Cho, Nam-Joon

2014-09-02

Planar lipid bilayers on solid supports mimic the fundamental structure of biological membranes and can be investigated using a wide range of surface-sensitive techniques. Despite these advantages, planar bilayer fabrication is challenging, and there are no simple universal methods to form such bilayers on diverse material substrates. One of the novel methods recently proposed and proven to form a planar bilayer on silicon dioxide involves lipid deposition in organic solvent and solvent exchange to influence the phase of adsorbed lipids. To scrutinize the specifics of this solvent-assisted lipid bilayer (SALB) formation method and clarify the limits of its applicability, we have developed a simplified, continuous solvent-exchange version to form planar bilayers on silicon dioxide, gold, and alkanethiol-coated gold (in the latter case, a lipid monolayer is formed to yield a hybrid bilayer) and varied the type of organic solvent and rate of solvent exchange. By tracking the SALB formation process with simultaneous quartz crystal microbalance-dissipation (QCM-D) and ellipsometry, it was determined that the acoustic, optical, and hydration masses along with the acoustic and optical thicknesses, measured at the end of the process, are comparable to those observed by employing conventional fabrication methods (e.g., vesicle fusion). As shown by QCM-D measurements, the obtained planar bilayers are highly resistant to protein adsorption, and several, but not all, water-miscible organic solvents could be successfully used in the SALB procedure, with isopropanol yielding particularly high-quality bilayers. In addition, fluorescence recovery after photobleaching (FRAP) measurements demonstrated that the coefficient of lateral lipid diffusion in the fabricated bilayers corresponds to that measured earlier in the planar bilayers formed by vesicle fusion. With increasing rate of solvent exchange, it was also observed that the bilayer became incomplete and a phenomenological model was developed in order to explain this feature. The results obtained allowed us to clarify and discriminate likely steps of the SALB formation process as well as determine the corresponding influence of organic solvent type and flow conditions on these steps. Taken together, the findings demonstrate that the SALB formation method can be adapted to a continuous solvent-exchange procedure that is technically minimal, quick, and efficient to form planar bilayers on solid supports.
Organic-inorganic hybrid perovskite quantum dots with high PLQY and enhanced carrier mobility through crystallinity control by solvent engineering and solid-state ligand exchange.

PubMed

Woo Choi, Jin; Woo, Hee Chul; Huang, Xiaoguang; Jung, Wan-Gil; Kim, Bong-Joong; Jeon, Sie-Wook; Yim, Sang-Youp; Lee, Jae-Suk; Lee, Chang-Lyoul

2018-05-22

The photoluminescence quantum yield (PLQY) and charge carrier mobility of organic-inorganic perovskite QDs were enhanced by the optimization of crystallinity and surface passivation as well as solid-state ligand exchange. The crystallinity of perovskite QDs was determined by the Effective solvent field (Esol) of various solvents for precipitation. The solvent with high Esol could more quickly countervail the localized field generated by the polar solvent, and it causes fast crystallization of the dissolved precursor, which results in poor crystallinity. The post-ligand adding process (PLAP) and post-ligand exchange process (PLEP) increase the PLQY of perovskite QDs by reducing non-radiative recombination and the density of surface defect states through surface passivation. Particularly, the post ligand exchange process (PLEP) in the solid-state improved the charge carrier mobility of perovskite QDs in addition to the PLQY enhancement. The ligand exchange with short alkyl chain length ligands could improve the packing density of perovskite QDs in films by reducing the inter-particle distance between perovskite QDs. The maximum hole mobility of 6.2 × 10-3 cm2 V-1 s-1, one order higher than that of pristine QDs without the PLEP, is obtained at perovskite QDs with hexyl ligands. By using PLEP treatment, compared to the pristine device, a 2.5 times higher current efficiency in perovskite QD-LEDs was achieved due to the improved charge carrier mobility and PLQY.
Theory of amorphous ices.

PubMed

Limmer, David T; Chandler, David

2014-07-01

We derive a phase diagram for amorphous solids and liquid supercooled water and explain why the amorphous solids of water exist in several different forms. Application of large-deviation theory allows us to prepare such phases in computer simulations. Along with nonequilibrium transitions between the ergodic liquid and two distinct amorphous solids, we establish coexistence between these two amorphous solids. The phase diagram we predict includes a nonequilibrium triple point where two amorphous phases and the liquid coexist. Whereas the amorphous solids are long-lived and slowly aging glasses, their melting can lead quickly to the formation of crystalline ice. Further, melting of the higher density amorphous solid at low pressures takes place in steps, transitioning to the lower-density glass before accessing a nonequilibrium liquid from which ice coarsens.
Regio-Selective Intramolecular Hydrogen/Deuterium Exchange in Gas-Phase Electron Transfer Dissociation

NASA Astrophysics Data System (ADS)

Hamuro, Yoshitomo

2017-05-01

Protein backbone amide hydrogen/deuterium exchange mass spectrometry (HDX-MS) typically utilizes enzymatic digestion after the exchange reaction and before MS analysis to improve data resolution. Gas-phase fragmentation of a peptic fragment prior to MS analysis is a promising technique to further increase the resolution. The biggest technical challenge for this method is elimination of intramolecular hydrogen/deuterium exchange (scrambling) in the gas phase. The scrambling obscures the location of deuterium. Jørgensen's group pioneered a method to minimize the scrambling in gas-phase electron capture/transfer dissociation. Despite active investigation, the mechanism of hydrogen scrambling is not well-understood. The difficulty stems from the fact that the degree of hydrogen scrambling depends on instruments, various parameters of mass analysis, and peptide analyzed. In most hydrogen scrambling investigations, the hydrogen scrambling is measured by the percentage of scrambling in a whole molecule. This paper demonstrates that the degree of intramolecular hydrogen/deuterium exchange depends on the nature of exchangeable hydrogen sites. The deuterium on Tyr amide of neurotensin (9-13), Arg-Pro-Tyr-Ile-Leu, migrated significantly faster than that on Ile or Leu amides, indicating the loss of deuterium from the original sites is not mere randomization of hydrogen and deuterium but more site-specific phenomena. This more precise approach may help understand the mechanism of intramolecular hydrogen exchange and provide higher confidence for the parameter optimization to eliminate intramolecular hydrogen/deuterium exchange during gas-phase fragmentation.
Regio-Selective Intramolecular Hydrogen/Deuterium Exchange in Gas-Phase Electron Transfer Dissociation.

PubMed

Hamuro, Yoshitomo

2017-05-01

Protein backbone amide hydrogen/deuterium exchange mass spectrometry (HDX-MS) typically utilizes enzymatic digestion after the exchange reaction and before MS analysis to improve data resolution. Gas-phase fragmentation of a peptic fragment prior to MS analysis is a promising technique to further increase the resolution. The biggest technical challenge for this method is elimination of intramolecular hydrogen/deuterium exchange (scrambling) in the gas phase. The scrambling obscures the location of deuterium. Jørgensen's group pioneered a method to minimize the scrambling in gas-phase electron capture/transfer dissociation. Despite active investigation, the mechanism of hydrogen scrambling is not well-understood. The difficulty stems from the fact that the degree of hydrogen scrambling depends on instruments, various parameters of mass analysis, and peptide analyzed. In most hydrogen scrambling investigations, the hydrogen scrambling is measured by the percentage of scrambling in a whole molecule. This paper demonstrates that the degree of intramolecular hydrogen/deuterium exchange depends on the nature of exchangeable hydrogen sites. The deuterium on Tyr amide of neurotensin (9-13), Arg-Pro-Tyr-Ile-Leu, migrated significantly faster than that on Ile or Leu amides, indicating the loss of deuterium from the original sites is not mere randomization of hydrogen and deuterium but more site-specific phenomena. This more precise approach may help understand the mechanism of intramolecular hydrogen exchange and provide higher confidence for the parameter optimization to eliminate intramolecular hydrogen/deuterium exchange during gas-phase fragmentation. Graphical Abstract ᅟ.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Kirka, Michael M.; Nandwana, Peeyush; Lee, Yousub

Additive manufacturing (AM) of metals is rapidly emerging as an established manufacturing process for metal components. Unlike traditional metals fabrication processes, metals fabricated via AM undergo localized thermal cycles during fabrication. As a result, AM presents the opportunity to control the liquid-solid phase transformation, i.e. material texture. But, thermal cycling presents challenges from the standpoint of solid-solid phase transformations. We will discuss the opportunities and challenges in metals AM in the context of texture control and associated solid-solid phase transformations in Ti-6Al-4V and Inconel 718.
Determination of bisphenols in beverages by mixed-mode solid-phase extraction and liquid chromatography coupled to tandem mass spectrometry.

PubMed

Regueiro, Jorge; Wenzl, Thomas

2015-11-27

Facing growing restrictions on the use of bisphenol A in food contact materials, several bisphenol analogs are arising as major alternatives to replace this chemical in most of its applications. This work reports a simple and robust method based on mixed-mode solid-phase extraction and stable-isotope dilution liquid chromatography-tandem mass spectrometry for the analysis of bisphenol A and its main analogs - bisphenol S, 4,4'-sulfonylbis(2-methylphenol), bisphenol F, bisphenol E, bisphenol B, bisphenol Z, bisphenol AF, bisphenol AP, tetrabromobisphenol A and bisphenol P - in alcoholic and non-alcoholic beverages. Mixed-mode solid-phase extraction, combining cationic exchange and reversed-phase mechanisms, was optimized to provide a selective extraction and purification of the target analytes. Derivatization of bisphenols with pyridine-3-sulfonyl chloride allowed increasing their ionization efficiency by electrospray ionization. Validation of the proposed method was performed in terms of selectivity, matrix effects, linearity, precision, measurement uncertainty, trueness and limits of detection. Satisfactory repeatability and intermediate precision were obtained; the related relative standard deviations were ≤9% and ≤12%, respectively. The relative expanded uncertainty (k=2) was below 20% for all bisphenol analogs and the trueness of the method was demonstrated by recovery experiments. Limits of detection (LOD) ranged from 1.6ngL(-1) to 27.9ngL(-1) for all compounds. Finally, several canned and non-canned beverages were analyzed to demonstrate the applicability of the method. Only bisphenol A and three bisphenol F isomers were detected in any of the samples. Bisphenol A concentration ranged from
Mineral transformation controls speciation and pore-fluid transmission of contaminants in waste-weathered Hanford sediments

NASA Astrophysics Data System (ADS)

Perdrial, Nicolas; Thompson, Aaron; O'Day, Peggy A.; Steefel, Carl I.; Chorover, Jon

2014-09-01

Portions of the Hanford Site (WA, USA) vadose zone were subjected to weathering by caustic solutions during documented releases of high level radioactive waste (containing Sr, Cs and I) from leaking underground storage tanks. Previous studies have shown that waste-sediment interactions can promote variable incorporation of contaminants into neo-formed mineral products (including feldspathoids and zeolites), but processes regulating the subsequent contaminant release from these phases into infiltrating background pore waters remain poorly known. In this paper, reactive transport experiments were conducted with Hanford sediments previously weathered for one year in simulated hyper-alkaline waste solutions containing high or low 88Sr, 127I, and 133Cs concentrations, with or without CO2(aq). These waste-weathered sediments were leached in flow-through column experiments with simulated background pore water (characteristic of meteoric recharge) to measure contaminant release from solids formed during waste-sediment interaction. Contaminant sorption-desorption kinetics and mineral transformation reactions were both monitored using continuous-flow and wet-dry cycling regimes for ca. 300 pore volumes. Less than 20% of contaminant 133Cs and 88Sr mass and less than 40% 127I mass were released over the course of the experiment. To elucidate molecular processes limiting contaminant release, reacted sediments were studied with micro- (TEM and XRD) and molecular- (Sr K-edge EXAFS) scale methods. Contaminant dynamics in column experiments were principally controlled by rapid dissolution of labile solids and competitive exchange reactions. In initially feldspathoidic systems, time-dependent changes in the local zeolitic bonding environment observed with X-ray diffraction and EXAFS are responsible for limiting contaminant release. Linear combination fits and shell-by-shell analysis of Sr K-edge EXAFS data revealed modification in Sr-Si/Al distances within the zeolite cage. Wet-dry cycling did not affect significantly molecular-scale transformations relative to continuous-flow controls. Results indicate that contaminants bound to the solid phase in distinct micro- and molecular-scale coordinative environments can generate similar macro-scale release behaviors, highlighting the need for multi-scale interrogations to constrain mechanisms of reactive transport. Data also indicate that weathering-induced change in ion exchange selectivity coefficients should be incorporated in simulations of contaminant release from caustic high-level radioactive waste impacted sediments.
Phase relations in the system NaCl-KCl-H2O: V. Thermodynamic-PTX analysis of solid-liquid equilibria at high temperatures and pressures

USGS Publications Warehouse

Sterner, S.M.; Chou, I.-Ming; Downs, R.T.; Pitzer, Kenneth S.

1992-01-01

The Gibbs energies of mixing for NaCl-KCl binary solids and liquids and solid-saturated NaCl-KCl-H2O ternary liquids were modeled using asymmetric Margules treatments. The coefficients of the expressions were calibrated using an extensive array of binary solvus and solidus data, and both binary and ternary liquidus data. Over the PTX range considered, the system exhibits complete liquid miscibility among all three components and extensive solid solution along the anhydrous binary. Solid-liquid and solid-solid phase equilibria were calculated by using the resulting equations and invoking the equality of chemical potentials of NaCl and KCl between appropriate phases at equilibrium. The equations reproduce the ternary liquidus and predict activity coefficients for NaCl and KCl components in the aqueous liquid under solid-saturation conditions between 673 and 1200 K from vapor saturation up to 5 kbar. In the NaCl-KCl anhydrous binary system, the equations describe phase equilibria and predict activity coefficients of the salt components for all stable compositions of solid and liquid phases between room temperature and 1200 K and from 1 bar to 5 kbar. ?? 1992.
Binary Solid-Liquid Phase Diagram of Phenol and t-Butanol: An Undergraduate Physical Chemistry Experiment

ERIC Educational Resources Information Center

Xu, Xinhua; Wang, Xiaogang; Wu, Meifen

2014-01-01

The determination of the solid-liquid phase diagram of a binary system is always used as an experiment in the undergraduate physical chemistry laboratory courses. However, most phase diagrams investigated in the lab are simple eutectic ones, despite the fact that complex binary solid-liquid phase diagrams are more common. In this article, the…
Phase transitions of amorphous solid acetone in confined geometry investigated by reflection absorption infrared spectroscopy.

PubMed

Shin, Sunghwan; Kang, Hani; Kim, Jun Soo; Kang, Heon

2014-11-26

We investigated the phase transformations of amorphous solid acetone under confined geometry by preparing acetone films trapped in amorphous solid water (ASW) or CCl4. Reflection absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) were used to monitor the phase changes of the acetone sample with increasing temperature. An acetone film trapped in ASW shows an abrupt change in the RAIRS features of the acetone vibrational bands during heating from 80 to 100 K, which indicates the transformation of amorphous solid acetone to a molecularly aligned crystalline phase. Further heating of the sample to 140 K produces an isotropic solid phase, and eventually a fluid phase near 157 K, at which the acetone sample is probably trapped in a pressurized, superheated condition inside the ASW matrix. Inside a CCl4 matrix, amorphous solid acetone crystallizes into a different, isotropic structure at ca. 90 K. We propose that the molecularly aligned crystalline phase formed in ASW is created by heterogeneous nucleation at the acetone-water interface, with resultant crystal growth, whereas the isotropic crystalline phase in CCl4 is formed by homogeneous crystal growth starting from the bulk region of the acetone sample.
Determination of phosphonoformate (foscarnet) in calf and human serum by automated solid-phase extraction and high-performance liquid chromatography with amperometric detection.

PubMed

Ba, B B; Corniot, A G; Ducint, D; Breilh, D; Grellet, J; Saux, M C

1999-03-05

An isocratic high-performance liquid chromatographic method with automated solid-phase extraction has been developed to determine foscarnet in calf and human serums. Extraction was performed with an anion exchanger, SAX, from which the analyte was eluted with a 50 mM potassium pyrophosphate buffer, pH 8.4. The mobile phase consisted of methanol-40 mM disodium hydrogenphosphate, pH 7.6 containing 0.25 mM tetrahexylammonium hydrogensulphate (25:75, v/v). The analyte was separated on a polyether ether ketone (PEEK) column 150x4.6 mm I.D. packed with Kromasil 100 C18, 5 microm. Amperometric detection allowed a quantification limit of 15 microM. The assay was linear from 15 to 240 microM. The recovery of foscarnet from calf serum ranged from 60.65+/-1.89% for 15 microM to 67.45+/-1.24% for 200 microM. The coefficient of variation was < or = 3.73% for intra-assay precision and < or =7.24% for inter-assay precision for calf serum concentrations ranged from 15 to 800 microM. For the same samples, the deviation from the nominal value ranged from -8.97% to +5.40% for same day accuracy and from -4.50% to +2.77% for day-to-day accuracy. Selectivity was satisfactory towards potential co-medications. Replacement of human serum by calf serum for calibration standards and quality control samples was validated. Automation brought more protection against biohazards and increase in productivity for routine monitoring and pharmacokinetic studies.
Methods and systems for concentrated solar power

DOEpatents

Ma, Zhiwen

2016-05-24

Embodiments described herein relate to a method of producing energy from concentrated solar flux. The method includes dropping granular solid particles through a solar flux receiver configured to transfer energy from concentrated solar flux incident on the solar flux receiver to the granular solid particles as heat. The method also includes fluidizing the granular solid particles from the solar flux receiver to produce a gas-solid fluid. The gas-solid fluid is passed through a heat exchanger to transfer heat from the solid particles in the gas-solid fluid to a working fluid. The granular solid particles are extracted from the gas-solid fluid such that the granular solid particles can be dropped through the solar flux receiver again.
Exploration and characterization of new synthesis methods for C60 colloidal suspensions in water

NASA Astrophysics Data System (ADS)

Hilburn, Martha E.

Buckminsterfullerene, C60, has been used in the production of several commercial products from badminton racquets and lubricants for their mechanical properties to cosmetics and even dietary supplements for their "antioxidant" properties. Multi-ton production of C60 began in 2003 encouraging serious consideration of its fate in the environment in the case of an accidental release or improper disposal. Although C60 is practically insoluble in water, it readily forms stable aqueous colloidal suspensions (termed nC60) through solvent exchange methods or long-term vigorous stirring in water. Two new solvent exchange methods for synthesizing nC60 are presented. These methods combine key advantages of multiple existing synthesis methods including high yield, narrow particle size distribution, short synthesis time, and an absence of solvents such as tetrahydrofuran that have historically caused problems in laboratory synthesized aggregates. The resulting samples are attractive candidates for use in controlled environmental impact, biological, and toxicity studies. An improved method for quantifying residual solvents in nC60 samples utilizing solid phase micro extraction gas chromatography mass spectrometry (SPME-GC-MS) is also discussed.
Bead mediated separation of microparticles in droplets.

PubMed

Wang, Sida; Sung, Ki-Joo; Lin, Xiaoxia Nina; Burns, Mark A

2017-01-01

Exchange of components such as particles and cells in droplets is important and highly desired in droplet microfluidic assays, and many current technologies use electrical or magnetic fields to accomplish this process. Bead-based microfluidic techniques offer an alternative approach that uses the bead's solid surface to immobilize targets like particles or biological material. In this paper, we demonstrate a bead-based technique for exchanging droplet content by separating fluorescent microparticles in a microfluidic device. The device uses posts to filter surface-functionalized beads from a droplet and re-capture the filtered beads in a new droplet. With post spacing of 7 μm, beads above 10 μm had 100% capture efficiency. We demonstrate the efficacy of this system using targeted particles that bind onto the functionalized beads and are, therefore, transferred from one solution to another in the device. Binding capacity tests performed in the bulk phase showed an average binding capacity of 5 particles to each bead. The microfluidic device successfully separated the targeted particles from the non-targeted particles with up to 98% purity and 100% yield.
Bead mediated separation of microparticles in droplets

PubMed Central

Sung, Ki-Joo; Lin, Xiaoxia Nina; Burns, Mark A.

2017-01-01

Exchange of components such as particles and cells in droplets is important and highly desired in droplet microfluidic assays, and many current technologies use electrical or magnetic fields to accomplish this process. Bead-based microfluidic techniques offer an alternative approach that uses the bead’s solid surface to immobilize targets like particles or biological material. In this paper, we demonstrate a bead-based technique for exchanging droplet content by separating fluorescent microparticles in a microfluidic device. The device uses posts to filter surface-functionalized beads from a droplet and re-capture the filtered beads in a new droplet. With post spacing of 7 μm, beads above 10 μm had 100% capture efficiency. We demonstrate the efficacy of this system using targeted particles that bind onto the functionalized beads and are, therefore, transferred from one solution to another in the device. Binding capacity tests performed in the bulk phase showed an average binding capacity of 5 particles to each bead. The microfluidic device successfully separated the targeted particles from the non-targeted particles with up to 98% purity and 100% yield. PMID:28282412
Assessing the performance of the Tran-Blaha modified Becke-Johnson exchange potential for optical constants of semiconductors in the ultraviolet-visible light region

NASA Astrophysics Data System (ADS)

Nakano, Kousuke; Sakai, Tomohiro

2018-01-01

We report on the performance of density functional theory (DFT) with the Tran-Blaha modified Becke-Johnson exchange potential and the random phase approximation dielectric function for optical constants of semiconductors in the ultraviolet-visible (UV-Vis) light region. We calculate optical bandgaps Eg, refractive indices n, and extinction coefficients k of 70 semiconductors listed in the Handbook of Optical Constants of Solids [(Academic Press, 1985), Vol. 1; (Academic Press, 1991), Vol. 2; and (Academic Press, 1998), Vol. 3] and compare the results with experimental values. The results show that the calculated bandgaps and optical constants agree well with the experimental values to within 0.440 eV for Eg, 0.246-0.299 for n, and 0.207-0.598 for k in root mean squared error (RMSE). The small values of the RMSEs indicate that the optical constants of semiconductors in the UV-Vis region can be quantitatively predicted even by a low-cost DFT calculation of this type.
Fission product ion exchange between zeolite and a molten salt

NASA Astrophysics Data System (ADS)

Gougar, Mary Lou D.

The electrometallurgical treatment of spent nuclear fuel (SNF) has been developed at Argonne National Laboratory (ANL) and has been demonstrated through processing the sodium-bonded SNF from the Experimental Breeder Reactor-II in Idaho. In this process, components of the SNF, including U and species more chemically active than U, are oxidized into a bath of lithium-potassium chloride (LiCl-KCl) eutectic molten salt. Uranium is removed from the salt solution by electrochemical reduction. The noble metals and inactive fission products from the SNF remain as solids and are melted into a metal waste form after removal from the molten salt bath. The remaining salt solution contains most of the fission products and transuranic elements from the SNF. One technique that has been identified for removing these fission products and extending the usable life of the molten salt is ion exchange with zeolite A. A model has been developed and tested for its ability to describe the ion exchange of fission product species between zeolite A and a molten salt bath used for pyroprocessing of spent nuclear fuel. The model assumes (1) a system at equilibrium, (2) immobilization of species from the process salt solution via both ion exchange and occlusion in the zeolite cage structure, and (3) chemical independence of the process salt species. The first assumption simplifies the description of this physical system by eliminating the complications of including time-dependent variables. An equilibrium state between species concentrations in the two exchange phases is a common basis for ion exchange models found in the literature. Assumption two is non-simplifying with respect to the mathematical expression of the model. Two Langmuir-like fractional terms (one for each mode of immobilization) compose each equation describing each salt species. The third assumption offers great simplification over more traditional ion exchange modeling, in which interaction of solvent species with each other is considered. (Abstract shortened by UMI.)
Preparation and storage of isotopically labeled reduced nicotinamide adenine dinucleotide

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

Northrop, D.B.; Duggleby, R.G.

1987-09-01

A method for obtaining highly purified NADH in a dry, solid, and stable form is described. The method involves improvements of the ion-exchange and reversed-phase chromatographic procedures of C. J. Newton and S. M. Faynor, and D. B. Northrop. The necessary time to prepare pure NADH has been reduced to a few hours. The final product, obtained by drying the nucleotide from absolute ethanol, shows no detectable decomposition either during the drying procedure or during storage under nitrogen gas at -20 degrees C for several months. Using dry product prepared from fixed volumes of ethanolic solution, standardized solutions of knownmore » amounts of the highly purified and stored NADH can be obtained in a few seconds.« less
Solid electrolyte-electrode system for an electrochemical cell

DOEpatents

Tuller, Harry L.; Kramer, Steve A.; Spears, Marlene A.

1995-01-01

An electrochemical device including a solid electrolyte and solid electrode composed of materials having different chemical compositions and characterized by different electrical properties but having the same crystalline phase is provided. A method for fabricating an electrochemical device having a solid electrode and solid electrolyte characterized by the same crystalline phase is also provided.

Investigation of two-phase heat transfer coefficients of argon-freon cryogenic mixed refrigerants

NASA Astrophysics Data System (ADS)

Baek, Seungwhan; Lee, Cheonkyu; Jeong, Sangkwon

2014-11-01

Mixed refrigerant Joule Thomson refrigerators are widely used in various kinds of cryogenic systems these days. Although heat transfer coefficient estimation for a multi-phase and multi-component fluid in the cryogenic temperature range is necessarily required in the heat exchanger design of mixed refrigerant Joule Thomson refrigerators, it has been rarely discussed so far. In this paper, condensation and evaporation heat transfer coefficients of argon-freon mixed refrigerant are measured in a microchannel heat exchanger. A Printed Circuit Heat Exchanger (PCHE) with 340 μm hydraulic diameter has been developed as a compact microchannel heat exchanger and utilized in the experiment. Several two-phase heat transfer coefficient correlations are examined to discuss the experimental measurement results. The result of this paper shows that cryogenic two-phase mixed refrigerant heat transfer coefficients can be estimated by conventional two-phase heat transfer coefficient correlations.
Validated method for determination of eight banned nitroimidazole residues in natural casings by LC/MS/MS with solid-phase extraction.

PubMed

Sun, Hanwen; Wang, Fengchi; Ai, Lianfeng; Guo, Chunhai; Chen, Ruichun

2009-01-01

A sensitive method based on solid-phase extraction-liquid chromatography-tandem mass spectrometry interfaced with electrospray ionization (SPE-LC-MS/MS-ESI) was developed for the simultaneous determination of 8 banned nitroimidazole (NOZ) drugs including metronidazole (MNZ), ronidazole (RNZ), dimetridazole (DMZ), tinidazole, ornidazole, secnidazole, metronidazole-OH (MNZOH, the metabolite of MNZ), and 2-hydroxymethyl-1-methyl-5-nitroimidazole (HMMNI, the metabolite of RNZ and DMZ) in natural casings. After extraction with ethyl acetate and evaporation, the NOZs were reconstituted in ethyl acetate and purified on a strong cation-exchange SPE column, and then LC/MS/MS analysis was performed by positive ESI applying multiple reaction monitoring of 2 transition reactions for each compound. The method was validated according to the European Union requirements (Commission Decision 2002/657/EC). Specificity, linearity, decision limit (CCalpha), detection capability (CCbeta), accuracy, and precision were determined. Average recoveries of the 8 NOZs from natural animal casing fortified at 3 levels (0.1, 0.5, and 1 microg/kg) ranged from 87.3 to 116.5%. The calculated CCalpha for NOZs ranged from 0.029 to 0.049 microg/kg, and CCbeta ranged from 0.049 to 0.083 microg/kg. Repeatability was in the range of 3.35-10.1%, and within-laboratory reproducibility was <10.3%.
Chloride leaching and solvent extraction of cadmium, cobalt and nickel from spent nickel-cadmium, batteries using Cyanex 923 and 272

NASA Astrophysics Data System (ADS)

Reddy, B. Ramachandra; Priya, D. Neela

Studies are conducted on the leaching and solvent extraction separation of metals from chloride leach liquor of spent nickel-cadmium batteries with Cyanex 923 and 272 diluted in kerosene as the extractants. Dissolution of the metals increases with increase in acid concentration and time but decreases with the solids-to-liquid ratio. Complete dissolution of Cd, Co and Ni can be achieved with 1.5 M HCl at 85 °C for 8 h and a solids-to-liquid ratio of 4. Treatment of leach liquor for the separation of metals with Cyanex 923 shows that increase of extractant and chloride ion concentration increases the percentage extraction of cadmium. The plot of log[distribution coefficient] versus log[extractant]/[Cl -] is linear with a slope of 2, which indicates that the extraction follows a solvation mechanism with the extracted species as CdCl 2·2S (S, Cyanex 923). Moreover, Cyanex 923 enables a clear separation of Cd from Co and Ni. Extraction of cobalt with Cyanex 272 involves a cation-exchange mechanism with the formation of a 1:2 metal-to-ligand complex in the organic phase. Based on the distribution data, extractant concentration and equilibrium pH of the aqueous phase, a possible separation process is proposed for the recovery of cadmium, cobalt and nickel with >99% efficiency.
Solid-phase extraction and GC-MS analysis of THC-COOH method optimized for a high-throughput forensic drug-testing laboratory.

PubMed

Stout, P R; Horn, C K; Klette, K L

2001-10-01

In order to facilitate the confirmation analysis of large numbers of urine samples previously screened positive for delta9-tetrahydrocannabinol (THC), an extraction, derivitization, and GC-MS analysis method was developed. This method utilized a positive pressure manifold anion-exchange polymer-based solid-phase extraction followed by elution directly into the automated liquid sampling (ALS) vials. Rapid derivitization was accomplished using pentafluoropropionic anhydride/pentafluoropropanol (PFPA/PFPOH). Recoveries averaged 95% with a limit of detection of 0.875 ng/mL with a 3-mL sample volume. Performance of 11-nor-delta9-tetrahydrocannabinol-9-carboxylic acid (THC-COOH)-d3 and THC-COOH-d9 internal standards were evaluated. The method was linear to 900 ng/mL THC-COOH using THC-COOH-d9 with negligible contribution from the internal standard to very weak samples. Excellent agreement was seen with previous quantitations of human urine samples. More than 1000 human urine samples were analyzed using the method with 300 samples analyzed using an alternate qualifier ion (m/z 622) after some interference was observed with a qualifier ion (m/z 489). The 622 ion did not exhibit any interference even in samples with interfering peaks present in the 489 ion. The method resulted in dramatic reductions in processing time, waste production, and exposure hazards to laboratory personnel.
Critical micelle concentration values for different surfactants measured with solid-phase microextraction fibers.

PubMed

Haftka, Joris J-H; Scherpenisse, Peter; Oetter, Günter; Hodges, Geoff; Eadsforth, Charles V; Kotthoff, Matthias; Hermens, Joop L M

2016-09-01

The amphiphilic nature of surfactants drives the formation of micelles at the critical micelle concentration (CMC). Solid-phase microextraction (SPME) fibers were used in the present study to measure CMC values of 12 nonionic, anionic, cationic, and zwitterionic surfactants. The SPME-derived CMC values were compared to values determined using a traditional surface tension method. At the CMC of a surfactant, a break in the relationship between the concentration in SPME fibers and the concentration in water is observed. The CMC values determined with SPME fibers deviated by less than a factor of 3 from values determined with a surface tension method for 7 out of 12 compounds. In addition, the fiber-water sorption isotherms gave information about the sorption mechanism to polyacrylate-coated SPME fibers. A limitation of the SPME method is that CMCs for very hydrophobic cationic surfactants cannot be determined when the cation exchange capacity of the SPME fibers is lower than the CMC value. The advantage of the SPME method over other methods is that CMC values of individual compounds in a mixture can be determined with this method. However, CMC values may be affected by the presence of compounds with other chain lengths in the mixture because of possible mixed micelle formation. Environ Toxicol Chem 2016;35:2173-2181. © 2016 SETAC. © 2016 SETAC.
A Liquid-Liquid Thermoelectric Heat Exchanger as a Heat Pump for Testing Phase Change Material Heat Exchangers

NASA Technical Reports Server (NTRS)

Sheth, Rubik B.; Makinen, Janice; Le, Hung V.

2016-01-01

The primary objective of the Phase Change HX payload on the International Space Station (ISS) is to test and demonstrate the viability and performance of Phase Change Material Heat Exchangers (PCM HX). The system was required to pump a working fluid through a PCM HX to promote the phase change material to freeze and thaw as expected on Orion's Multipurpose Crew Vehicle. Due to limitations on ISS's Internal Thermal Control System, a heat pump was needed on the Phase Change HX payload to help with reducing the working fluid's temperature to below 0degC (32degF). This paper will review the design and development of a TEC based liquid-liquid heat exchanger as a way to vary to fluid temperature for the freeze and thaw phase of the PCM HX. Specifically, the paper will review the design of custom coldplates and sizing for the required heat removal of the HX.
Adsorption of the Three-phase Emulsion on Various Solid Surfaces.

PubMed

Enomoto, Yasutaka; Imai, Yoko; Tajima, Kazuo

2017-07-01

The present study investigates the adsorption of the three-phase emulsion on various solid/water interfaces. Vesicles can be used as emulsifiers in the three-phase emulsions and act as an independent phase unlike the surfactant used in conventional emulsions; therefore, it is expected that the three-phase emulsion formed by the adhesion of vesicles to the oil/water interface will adsorb on various solid/water interfaces. The cationic three-phase emulsion was prepared to encourage emulsion adsorption on negatively charged solid substrates in water. The emulsifier polyoxyethylene-(10) hydrogenated castor oil was rendered cationic by mixing with the surfactant cetyltrimethylammonium bromide and then used to prepare the cationic three-phase emulsion of hexadecane-in-water. Three solid substrates (silicon, glass, and copper) were dipped in the cationic emulsion and the emulsion was found to adsorb on the solid substrates while maintaining its structure. The amount of hexadecane adsorbed on the various surfaces was investigated by gas chromatography and found to increase with increasing hexadecane concentration in the emulsion and eventually plateaued just like molecular adsorption. The maximum surface coverage of the emulsion on the substrates was approximately 80%. However, even the equivalent nonionic three-phase emulsion was found to adsorb on the three solid surfaces. This was attributed to a novel mechanism of irreversible adhesion via the van der Waals attractive force.
Manual Solid-Phase Peptide Synthesis of Metallocene-Peptide Bioconjugates

ERIC Educational Resources Information Center

Kirin, Srecko I.; Noor, Fozia; Metzler-Nolte, Nils; Mier, Walter

2007-01-01

A simple and relatively inexpensive procedure for preparing a biologically active peptide using solid phase peptide synthesis (SPPS) is described. Fourth-year undergraduate students have gained firsthand experience from the solid-phase synthesis techniques and they have become familiar with modern analytical techniques based on the particular…
THE ROLE OF AQUEOUS THIN FILM EVAPORATIVE COOLING ON RATES OF ELEMENTAL MERCURY AIR-WATER EXCHANGE UNDER TEMPERATURE DISEQUILIBRIUM CONDITIONS

EPA Science Inventory

The technical conununity has only recently addressed the role of atmospheric temperature variations on rates of air-water vapor phase toxicant exchange. The technical literature has documented that: 1) day time rates of elemental mercury vapor phase air-water exchange can exceed ...
Effect of solid-meal caloric content on gastric emptying kinetics of solids and liquids.

PubMed

Urbain, J L; Siegel, J A; Mortelmans, L; van Cutsem, E; van den Maegdenbergh, V; de Roo, M

1989-08-01

In this study, we have evaluated the effect of the caloric content of a physiological test meal on the gastric emptying kinetics of solids and liquids. 22 healthy male volunteers were studied in two groups matched for age. After an overnight fast, each volunteer underwent the same test procedure; in the first group (G I), 10 volunteers received a meal consisting of bread, 111In-DTPA water and 1 scrambled egg labeled with 99mTc-labelled sulphur colloid; in the second group (G II) 12 volunteers were given the same meal but with 2 labeled eggs in order to increase the caloric content of the solid phase meal. Simultaneous anterior and posterior images were recorded using a dual-headed gamma camera. Solid and liquid geometric mean data were analyzed to determine the lag phase, the emptying rate and the half-emptying time for both solids and liquids. Solid and liquid gastric half-emptying times were significantly prolonged in G II compared to G I volunteers. For the solid phased, the delay was accounted for by a longer lag phase and a decrease in the equilibrium emptying rate. The emptying rate of the liquid phase was significantly decreased in G II compared to G I. Within each group, no statistically significant difference was observed between solid and liquid emptying rates. We conclude that the caloric content of the solid portion of a meal not only alters the emptying of the solid phase but also affects the emptying of the liquid component of the meal.
Interaction of ammonium with birnessite: Evidence of a chemical and structural transformation in alkaline aqueous medium

NASA Astrophysics Data System (ADS)

Boumaiza, Hella; Coustel, Romain; Despas, Christelle; Ruby, Christian; Bergaoui, Latifa

2018-02-01

The ammonium cation interaction with Na-birnessite in aqueous alkaline medium was studied. Solution and solid analysis give evidence that birnessite is not only acting as a cationic exchanger toward NH4+. The surface analysis performed by XPS showed that N1s spectra are characterized by the existence of two different environments: one assignable to an interlayer NH4+ and the second to a chemisorbed N-species. Structural and chemical transformations were observed on birnessite with nitrogen mass balance deficit. The monitoring of NH4+, Na+, Mn2+, NO3- and NO2- and solid changes (average oxidation state of Mn, cation exchange capacity, solid nitrogen content and symmetry evolution identified by XRD and FTIR) indicate unambiguously that NH4+ reacts chemically with the birnessite.
Theory of amorphous ices

PubMed Central

Limmer, David T.; Chandler, David

2014-01-01

We derive a phase diagram for amorphous solids and liquid supercooled water and explain why the amorphous solids of water exist in several different forms. Application of large-deviation theory allows us to prepare such phases in computer simulations. Along with nonequilibrium transitions between the ergodic liquid and two distinct amorphous solids, we establish coexistence between these two amorphous solids. The phase diagram we predict includes a nonequilibrium triple point where two amorphous phases and the liquid coexist. Whereas the amorphous solids are long-lived and slowly aging glasses, their melting can lead quickly to the formation of crystalline ice. Further, melting of the higher density amorphous solid at low pressures takes place in steps, transitioning to the lower-density glass before accessing a nonequilibrium liquid from which ice coarsens. PMID:24858957
Electron drift in a large scale solid xenon

DOE PAGES

Yoo, J.; Jaskierny, W. F.

2015-08-21

A study of charge drift in a large scale optically transparent solid xenon is reported. A pulsed high power xenon light source is used to liberate electrons from a photocathode. The drift speeds of the electrons are measured using a 8.7 cm long electrode in both the liquid and solid phase of xenon. In the liquid phase (163 K), the drift speed is 0.193 ± 0.003 cm/μs while the drift speed in the solid phase (157 K) is 0.397 ± 0.006 cm/μs at 900 V/cm over 8.0 cm of uniform electric fields. Furthermore, it is demonstrated that a factor twomore » faster electron drift speed in solid phase xenon compared to that in liquid in a large scale solid xenon.« less
Electromagnon dispersion probed by inelastic X-ray scattering in LiCrO2

PubMed Central

Tóth, Sándor; Wehinger, Björn; Rolfs, Katharina; Birol, Turan; Stuhr, Uwe; Takatsu, Hiroshi; Kimura, Kenta; Kimura, Tsuyoshi; Rønnow, Henrik M.; Rüegg, Christian

2016-01-01

Inelastic X-ray scattering with meV energy resolution (IXS) is an ideal tool to measure collective excitations in solids and liquids. In non-resonant scattering condition, the cross-section is strongly dominated by lattice vibrations (phonons). However, it is possible to probe additional degrees of freedom such as magnetic fluctuations that are strongly coupled to the phonons. The IXS spectrum of the coupled system contains not only the phonon dispersion but also the so far undetected magnetic correlation function. Here we report the observation of strong magnon–phonon coupling in LiCrO2 that enables the measurement of magnetic correlations throughout the Brillouin zone via IXS. We find electromagnon excitations and electric dipole active two-magnon excitations in the magnetically ordered phase and heavily damped electromagnons in the paramagnetic phase of LiCrO2. We predict that several (frustrated) magnets with dominant direct exchange and non-collinear magnetism show surprisingly large IXS cross-section for magnons and multi-magnon processes. PMID:27882928
Production and Characterization of a New α-Glucosidase Inhibitory Peptide from Aspergillus oryzae N159-1

PubMed Central

Kang, Min-Gu; Yi, Sung-Hun

2013-01-01

An α-glucosidase inhibitor was developed from Aspergillus oryzae N159-1, which was screened from traditional fermented Korean foods. The intracellular concentration of the inhibitor reached its highest level when the fungus was cultured in tryptic soy broth medium at 27℃ for five days. The inhibitor was purified using a series of purification steps involving ultrafiltration, Sephadex G-25 gel permeation chromatography, strong cation exchange solid phase extraction, reverse-phase high performance liquid chromatography, and size exclusion chromatography. The final yield of the purification was 1.9%. Results of the liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis indicated that the purified α-glucosidase inhibitor was a tri-peptide, Pro-Phe-Pro, with the molecular weight of 360.1 Da. The IC50 value of the peptide against α-glucosidase activity was 3.1 mg/mL. Using Lineweaver-Burk plot analysis, the inhibition pattern indicated that the inhibitor acts as a mixed type inhibitor. PMID:24198670
Sequential Extraction Results and Mineralogy of Mine Waste and Stream Sediments Associated With Metal Mines in Vermont, Maine, and New Zealand

USGS Publications Warehouse

Piatak, N.M.; Seal, R.R.; Sanzolone, R.F.; Lamothe, P.J.; Brown, Z.A.; Adams, M.

2007-01-01

We report results from sequential extraction experiments and the quantitative mineralogy for samples of stream sediments and mine wastes collected from metal mines. Samples were from the Elizabeth, Ely Copper, and Pike Hill Copper mines in Vermont, the Callahan Mine in Maine, and the Martha Mine in New Zealand. The extraction technique targeted the following operationally defined fractions and solid-phase forms: (1) soluble, adsorbed, and exchangeable fractions; (2) carbonates; (3) organic material; (4) amorphous iron- and aluminum-hydroxides and crystalline manganese-oxides; (5) crystalline iron-oxides; (6) sulfides and selenides; and (7) residual material. For most elements, the sum of an element from all extractions steps correlated well with the original unleached concentration. Also, the quantitative mineralogy of the original material compared to that of the residues from two extraction steps gave insight into the effectiveness of reagents at dissolving targeted phases. The data are presented here with minimal interpretation or discussion and further analyses and interpretation will be presented elsewhere.
β-Na2TeO4: Phase Transition from an Orthorhombic to a Monoclinic Form. Reversible CO2 Capture.

PubMed

Galven, Cyrille; Pagnier, Thierry; Rosman, Noël; Le Berre, Françoise; Crosnier-Lopez, Marie-Pierre

2018-06-18

The present work concerns the tellurate Na 2 TeO 4 which has a 1D structure and could then present a CO 2 capture ability. It has been synthesized in a powder form via a solid-state reaction and structurally characterized by thermal X-ray diffraction experiments, Raman spectroscopy, and differential scanning calorimetry. The room temperature structure corresponds to the β-Na 2 TeO 4 orthorhombic form, and we show that it undergoes a reversible structural transition near 420 °C toward a monoclinic system. Ab initio computations were also performed on the room temperature structure, the Raman vibration modes calculated, and a normal mode attribution proposed. In agreement with our expectations, this sodium oxide is able to trap CO 2 by a two-step mechanism: Na + /H + exchange and carbonation of the released sodium as NaHCO 3 . This capture is reversible since CO 2 can be released upon heating by recombination of the mother phase.
Grain Floatation During Equiaxed Solidification of an Al-Cu Alloy in a Side-Cooled Cavity: Part II—Numerical Studies

NASA Astrophysics Data System (ADS)

Kumar, Arvind; Walker, Mike J.; Sundarraj, Suresh; Dutta, Pradip

2011-08-01

In this article, a single-phase, one-domain macroscopic model is developed for studying binary alloy solidification with moving equiaxed solid phase, along with the associated transport phenomena. In this model, issues such as thermosolutal convection, motion of solid phase relative to liquid and viscosity variations of the solid-liquid mixture with solid fraction in the mobile zone are taken into account. Using the model, the associated transport phenomena during solidification of Al-Cu alloys in a rectangular cavity are predicted. The results for temperature variation, segregation patterns, and eutectic fraction distribution are compared with data from in-house experiments. The model predictions compare well with the experimental results. To highlight the influence of solid phase movement on convection and final macrosegregation, the results of the current model are also compared with those obtained from the conventional solidification model with stationary solid phase. By including the independent movement of the solid phase into the fluid transport model, better predictions of macrosegregation, microstructure, and even shrinkage locations were obtained. Mechanical property prediction models based on microstructure will benefit from the improved accuracy of this model.
Mechanism of Formation of Li 7 P 3 S 11 Solid Electrolytes through Liquid Phase Synthesis

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

Wang, Yuxing; Lu, Dongping; Bowden, Mark

Crystalline Li7P3S11 is a promising solid electrolyte for all solid state lithium/lithium ion batteries. A controllable liquid phase synthesis of Li7P3S11 is more desirable compared to conventional mechanochemical synthesis, but recent attempts suffer from reduced ionic conductivities. Here we elucidate the formation mechanism of crystalline Li7P3S11 synthesized in the liquid phase (acetonitrile, or ACN). We conclude that the crystalline Li7P3S11 forms through a two-step reaction: 1) formation of solid Li3PS4∙ACN and amorphous Li2S∙P2S5 phases in the liquid phase; 2) solid-state conversion of the two phases. The implication of this two-step reaction mechanism to the morphology control and the transport propertiesmore » of liquid phase synthesized Li7P3S11 is identified and discussed.« less
Solid oxide MEMS-based fuel cells

DOEpatents

Jankowksi, Alan F.; Morse, Jeffrey D.

2007-03-13

A micro-electro-mechanical systems (MEMS) based thin-film fuel cells for electrical power applications. The MEMS-based fuel cell may be of a solid oxide type (SOFC), a solid polymer type (SPFC), or a proton exchange membrane type (PEMFC), and each fuel cell basically consists of an anode and a cathode separated by an electrolyte layer. The electrolyte layer can consist of either a solid oxide or solid polymer material, or proton exchange membrane electrolyte materials may be used. Additionally catalyst layers can also separate the electrodes (cathode and anode) from the electrolyte. Gas manifolds are utilized to transport the fuel and oxidant to each cell and provide a path for exhaust gases. The electrical current generated from each cell is drawn away with an interconnect and support structure integrated with the gas manifold. The fuel cells utilize integrated resistive heaters for efficient heating of the materials. By combining MEMS technology with thin-film deposition technology, thin-film fuel cells having microflow channels and full-integrated circuitry can be produced that will lower the operating temperature an will yield an order of magnitude greater power density than the currently known fuel cells.

Solid polymer MEMS-based fuel cells

DOEpatents

Jankowski, Alan F [Livermore, CA; Morse, Jeffrey D [Pleasant Hill, CA

2008-04-22

A micro-electro-mechanical systems (MEMS) based thin-film fuel cells for electrical power applications. The MEMS-based fuel cell may be of a solid oxide type (SOFC), a solid polymer type (SPFC), or a proton exchange membrane type (PEMFC), and each fuel cell basically consists of an anode and a cathode separated by an electrolyte layer. The electrolyte layer can consist of either a solid oxide or solid polymer material, or proton exchange membrane electrolyte materials may be used. Additionally catalyst layers can also separate the electrodes (cathode and anode) from the electrolyte. Gas manifolds are utilized to transport the fuel and oxidant to each cell and provide a path for exhaust gases. The electrical current generated from each cell is drawn away with an interconnect and support structure integrated with the gas manifold. The fuel cells utilize integrated resistive heaters for efficient heating of the materials. By combining MEMS technology with thin-film deposition technology, thin-film fuel cells having microflow channels and full-integrated circuitry can be produced that will lower the operating temperature an will yield an order of magnitude greater power density than the currently known fuel cells.
Hydrophilic interaction liquid chromatographic analysis of aminohydroxyphenylalanines from melanin pigments.

PubMed

Nezirević, Dzeneta; Arstrand, Kerstin; Kågedal, Bertil

2007-09-07

Malignant melanomas are more often seen in subjects with light colored skin who tan poorly than in persons who tan more rapidly. This has been attributed to the structure of their pigment, pheomelanin, which differs markedly from the eumelanin of persons with darker skin. To study the hydrolysis products of pheomelanin pigments a new method was developed for analysis of 4-amino-3-hydroxyphenylalanine (4-AHP) and 3-amino-4-hydroxyphenylalanine (3-AHP). Pheomelanin samples were hydrolyzed and extracted with solid-phase extraction columns using strong cation-exchange (SCX) cartridges. Separation of 4-AHP and 3-AHP was achieved on a ZIC-HILIC column (150 mm x 2.1mm I.D.) with a mobile phase consisting of acetonitrile: 0.1 M ammonium acetate buffer, pH 4.5 (82:18, v/v). Detection was performed with an electrochemical detector at +400 mV. Run time was 30 min. The limits of detection were 73 pg and 51 pg for 4-AHP and 3-AHP respectively, using 2 microl injections. Good linearity was found within the range 0.05-5.0 microg/ml. Absolute recovery was 70% and relative recovery was 100%. The AHPs were stable for 1 year in the hydrolyzed samples, for 4 days in the eluates from solid-phase sorbents stored in the refrigerator, and for 2 days diluted with mobile phase and stored in the autosampler at 10 degrees C. The within-day imprecision was <5% and the between-day imprecision was <7% for the two analytes. The method, applied to the analysis of pheomelanin in urine from human melanoma patients, allows the analysis of 30 samples in one set and is suitable for routine work with human hair and melanoma cells. By using the ZIC-HILIC stationary phase, ion-pairing reagents could be avoided, which makes the method suitable to further analysis of degradation products from pheomelanins using mass spectrometric detection.
Computational methods for reactive transport modeling: An extended law of mass-action, xLMA, method for multiphase equilibrium calculations

NASA Astrophysics Data System (ADS)

Leal, Allan M. M.; Kulik, Dmitrii A.; Kosakowski, Georg; Saar, Martin O.

2016-10-01

We present an extended law of mass-action (xLMA) method for multiphase equilibrium calculations and apply it in the context of reactive transport modeling. This extended LMA formulation differs from its conventional counterpart in that (i) it is directly derived from the Gibbs energy minimization (GEM) problem (i.e., the fundamental problem that describes the state of equilibrium of a chemical system under constant temperature and pressure); and (ii) it extends the conventional mass-action equations with Lagrange multipliers from the Gibbs energy minimization problem, which can be interpreted as stability indices of the chemical species. Accounting for these multipliers enables the method to determine all stable phases without presuming their types (e.g., aqueous, gaseous) or their presence in the equilibrium state. Therefore, the here proposed xLMA method inherits traits of Gibbs energy minimization algorithms that allow it to naturally detect the phases present in equilibrium, which can be single-component phases (e.g., pure solids or liquids) or non-ideal multi-component phases (e.g., aqueous, melts, gaseous, solid solutions, adsorption, or ion exchange). Moreover, our xLMA method requires no technique that tentatively adds or removes reactions based on phase stability indices (e.g., saturation indices for minerals), since the extended mass-action equations are valid even when their corresponding reactions involve unstable species. We successfully apply the proposed method to a reactive transport modeling problem in which we use PHREEQC and GEMS as alternative backends for the calculation of thermodynamic properties such as equilibrium constants of reactions, standard chemical potentials of species, and activity coefficients. Our tests show that our algorithm is efficient and robust for demanding applications, such as reactive transport modeling, where it converges within 1-3 iterations in most cases. The proposed xLMA method is implemented in Reaktoro, a unified open-source framework for modeling chemically reactive systems.
Effects of Inert Dust Clouds on the Extinction of Strained, Laminar Flames at Normal and Micro Gravity

NASA Technical Reports Server (NTRS)

Andac, M. Gurhan; Egolfopoulos, Fokion N.; Campbell, Charles S.; Lauvergne, Romain; Wu, Ming-Shin (Technical Monitor)

2000-01-01

A combined experimental and detailed numerical study was conducted on the interaction between chemically inert solid particles and strained, atmospheric methane/air and propane/air laminar flames, both premixed and non-premixed. Experimentally, the opposed jet configuration was used with the addition of a particle seeder capable of operating in conditions of varying gravity. The particle seeding system was calibrated under both normal and micro gravity and a noticeable gravitational effect was observed. Flame extinction experiments were conducted at normal gravity by seeding inert particles at various number densities and sizes into the reacting gas phase. Experimental data were taken for 20 and 37 (mu) nickel alloy and 25 and 60 (mu) aluminum oxide particles. The experiments were simulated by solving along the stagnation streamline the conservation equations of mass, momentum, energy, and species conservation for both phases, with detailed descriptions of chemical kinetics, molecular transport, and thermal radiation. The experimental data were compared with numerical simulations, and insight was provided into the effects on extinction of the fuel type, equivalence ratio, flame configuration, strain rate. particle type. particle size. particle mass, delivery rate. the orientation of particle injection with respect to the flame and gravity. It was found that for the same injected solid mass, larger particles can result in more effective flame cooling compared to smaller particles, despite the fact that equivalent masses of the larger particles have smaller total surface area to volume ratio. This counter-intuitive finding resulted from the fact that the heat exchange between the two phases is controlled by the synergistic effect of the total contact area and the temperature difference between the two phases. Results also demonstrate that meaningful scaling of interactions between the two phases may not be possible due to the complexity of the couplings between the dynamic and thermal parameters of the problem.
Engineered glass seals for solid-oxide fuel cells

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

Surdoval, Wayne; Lara-Curzio, Edgar; Stevenson, Jeffry

2017-02-07

A seal for a solid oxide fuel cell includes a glass matrix having glass percolation therethrough and having a glass transition temperature below 650.degree. C. A deformable second phase material is dispersed in the glass matrix. The second phase material can be a compliant material. The second phase material can be a crushable material. A solid oxide fuel cell, a precursor for forming a seal for a solid oxide fuel cell, and a method of making a seal for a solid oxide fuel cell are also disclosed.
Impacts of ocean acidification on the carbonate system at the sediment-water interface: a case-study in the NW Mediterranean Sea

NASA Astrophysics Data System (ADS)

Rassmann, Jens; Lansard, Bruno; Gazeau, Frédéric; Grenz, Christian; Alliouane, Samir; Petit, Franck; Pozzato, Lara; Bombled, Bruno; Rabouille, Christophe

2016-04-01

According to common predictions, carbon dioxide (CO2) uptake from the atmosphere into the oceans will decrease the average pH of seawater by 0.06-0.32 pH units by 2100. Ocean acidification alters chemical equilibria in seawater and thus potentially impacts marine ecosystem structure and functioning. Shelf regions play a key role for an important fraction of marine life and represent an important part of the global carbon cycle. Due to shallow water depth, chemistry in the water column is strongly coupled with biogeochemistry in the sediments. The aim of the present work is to investigate the impact of ocean acidification on carbonate chemistry. It focuses especially on exchange fluxes of dissolved inorganic carbon (DIC), total alkalinity (TA) and calcium through the sediment-water interface, and its impact on calcium carbonate precipitation or dissolution. For this purpose, sediment cores were incubated ex situ with an open flow of CO2 enriched seawater for 22 days (pHT=7,4, pH reported on the total proton scale). In parallel, sediment cores were incubated as a control with untreated seawater. Incubations took place in a water bath in a dark room with controlled temperature (14°C). Oxygen and pH microprofiles were recorded in the top first mm of the sediment during the whole experiment every 3 days. On 7 occasions, cores were isolated and incubated for 12 hours to estimate fluxes of DIC, TA, oxygen and nutrients. Porewater profiles of DIC, TA, calcium and nutrients were analyzed before and after incubation. On the solid phase, the content of particulate organic carbon, the C:N ratio and its isotopic δ15N and δ13C signature have been determined. In addition, total carbon contents have been measured and X-Ray diffraction was used to look for phase shifts between calcite and aragonite. A net decrease of pH was observed in the upper sediment layers, as well as an increase of DIC and TA pore water concentrations. The acidified cores showed higher DIC and TA exchange fluxes during the incubations in isolation, whereas oxygen exchange fluxes were independent of pH. Significant changes in the solid phase of the sediments could not be identified and the calcium pore water concentrations seemed not to be affected by acidification of the overlying waters during the given time scale. These results are put in the framework of coastal ocean acidification and are used to understand how the acidification changes the carbonate chemistry in the pore waters and constrain dissolution/precipitation of calcium carbonate.
Solid electrolyte-electrode system for an electrochemical cell

DOEpatents

Tuller, H.L.; Kramer, S.A.; Spears, M.A.

1995-04-04

An electrochemical device including a solid electrolyte and solid electrode composed of materials having different chemical compositions and characterized by different electrical properties but having the same crystalline phase is provided. A method for fabricating an electrochemical device having a solid electrode and solid electrolyte characterized by the same crystalline phase is also provided. 17 figures.
Rapid determination of the volatile components in tobacco by ultrasound-microwave synergistic extraction coupled to headspace solid-phase microextraction with gas chromatography-mass spectrometry.

PubMed

Yang, Yanqin; Chu, Guohai; Zhou, Guojun; Jiang, Jian; Yuan, Kailong; Pan, Yuanjiang; Song, Zhiyu; Li, Zuguang; Xia, Qian; Lu, Xinbo; Xiao, Weiqiang

2016-03-01

An ultrasound-microwave synergistic extraction coupled to headspace solid-phase microextraction was first employed to determine the volatile components in tobacco samples. The method combined the advantages of ultrasound, microwave, and headspace solid-phase microextraction. The extraction, separation, and enrichment were performed in a single step, which could greatly simplify the operation and reduce the whole pretreatment time. In the developed method, several experimental parameters, such as fiber type, ultrasound power, and irradiation time, were optimized to improve sampling efficiency. Under the optimal conditions, there were 37, 36, 34, and 36 components identified in tobacco from Guizhou, Hunan, Yunnan, and Zimbabwe, respectively, including esters, heterocycles, alkanes, ketones, terpenoids, acids, phenols, and alcohols. The compound types were roughly the same while the contents were varied from different origins due to the disparity of their growing conditions, such as soil, water, and climate. In addition, the ultrasound-microwave synergistic extraction coupled to headspace solid-phase microextraction method was compared with the microwave-assisted extraction coupled to headspace solid-phase microextraction and headspace solid-phase microextraction methods. More types of volatile components were obtained by using the ultrasound-microwave synergistic extraction coupled to headspace solid-phase microextraction method, moreover, the contents were high. The results indicated that the ultrasound-microwave synergistic extraction coupled to headspace solid-phase microextraction technique was a simple, time-saving and highly efficient approach, which was especially suitable for analysis of the volatile components in tobacco. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Liquid-phase and solid-phase microwave irradiations for reduction of graphite oxide

NASA Astrophysics Data System (ADS)

Zhao, Na; Wen, Chen-Yu; Zhang, David Wei; Wu, Dong-Ping; Zhang, Zhi-Bin; Zhang, Shi-Li

2014-12-01

In this paper, two microwave irradiation methods: (i) liquid-phase microwave irradiation (MWI) reduction of graphite oxide suspension dissolved in de-ionized water and N, N-dimethylformamide, respectively, and (ii) solid-phase MWI reduction of graphite oxide powder have been successfully carried out to reduce graphite oxide. The reduced graphene oxide products are thoroughly characterized by scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectral analysis, Raman spectroscopy, UV-Vis absorption spectral analysis, and four-point probe conductivity measurements. The results show that both methods can efficiently remove the oxygen-containing functional groups attached to the graphite layers, though the solid-phase MWI reduction method can obtain far more efficiently a higher quality-reduced graphene oxide with fewer defects. The I(D)/I(G) ratio of the solid-phase MWI sample is as low as 0.46, which is only half of that of the liquid-phase MWI samples. The electrical conductivity of the reduced graphene oxide by the solid method reaches 747.9 S/m, which is about 25 times higher than that made by the liquid-phase method.
Estimating production and consumption of solid reactive Fe phases in marine sediments from concentration profiles

EPA Science Inventory

1D diffusion models may be used to estimate rates of production and consumption of dissolved metabolites in marine sediments, but are applied less often to the solid phase. Here we used a numerical inverse method to estimate solid phase Fe(III) and Fe(II) consumption and product...
Hydrothermal replacement of calcite by Mg-carbonates

NASA Astrophysics Data System (ADS)

Jonas, Laura; Mueller, Thomas; Dohmen, Ralf

2014-05-01

The transport of heat and mass through the Earth's crust is coupled to mineral reactions and the exchange of isotopes and elements between different phases. Carbonate minerals are a major constituent of the Earth's crust and play an important role in different physical, chemical and even biological processes. In this experimental study, the element exchange reaction between calcite (CaCO3) and a Mg-rich fluid phase is investigated under hydrothermal conditions. Single crystals of calcite (2x2x2 mm) react with 1 ml of a 1 M MgCl2 solution at 200° C in a Teflon-lined steel autoclave for different times between one day and four weeks. The reaction leads to the formation of a porous reaction front and the pseudomorphic replacement of calcite by dolomite [CaMg(CO3)2] and magnesite (MgCO3). Scanning electron microscopy revealed that the reaction rim consists of small Mg-carbonate rhombs closely attached to each other, suggesting that the replacement reaction takes place by a dissolution-precipitation mechanism. Typically, the observed reaction front can be divided into two different domains. The outer part of the reaction rim, i.e. from the mineral surface in contact to the fluid inwards, consists of magnesite, whereas the inner part of the rim surrounding the unreacted calcite core consists of Ca-rich dolomite. The formation of a porous microstructure that varies in different parts of the reaction rim is a direct result of the large molar volume change induced by the replacement of calcite by magnesite and dolomite. The developing porosity therefore creates fluid pathways that promote the progress of the reaction front towards the unreacted core of the single crystal. Compositional profiles measured perpendicular to the mineral surface across the reactions rims using electron microprobe (EMPA) further revealed a compositional gradient within the reaction rim with regard to the structure-forming elements Mg and Ca. Here, the amount of Mg incorporated in both product phases increases with increasing distance from the unreacted calcite core, countered by a decrease of Ca incorporated. Both the coexistence of two different product phases and the distinct compositional gradient within the forming reaction rim are unequivocal signs of a chemical zonation of Ca and Mg in the fluid phase which mediates the element exchange between the reaction interface and the bulk solution. Atomic adsorption spectroscopy revealed that the Ca/Mg ratio in the reacted fluid increases as a function of time, reflecting the progressive exchange of Mg and Ca between the fluid and the solid phase. The time-dependence of the evolving Ca/Mg ratio can be fitted with a square root of time relation that indicates a transport controlled reaction. We interpret the hydrothermal replacement of calcite to operate via a dissolution/re-precipitation mechanism, whereas the reaction progress is controlled by the transport of the structure forming elements through the developing reaction rim.
Ion-exchange hollow fibers

NASA Technical Reports Server (NTRS)

Rembaum, A.; Yen, S. P. S.; Klein, E. (Inventor)

1976-01-01

An ion-exchange hollow fiber is prepared by introducing into the wall of the fiber polymerizable liquid monomers, and polymerizing the monomers therein to form solid, insoluble, crosslinked, ion-exchange resin particles which embed in the wall of the fiber. Excess particles blocking the central passage or bore of the fiber are removed by forcing liquid through the fiber. The fibers have high ion-exchange capacity, a practical wall permeability and good mechanical strength even with very thin wall dimensions. Experimental investigation of bundles of ion-exchange hollow fibers attached to a header assembly have shown the fiber to be very efficient in removing counterions from solution.
Phase correlation of foreign exchange time series

NASA Astrophysics Data System (ADS)

Wu, Ming-Chya

2007-03-01

Correlation of foreign exchange rates in currency markets is investigated based on the empirical data of USD/DEM and USD/JPY exchange rates for a period from February 1 1986 to December 31 1996. The return of exchange time series is first decomposed into a number of intrinsic mode functions (IMFs) by the empirical mode decomposition method. The instantaneous phases of the resultant IMFs calculated by the Hilbert transform are then used to characterize the behaviors of pricing transmissions, and the correlation is probed by measuring the phase differences between two IMFs in the same order. From the distribution of phase differences, our results show explicitly that the correlations are stronger in daily time scale than in longer time scales. The demonstration for the correlations in periods of 1986-1989 and 1990-1993 indicates two exchange rates in the former period were more correlated than in the latter period. The result is consistent with the observations from the cross-correlation calculation.
Digital Resource Exchange About Music (DREAM): Phase 2 Usability Testing

ERIC Educational Resources Information Center

Upitis, Rena; Boese, Karen; Abrami, Philip C.; Anwar, Zaeem

2015-01-01

The Digital Resource Exchange About Music (DREAM) is a virtual space for exchanging information about digital learning tools. The purpose of the present study was to determine how users responded to DREAM in the first four months after its public release. This study is the second phase of usability research on DREAM, and was conducted to guide…
THE RECIPROCAL SYSTEM FORMED BY THE CHLORIDES AND THE BROMIDES OF LITHIUM AND THALLIUM (in Russian)

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

Bergman, A.G.; Arabadzhan, A.S.

1963-06-01

The phase diagrams of 2 series of continuous solid solutions, the Li, K:: Cl,Br and the Li,Tl:: Cl,Br were investigated, as part of a study of the relation between thermal effect of equilibrium reactions and the structure of the melts. In the second system, the heat of the exchange reaction LiCl + TlBr in equilibrium LiBr + TlCl amounts to 8.19 kcal/mole, being larger than that of the corresponding reaction in the Li,K:: Cl,Br system; this affects the crystallization surface in the system. A Pt crucible and Pt, Au, Pd/Pt-Rh thermocouple were used in the thermal studies. It was foundmore » that the liquidus surface consists of 2 fields of continuous series of solid solutions. The joint crystallization curve has a maximum at 392 deg C at the stable portion of the LiCl-TlBr system. There is crest in the liquidus surface corresponding to the stable diagonal LiCl--TlBr; this is visible more markedly in the Li(Cl,Br) field. (TTT)« less
Computer-controlled high-resolution capacitance dilatometer/oven system: Design, instrumentation, and performance

NASA Astrophysics Data System (ADS)

Johansen, T. H.; Feder, J.; Jøssang, T.

1986-06-01

A fully automated apparatus has been designed for measurements of dilatation in solid samples under well-defined thermal conditions. The oven can be thermally stabilized to better than 0.1 mK over a temperature range of -60 to 150 °C using a two-stage control strategy. Coarse control is obtained by heat exchange with a circulating thermal fluid, whereas the fine regulation is based on a solid-state heat pump—a Peltier element, acting as heating and cooling source. The bidirectional action of the Peltier element permits the sample block to be controlled at the average temperature of the surroundings, thus making an essentially adiabatic system with a minimum of thermal gradients in the sample block. The dilatometer cell integrated in the oven assembly is of the parallel plate air capacitor type, and the apparatus has been successfully used with a sensitivity of 0.07 Å. Our system is well suited for measurements near structural phase transitions with a relative resolution of Δt=(T-Tc)/Tc=2×10-7 in temperature and ΔL/L=1×10-9 in strain.
Heat exchanger life extension via in-situ reconditioning

DOEpatents

Holcomb, David E.; Muralidharan, Govindarajan

2016-06-28

A method of in-situ reconditioning a heat exchanger includes the steps of: providing an in-service heat exchanger comprising a precipitate-strengthened alloy wherein at least one mechanical property of the heat exchanger is degraded by coarsening of the precipitate, the in-service heat exchanger containing a molten salt working heat exchange fluid; deactivating the heat exchanger from service in-situ; in a solution-annealing step, in-situ heating the heat exchanger and molten salt working heat exchange fluid contained therein to a temperature and for a time period sufficient to dissolve the coarsened precipitate; in a quenching step, flowing the molten salt working heat-exchange fluid through the heat exchanger in-situ to cool the alloy and retain a supersaturated solid solution while preventing formation of large precipitates; and in an aging step, further varying the temperature of the flowing molten salt working heat-exchange fluid to re-precipitate the dissolved precipitate.
Conceptual design of a hybrid parallel mechanism for mask exchanging of TMT

NASA Astrophysics Data System (ADS)

Wang, Jianping; Zhou, Hongfei; Li, Kexuan; Zhou, Zengxiang; Zhai, Chao

2015-10-01

Mask exchange system is an important part of the Multi-Object Broadband Imaging Echellette (MOBIE) on the Thirty Meter Telescope (TMT). To solve the problem of stiffness changing with the gravity vector of the mask exchange system in the MOBIE, the hybrid parallel mechanism design method was introduced into the whole research. By using the characteristics of high stiffness and precision of parallel structure, combined with large moving range of serial structure, a conceptual design of a hybrid parallel mask exchange system based on 3-RPS parallel mechanism was presented. According to the position requirements of the MOBIE, the SolidWorks structure model of the hybrid parallel mask exchange robot was established and the appropriate installation position without interfering with the related components and light path in the MOBIE of TMT was analyzed. Simulation results in SolidWorks suggested that 3-RPS parallel platform had good stiffness property in different gravity vector directions. Furthermore, through the research of the mechanism theory, the inverse kinematics solution of the 3-RPS parallel platform was calculated and the mathematical relationship between the attitude angle of moving platform and the angle of ball-hinges on the moving platform was established, in order to analyze the attitude adjustment ability of the hybrid parallel mask exchange robot. The proposed conceptual design has some guiding significance for the design of mask exchange system of the MOBIE on TMT.
Recent Application of Solid Phase Based Techniques for Extraction and Preconcentration of Cyanotoxins in Environmental Matrices.

PubMed

Mashile, Geaneth Pertunia; Nomngongo, Philiswa N

2017-03-04

Cyanotoxins are toxic and are found in eutrophic, municipal, and residential water supplies. For this reason, their occurrence in drinking water systems has become a global concern. Therefore, monitoring, control, risk assessment, and prevention of these contaminants in the environmental bodies are important subjects associated with public health. Thus, rapid, sensitive, selective, simple, and accurate analytical methods for the identification and determination of cyanotoxins are required. In this paper, the sampling methodologies and applications of solid phase-based sample preparation methods for the determination of cyanotoxins in environmental matrices are reviewed. The sample preparation techniques mainly include solid phase micro-extraction (SPME), solid phase extraction (SPE), and solid phase adsorption toxin tracking technology (SPATT). In addition, advantages and disadvantages and future prospects of these methods have been discussed.
A Quantitative Model for the Exchange Current of Porous Molybdenum Electrodes on Sodium Beta-Alumina in Sodium Vapor

NASA Technical Reports Server (NTRS)

Williams, R. M.; Ryan, M. A.; LeDuc, H.; Cortez, R. H.; Saipetch, C.; Shields, V.; Manatt, K.; Homer, M. L.

1998-01-01

This paper presents a model of the exchange current developed for porous molybdenum electrodes on sodium beta-alumina ceramics in low pressure sodium vapor, but which has general applicability to gas/porous metal electrodes on solid electrolytes.

Feasibility of Renewable Energy Technology at the Afghanistan National Security University: A Site-Specific Study Focused on Potential Renewable Energy Technologies in Northwest Kabul, Afghanistan

DTIC Science & Technology

2011-04-26

70% H2, O2 Proton exchange membrane fuel cell ( PEMFC ) Proton exchange membrane Rm temp to 80 °C 40–60% H2, O2, Air Direct methanol fuel cell...Cell PEMFC Proton Exchange Membrane Fuel Cell PV Photovoltaic SHGC Solar Heat Gain Coefficient SIR savings to investment ratio SOFC Solid Oxide
Modulated structure and molecular dissociation of solid chlorine at high pressures

NASA Astrophysics Data System (ADS)

Li, Peifang; Gao, Guoying; Ma, Yanming

2012-08-01

Among diatomic molecular halogen solids, high pressure structures of solid chlorine (Cl2) remain elusive and least studied. We here report first-principles structural search on solid Cl2 at high pressures through our developed particle-swarm optimization algorithm. We successfully reproduced the known molecular Cmca phase (phase I) at low pressure and found that it remains stable up to a high pressure 142 GPa. At 150 GPa, our structural searches identified several energetically competitive, structurally similar, and modulated structures. Analysis of the structural results and their similarity with those in solid Br2 and I2, it was suggested that solid Cl2 adopts an incommensurate modulated structure with a modulation wave close to 2/7 in a narrow pressure range 142-157 GPa. Eventually, our simulations at >157 GPa were able to predict the molecular dissociation of solid Cl2 into monatomic phases having body centered orthorhombic (bco) and face-centered cubic (fcc) structures, respectively. One unique monatomic structural feature of solid Cl2 is the absence of intermediate body centered tetragonal (bct) structure during the bco → fcc transition, which however has been observed or theoretically predicted in solid Br2 and I2. Electron-phonon coupling calculations revealed that solid Cl2 becomes superconductors within bco and fcc phases possessing a highest superconducting temperature of 13.03 K at 380 GPa. We further probed the molecular Cmca → incommensurate phase transition mechanism and found that the softening of the Ag vibrational (rotational) Raman mode in the Cmca phase might be the driving force to initiate the transition.
Solid-solution CrCoCuFeNi high-entropy alloy thin films synthesized by sputter deposition

DOE PAGES

An, Zhinan; Jia, Haoling; Wu, Yueying; ...

2015-05-04

The concept of high configurational entropy requires that the high-entropy alloys (HEAs) yield single-phase solid solutions. However, phase separations are quite common in bulk HEAs. A five-element alloy, CrCoCuFeNi, was deposited via radio frequency magnetron sputtering and confirmed to be a single-phase solid solution through the high-energy synchrotron X-ray diffraction, energy-dispersive spectroscopy, wavelength-dispersive spectroscopy, and transmission electron microscopy. The formation of the solid-solution phase is presumed to be due to the high cooling rate of the sputter-deposition process.
Tuning a High Transmission Ion Guide to Prevent Gas-Phase Proton Exchange During H/D Exchange MS Analysis.

PubMed

Guttman, Miklos; Wales, Thomas E; Whittington, Dale; Engen, John R; Brown, Jeffery M; Lee, Kelly K

2016-04-01

Hydrogen/deuterium exchange (HDX) mass spectrometry (MS) for protein structural analysis has been adopted for many purposes, including biopharmaceutical development. One of the benefits of examining amide proton exchange by mass spectrometry is that it can readily resolve different exchange regimes, as evidenced by either binomial or bimodal isotope patterns. By careful analysis of the isotope pattern during exchange, more insight can be obtained on protein behavior in solution. However, one must be sure that any observed bimodal isotope patterns are not artifacts of analysis and are reflective of the true behavior in solution. Sample carryover and certain stationary phases are known as potential sources of bimodal artifacts. Here, we describe an additional undocumented source of deuterium loss resulting in artificial bimodal patterns for certain highly charged peptides. We demonstrate that this phenomenon is predominantly due to gas-phase proton exchange between peptides and bulk solvent within the initial stages of high-transmission conjoined ion guides. Minor adjustments of the ion guide settings, as reported here, eliminate the phenomenon without sacrificing signal intensity. Such gas-phase deuterium loss should be appreciated for all HDX-MS studies using such ion optics, even for routine studies not focused on interpreting bimodal spectra. Graphical Abstract ᅟ.
Heat exchanger and related methods

DOEpatents

Turner, Terry D.; McKellar, Michael G.

2015-12-22

Heat exchangers include a housing having an inlet and an outlet and forming a portion of a transition chamber. A heating member may form another portion of the transition chamber. The heating member includes a first end having a first opening and a second end having a second opening larger than the first opening. Methods of conveying a fluid include supplying a first fluid into a transition chamber of a heat exchanger, supplying a second fluid into the transition chamber, and altering a state of a portion of the first fluid with the second fluid. Methods of sublimating solid particles include conveying a first fluid comprising a material in a solid state into a transition chamber, heating the material to a gaseous state by directing a second fluid through a heating member and mixing the first fluid and the second fluid.
Importance of the Kinetic Energy Density for Band Gap Calculations in Solids with Density Functional Theory.

PubMed

Tran, Fabien; Blaha, Peter

2017-05-04

Recently, exchange-correlation potentials in density functional theory were developed with the goal of providing improved band gaps in solids. Among them, the semilocal potentials are particularly interesting for large systems since they lead to calculations that are much faster than with hybrid functionals or methods like GW. We present an exhaustive comparison of semilocal exchange-correlation potentials for band gap calculations on a large test set of solids, and particular attention is paid to the potential HLE16 proposed by Verma and Truhlar. It is shown that the most accurate potential is the modified Becke-Johnson potential, which, most noticeably, is much more accurate than all other semilocal potentials for strongly correlated systems. This can be attributed to its additional dependence on the kinetic energy density. It is also shown that the modified Becke-Johnson potential is at least as accurate as the hybrid functionals and more reliable for solids with large band gaps.
Role of particle size and composition in metal adsorption by solids deposited on urban road surfaces.

PubMed

Gunawardana, Chandima; Egodawatta, Prasanna; Goonetilleke, Ashantha

2014-01-01

Despite common knowledge that the metal content adsorbed by fine particles is relatively higher compared to coarser particles, the reasons for this phenomenon have gained little research attention. The research study discussed in the paper investigated the variations in metal content for different particle sizes of solids associated with pollutant build-up on urban road surfaces. Data analysis confirmed that parameters favourable for metal adsorption to solids such as specific surface area, organic carbon content, effective cation exchange capacity and clay forming minerals content decrease with the increase in particle size. Furthermore, the mineralogical composition of solids was found to be the governing factor influencing the specific surface area and effective cation exchange capacity. There is high quartz content in particles >150 μm compared to particles <150 μm. As particle size reduces below 150 μm, the clay forming minerals content increases, providing favourable physical and chemical properties that influence adsorption. Copyright © 2013 Elsevier Ltd. All rights reserved.
Adsorption and mobility of metals in build-up on road surfaces.

PubMed

Gunawardana, Chandima; Egodawatta, Prasanna; Goonetilleke, Ashantha

2015-01-01

The study investigated the adsorption and bioavailability characteristics of traffic generated metals common to urban land uses, in road deposited solids particles. To validate the outcomes derived from the analysis of field samples, adsorption and desorption experiments were undertaken. The analysis of field samples revealed that metals are selectively adsorbed to different charge sites on solids. Zinc, copper, lead and nickel are adsorbed preferentially to oxides of manganese, iron and aluminium. Lead is adsorbed to organic matter through chemisorption. Cadmium and chromium form weak bonding through cation exchange with most of the particle sizes. Adsorption and desorption experiments revealed that at high metal concentrations, chromium, copper and lead form relatively strong bonds with solids particles while zinc is adsorbed through cation exchange with high likelihood of being released back into solution. Outcomes from this study provide specific guidance for the removal of metals from stormwater based on solids removal. Copyright © 2014 Elsevier Ltd. All rights reserved.
Method for making an electrochemical cell

DOEpatents

Tuller, Harry L.; Kramer, Steve A.; Spears, Marlene A.; Pal, Uday B.

1996-01-01

An electrochemical device including a solid electrolyte and solid electrode composed of materials having different chemical compositions and characterized by different electrical properties but having the same crystalline phase is provided. A method for fabricating an electrochemical device having a solid electrode and solid electrolyte characterized by the same crystalline phase is provided.
Pressure induced solid-solid reconstructive phase transition in LiGa O2 dominated by elastic strain

NASA Astrophysics Data System (ADS)

Hu, Qiwei; Yan, Xiaozhi; Lei, Li; Wang, Qiming; Feng, Leihao; Qi, Lei; Zhang, Leilei; Peng, Fang; Ohfuji, Hiroaki; He, Duanwei

2018-01-01

Pressure induced solid-solid reconstructive phase transitions for graphite-diamond, and wurtzite-rocksalt in GaN and AlN occur at significantly higher pressure than expected from equilibrium coexistence and their transition paths are always inconsistent with each other. These indicate that the underlying nucleation and growth mechanism in the solid-solid reconstructive phase transitions are poorly understood. Here, we propose an elastic-strain dominated mechanism in a reconstructive phase transition, β -LiGa O2 to γ -LiGa O2 , based on in situ high-pressure angle dispersive x-ray diffraction and single-crystal Raman scattering. This mechanism suggests that the pressure induced solid-solid reconstructive phase transition is neither purely diffusionless nor purely diffusive, as conventionally assumed, but a combination. The large elastic strains are accumulated, with the coherent nucleation, in the early stage of the transition. The elastic strains along the 〈100 〉 and 〈001 〉 directions are too large to be relaxed by the shear stress, so an intermediate structure emerges reducing the elastic strains and making the transition energetically favorable. At higher pressures, when the elastic strains become small enough to be relaxed, the phase transition to γ -LiGa O2 begins and the coherent nucleation is substituted with a semicoherent one with Li and Ga atoms disordered.
Comparison of the solid-phase extraction efficiency of a bounded and an included cyclodextrin-silica microporous composite for polycyclic aromatic hydrocarbons determination in water samples.

PubMed

Mauri-Aucejo, Adela; Amorós, Pedro; Moragues, Alaina; Guillem, Carmen; Belenguer-Sapiña, Carolina

2016-08-15

Solid-phase extraction is one of the most important techniques for sample purification and concentration. A wide variety of solid phases have been used for sample preparation over time. In this work, the efficiency of a new kind of solid-phase extraction adsorbent, which is a microporous material made from modified cyclodextrin bounded to a silica network, is evaluated through an analytical method which combines solid-phase extraction with high-performance liquid chromatography to determine polycyclic aromatic hydrocarbons in water samples. Several parameters that affected the analytes recovery, such as the amount of solid phase, the nature and volume of the eluent or the sample volume and concentration influence have been evaluated. The experimental results indicate that the material possesses adsorption ability to the tested polycyclic aromatic hydrocarbons. Under the optimum conditions, the quantification limits of the method were in the range of 0.09-2.4μgL(-1) and fine linear correlations between peak height and concentration were found around 1.3-70μgL(-1). The method has good repeatability and reproducibility, with coefficients of variation under 8%. Due to the concentration results, this material may represent an alternative for trace analysis of polycyclic aromatic hydrocarbons in water trough solid-phase extraction. Copyright © 2016 Elsevier B.V. All rights reserved.
FAST TRACK COMMUNICATION: Magnetic exchange hardening in polycrystalline GdN thin films

NASA Astrophysics Data System (ADS)

Senapati, K.; Fix, T.; Vickers, M. E.; Blamire, M. G.; Barber, Z. H.

2010-08-01

We report the observation of intrinsic exchange hardening in polycrystalline GdN thin films grown at room temperature by magnetron sputtering. We find, in addition to the ferromagnetic phase, that a fraction of GdN crystallizes in a structural polymorphic form which orders antiferromagnetically. The relative fraction of these two phases was controlled by varying the relative abundance of reactive species in the sputtering plasma by means of the sputtering power and N2 partial pressure. An exchange bias of ~ 30 Oe was observed at 10 K. The exchange coupling between the ferromagnetic and the antiferromagnetic phases resulted in an order of magnitude enhancement in the coercive field in these films.
The Iron-Iron Carbide Phase Diagram: A Practical Guide to Some Descriptive Solid State Chemistry.

ERIC Educational Resources Information Center

Long, Gary J.; Leighly, H. P., Jr.

1982-01-01

Discusses the solid state chemistry of iron and steel in terms of the iron-iron carbide phase diagram. Suggests that this is an excellent way of introducing the phase diagram (equilibrium diagram) to undergraduate students while at the same time introducing the descriptive solid state chemistry of iron and steel. (Author/JN)
A bi-directional two-phase/two-phase heat exchanger

NASA Technical Reports Server (NTRS)

Ku, Jentung; Ottenstein, Laura

1993-01-01

This paper describes the design and test of a heat exchanger that transfers heat from one two-phase thermal loop to another with very small drops in temperature and pressure. The heat exchanger condenses the vapor in one loop while evaporating the liquid in the other without mixing of the condensing and evaporating fluids. The heat exchanger is bidirectional in that it can transfer heat in reverse, condensing on the normally evaporating side and vice versa. It is fully compatible with capillary pumped loops and mechanically pumped loops. Test results verified that performance of the heat exchanger met the design requirements. It demonstrated a heat transfer rate of 6800 watts in the normal mode of operation and 1000 watts in the reverse mode with temperature drops of less than 5 C between two thermal loops.
Evaluation of bi-functionalized mesoporous silicas as reversed phase/cation-exchange mixed-mode sorbents for multi-residue solid phase extraction of veterinary drug residues in meat samples.

PubMed

Casado, Natalia; Pérez-Quintanilla, Damián; Morante-Zarcero, Sonia; Sierra, Isabel

2017-04-01

A SBA-15 type mesoporous silica was synthesized and bi-functionalized with octadecylsilane (C18) or octylsilane (C8), and sulfonic acid (SO 3 - ) groups in order to obtain materials with reversed-phase/strong cation-exchange mixed-mode retention mechanism. The resulting hybrid materials (SBA-15-C18-SO 3 - and SBA-15-C8-SO 3 - ) were comprehensively characterized. They showed high surface area, high pore volume and controlled porous size. Elemental analysis of the materials revealed differences in the amount of C18 and C8. SBA-15-C18-SO 3 - contained 0.19mmol/g of C18, while SBA-15-C8-SO 3 - presented 0.54mmol/g of C8. The SO 3 - groups anchored to the silica surface of the pore walls were 0.20 and 0.09mmol/g, respectively. The bi-functionalized materials were evaluated as SPE sorbents for the multi-residue extraction of 26 veterinary drug residues in meat samples using ultra-high-performance liquid chromatography coupled to mass spectrometry detector (UHPLC-MS/MS). Different sorbent amounts (100 and 200mg) and organic solvents were tested to optimize the extraction procedure. Both silicas showed big extraction potential and were successful in the extraction of the target analytes. The mixed-mode retention mechanism was confirmed by comparing both silicas with SBA-15 mesoporous silica mono-functionalized with C18 and C8. Best results were achieved with 200mg of SBA-15-C18-SO 3 - obtaining recoveries higher than 70% for the majority of analytes. Copyright © 2016 Elsevier B.V. All rights reserved.
MAX phase – Alumina composites via elemental and exchange reactions in the Ti{sub n+1}AC{sub n} systems (A=Al, Si, Ga, Ge, In and Sn)

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

Cuskelly, Dylan, E-mail: dylan.cuskelly@uon.edu.au; Richards, Erin; Kisi, Erich, E-mail: Erich.Kisi@newcastle.edu.au

2016-05-15

Extension of the aluminothermal exchange reaction synthesis of M{sub n+1}AX{sub n} phases to systems where the element ‘A’ is not the reducing agent was investigated in systems TiO{sub 2}–A–Al–C for A=Al, Si, Ga, Ge, In and Sn as well as Cr{sub 2}O{sub 3}–Ga–Al–C. MAX phase-Al{sub 2}O{sub 3} composites were made in all systems except those with A=Ga or In. The effectiveness of conversion to MAX phases was generally in the range 63–96% without optimisation of starting ratios. Optimisation in the Ti–Si–C system gave a MAX phase component with >98% Ti{sub 3}SiC{sub 2}. - Graphical abstract: A range of Ti{sub n+1}AX{submore » n} phases with different A elements were synthesised directly from the M oxide via exchange reactions. The process has now been shown to be general in all the systems marked in green in the table. - Highlights: • Ti{sub n+1}AC{sub n} phases were produced via a single step exchange reaction. • 3 MAX phase systems were successful via this method for the first time. • Cr{sub 2}GeC was also able to be produced via an exchange reaction. • The interconversion reaction in MAX phases is more general than previously thought.« less
LOW ACTIVITY WASTE FEED SOLIDS CARACTERIZATION AND FILTERABILITY TESTS

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

McCabe, D.; Crawford, C.; Duignan, M.

The primary treatment of the tank waste at the DOE Hanford site will be done in the Waste Treatment and Immobilization Plant (WTP) that is currently under construction. The baseline plan for the WTP Pretreatment facility is to treat the waste, splitting it into High Level Waste (HLW) feed and Low Activity Waste (LAW) feed. Both waste streams are then separately vitrified as glass and sealed in canisters. The LAW glass will be disposed onsite in the Integrated Disposal Facility (IDF). There are currently no plans to treat the waste to remove technetium in the WTP Pretreatment facility, so itsmore » disposition path is the LAW glass. Options are being explored to immobilize the LAW portion of the tank waste, i.e., the LAW feed from the WTP Pretreatment facility. Removal of {sup 99}Tc from the LAW Feed, followed by off-site disposal of the {sup 99}Tc, would eliminate a key risk contributor for the IDF Performance Assessment (PA) for supplemental waste forms, and has potential to reduce treatment and disposal costs. Washington River Protection Solutions (WRPS) is developing some conceptual flow sheets for LAW treatment and disposal that could benefit from technetium removal. One of these flowsheets will specifically examine removing {sup 99}Tc from the LAW feed stream to supplemental immobilization. The conceptual flow sheet of the {sup 99}Tc removal process includes a filter to remove insoluble solids prior to processing the stream in an ion exchange column, but the characteristics and behavior of the liquid and solid phases has not previously been investigated. This report contains results of testing of a simulant that represents the projected composition of the feed to the Supplemental LAW process. This feed composition is not identical to the aqueous tank waste fed to the Waste Treatment Plant because it has been processed through WTP Pretreatment facility and therefore contains internal changes and recycle streams that will be generated within the WTP process. Although a Supplemental LAW feed simulant has previously been prepared, this feed composition differs from that simulant because those tests examined only the fully soluble aqueous solution at room temperature, not the composition formed after evaporation, including the insoluble solids that precipitate after it cools. The conceptual flow sheet for Supplemental LAW immobilization has an option for removal of {sup 99}Tc from the feed stream, if needed. Elutable ion exchange has been selected for that process. If implemented, the stream would need filtration to remove the insoluble solids prior to processing in an ion exchange column. The characteristics, chemical speciation, physical properties, and filterability of the solids are important to judge the feasibility of the concept, and to estimate the size and cost of a facility. The insoluble solids formed during these tests were primarily natrophosphate, natroxalate, and a sodium aluminosilicate compound. At the elevated temperature and 8 M [Na+], appreciable insoluble solids (1.39 wt%) were present. Cooling to room temperature and dilution of the slurry from 8 M to 5 M [Na+] resulted in a slurry containing 0.8 wt% insoluble solids. The solids (natrophosphate, natroxalate, sodium aluminum silicate, and a hydrated sodium phosphate) were relatively stable and settled quickly. Filtration rates were in the range of those observed with iron-based simulated Hanford tank sludge simulants, e.g., 6 M [Na+] Hanford tank 241-AN-102, even though their chemical speciation is considerably different. Chemical cleaning of the crossflow filter was readily accomplished with acid. As this simulant formulation was based on an average composition of a wide range of feeds using an integrated computer model, this exact composition may never be observed. But the test conditions were selected to enable comparison to the model to enable improving its chemical prediction capability.« less
Valley Phase and Voltage Control of Coherent Manipulation in Si Quantum Dots.

PubMed

Zimmerman, Neil M; Huang, Peihao; Culcer, Dimitrie

2017-07-12

With any roughness at the interface of an indirect-bandgap semiconducting dot, the phase of the valley-orbit coupling can take on a random value. This random value, in double quantum dots, causes a large change in the exchange splitting. We demonstrate a simple analytical method to calculate the phase, and thus the exchange splitting and singlet-triplet qubit frequency, for an arbitrary interface. We then show that, with lateral control of the position of a quantum dot using a gate voltage, the valley-orbit phase can be controlled over a wide range, so that variations in the exchange splitting can be controlled for individual devices. Finally, we suggest experiments to measure the valley phase and the concomitant gate voltage control.
An Investigation into the Polymorphism and Crystallization of Levetiracetam and the Stability of its Solid Form.

PubMed

Xu, Kailin; Xiong, Xinnuo; Guo, Liuqi; Wang, Lili; Li, Shanshan; Tang, Peixiao; Yan, Jin; Wu, Di; Li, Hui

2015-12-01

Levetiracetam (LEV) crystals were prepared using different solvents at different temperatures. The LEV crystals were systematically characterized by X-ray powder diffraction (XRPD) and morphological analysis. The results indicated that many kinds of crystal habits exist in a solid form of LEV. To investigate the effects of LEV concentration, crystallization temperature, and crystallization type on crystallization and solid phase transformation of LEV, multiple methods were performed for LEV aqueous solution to determine if a new solid form exists in solid-state LEV. However, XRPD data demonstrate that the LEV solid forms possess same spatial arrangements that are similar to the original solid form. This result indicates that the LEV concentration, crystallization temperature, and crystallization type in aqueous solution have no influence on the crystallization and solid phase transformation of LEV. Moreover, crystallization by sublimation, melt cooling, and quench cooling, as well as mechanical effect, did not result in the formation of new LEV solid state. During melt cooling, the transformation of solid form LEV is a direct process from melting amorphous phase to the original LEV crystal phase, and the conversion rate is very quick. In addition, stability investigation manifested that LEV solid state is very stable under various conditions. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.
Building of Equations of State with Numerous Phase Transitions — Application to Bismuth

NASA Astrophysics Data System (ADS)

Heuzé, Olivier

2006-07-01

We propose an algorithm to build complete equation of state EOS including several solid/solid or solid/liquid phase transitions. Each phase has its own EOS and independent parameters. The phase diagram is deduced from the thermodynamic equilibrium assumption. Until now, such an approach was used in simple cases and limited to 2 or 3 phases. We have applied it in the general case to bismuth for which up to 13 phases have been identified. This study shows the great influence of binary mixtures and triple points properties in released isentropes after shock waves.

Creation and Annihilation of Skyrmions in the Frustrated Magnets with Competing Exchange Interactions.

PubMed

Hu, Yong; Chi, Xiaodan; Li, Xuesi; Liu, Yan; Du, An

2017-11-22

In triangular-lattice magnets, the coexistence of third-neighbor antiferromagnetic and nearest-neighbor ferromagnetic exchange interactions can induce rich magnetic phases including noncoplanar skyrmion crystals. Based on Monte Carlo simulation, we studied the dependence of magnetic phase transition on exchange interaction strength. Under the consideration of uniaxial anisotropy and magnetic field both perpendicular to the film plane, a large antiferromagnetic exchange interaction induces a high frustration. When the value of antiferromagnetic exchange interaction is one and a half times larger than the ferromagnetic one, a magnetic phase composed of canting spin stripes, never observed in the chiral magnets, forms. Interestingly, different canting spin stripes along three 120 degree propagation directions may coexist randomly in a magnetic phase, attesting that the canting spin stripes are three-fold degenerate states akin to helices and the multiple state of canting spin stripes is a circular configuration with zero skyrmion charge number. Moreover, skyrmions and antiskyrmions can be observed simultaneously in the configuration at the low temperature nearly close to 0 K, and their configuration and diameter properties are discussed. Finally, the mechanisms of skyrmion creation and annihilation are properly interpreted by comparing exchange and Zeeman energy terms.
Performance of exchange-correlation functionals in density functional theory calculations for liquid metal: A benchmark test for sodium.

PubMed

Han, Jeong-Hwan; Oda, Takuji

2018-04-14

The performance of exchange-correlation functionals in density-functional theory (DFT) calculations for liquid metal has not been sufficiently examined. In the present study, benchmark tests of Perdew-Burke-Ernzerhof (PBE), Armiento-Mattsson 2005 (AM05), PBE re-parameterized for solids, and local density approximation (LDA) functionals are conducted for liquid sodium. The pair correlation function, equilibrium atomic volume, bulk modulus, and relative enthalpy are evaluated at 600 K and 1000 K. Compared with the available experimental data, the errors range from -11.2% to 0.0% for the atomic volume, from -5.2% to 22.0% for the bulk modulus, and from -3.5% to 2.5% for the relative enthalpy depending on the DFT functional. The generalized gradient approximation functionals are superior to the LDA functional, and the PBE and AM05 functionals exhibit the best performance. In addition, we assess whether the error tendency in liquid simulations is comparable to that in solid simulations, which would suggest that the atomic volume and relative enthalpy performances are comparable between solid and liquid states but that the bulk modulus performance is not. These benchmark test results indicate that the results of liquid simulations are significantly dependent on the exchange-correlation functional and that the DFT functional performance in solid simulations can be used to roughly estimate the performance in liquid simulations.
Performance of exchange-correlation functionals in density functional theory calculations for liquid metal: A benchmark test for sodium

NASA Astrophysics Data System (ADS)

Han, Jeong-Hwan; Oda, Takuji

2018-04-01

The performance of exchange-correlation functionals in density-functional theory (DFT) calculations for liquid metal has not been sufficiently examined. In the present study, benchmark tests of Perdew-Burke-Ernzerhof (PBE), Armiento-Mattsson 2005 (AM05), PBE re-parameterized for solids, and local density approximation (LDA) functionals are conducted for liquid sodium. The pair correlation function, equilibrium atomic volume, bulk modulus, and relative enthalpy are evaluated at 600 K and 1000 K. Compared with the available experimental data, the errors range from -11.2% to 0.0% for the atomic volume, from -5.2% to 22.0% for the bulk modulus, and from -3.5% to 2.5% for the relative enthalpy depending on the DFT functional. The generalized gradient approximation functionals are superior to the LDA functional, and the PBE and AM05 functionals exhibit the best performance. In addition, we assess whether the error tendency in liquid simulations is comparable to that in solid simulations, which would suggest that the atomic volume and relative enthalpy performances are comparable between solid and liquid states but that the bulk modulus performance is not. These benchmark test results indicate that the results of liquid simulations are significantly dependent on the exchange-correlation functional and that the DFT functional performance in solid simulations can be used to roughly estimate the performance in liquid simulations.
Density-functional theory for fluid-solid and solid-solid phase transitions.

PubMed

Bharadwaj, Atul S; Singh, Yashwant

2017-03-01

We develop a theory to describe solid-solid phase transitions. The density functional formalism of classical statistical mechanics is used to find an exact expression for the difference in the grand thermodynamic potentials of the two coexisting phases. The expression involves both the symmetry conserving and the symmetry broken parts of the direct pair correlation function. The theory is used to calculate phase diagram of systems of soft spheres interacting via inverse power potentials u(r)=ε(σ/r)^{n}, where parameter n measures softness of the potential. We find that for 1/n<0.154 systems freeze into the face centered cubic (fcc) structure while for 1/n≥0.154 the body-centred-cubic (bcc) structure is preferred. The bcc structure transforms into the fcc structure upon increasing the density. The calculated phase diagram is in good agreement with the one found from molecular simulations.
Equilibrium aluminium hydroxo-oxalate phases during initial clay formation; H +-Al 3+-oxalic acid-Na + system

NASA Astrophysics Data System (ADS)

Bilinski, Halka; Horvath, Laszlo; Ingri, Nils; Sjöberg, Staffan

1986-09-01

The conditions necessary for initial clay formation have been studied in different model systems comprising different organic acids besides Si and Al. In the present paper the solid phases and the precipitation boundary characterizing the subsystem H +-Al 3+-oxalic acid (H 2L) are discussed. pH and tyndallometric measurements were performed in an ionic medium of 0.6 M Na(Cl) at 25 °C. The two phases Al 3(OH) 7(C 2O 4) · 3H 2O (phase I) and NaAl(OH) 2(C 2O 4) · 3H 2O (phase II) determine the precipitation boundary. The following formation constants for the two phases were deduced: lgβ1 = lg([ Al3+] -3[ H2C2O4] -1[ H+] 9 = -21.87 ± 0.08 and lgβ11 = lg([ Al3+] -1[ H2C2O4] -1[ H+] 4 = -5.61 ± 0.06. Phase I exists in the range [ Al] tot≥ 10 -4.4moldm-3,[ H2C2O4] tot ≥ 10 -4.9moldm-3 and at pH < 6.8, thus being a possible precipitate in oxalic-rich natural waters. The more soluble sodium phase is unlikely to exist in natural waters. The two phases are metastable relative to crystalline gibbsite and may be considered as the first precipitation step in the transition from aqueous Al oxalates down to stable Al hydroxide. Model calculations illustrating these competing hydrolysis-complexation reactions are discussed in terms of predominance and speciation diagrams. The solid phases have been characterized by X-ray analysis of powders, TGA and IR spectra, and tentative structures are proposed. Phase I seems to be an octahedral layer structure, in which 3/5 of the octahedral sites between two close packed oxygen sheets are occupied by Al 3+ and the oxalate ion acts as a bridge ligand between two aluminium atoms. Phase II forms a more open sheet structure and has ion exchange properties. Powder data for a phase crystallized from the studied solution after a year are also presented. This phase, Na 4Al 2(OH) 2(C 2O 4) 4 · 10H 2O, supports the results from the equilibrium analysis of recent solution data by SJöBERG and ÖHMAN (1985), who have found the dinuclear complex Al 2(OH) 2(C 2O 4) 44- to exist in a solution in which the ligand is in excess.
40 CFR 261.3 - Definition of hazardous waste.

Code of Federal Regulations, 2014 CFR

2014-07-01

... discharged to the refinery oil recovery sewer before primary oil/water/solids separation—heat exchanger bundle cleaning sludge from the petroleum refining industry (EPA Hazardous Waste No. K050), crude oil... oil tank sediment and/or in-line filter/separation solids from petroleum refining operations (EPA...
40 CFR 261.3 - Definition of hazardous waste.

Code of Federal Regulations, 2012 CFR

2012-07-01

... discharged to the refinery oil recovery sewer before primary oil/water/solids separation—heat exchanger bundle cleaning sludge from the petroleum refining industry (EPA Hazardous Waste No. K050), crude oil... oil tank sediment and/or in-line filter/separation solids from petroleum refining operations (EPA...
40 CFR 261.3 - Definition of hazardous waste.

Code of Federal Regulations, 2013 CFR

2013-07-01

... discharged to the refinery oil recovery sewer before primary oil/water/solids separation—heat exchanger bundle cleaning sludge from the petroleum refining industry (EPA Hazardous Waste No. K050), crude oil... oil tank sediment and/or in-line filter/separation solids from petroleum refining operations (EPA...
Calculation of individual isotope equilibrium constants for implementation in geochemical models

USGS Publications Warehouse

Thorstenson, Donald C.; Parkhurst, David L.

2002-01-01

Theory is derived from the work of Urey to calculate equilibrium constants commonly used in geochemical equilibrium and reaction-transport models for reactions of individual isotopic species. Urey showed that equilibrium constants of isotope exchange reactions for molecules that contain two or more atoms of the same element in equivalent positions are related to isotope fractionation factors by , where is n the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example and , and to include the effects of nonideality. The equilibrium constants of the isotope exchange reactions provide a basis for calculating the individual isotope equilibrium constants for the geochemical modeling reactions. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation factors. Equilibrium constants are calculated for all species that can be formed from and selected species containing , in the molecules and the ion pairs with where the subscripts g, aq, l, and s refer to gas, aqueous, liquid, and solid, respectively. These equilibrium constants are used in the geochemical model PHREEQC to produce an equilibrium and reaction-transport model that includes these isotopic species. Methods are presented for calculation of the individual isotope equilibrium constants for the asymmetric bicarbonate ion. An example calculates the equilibrium of multiple isotopes among multiple species and phases.
Two-phase anaerobic digestion of vegetable market waste fraction of municipal solid waste and development of improved technology for phase separation in two-phase reactor.

PubMed

Majhi, Bijoy Kumar; Jash, Tushar

2016-12-01

Biogas production from vegetable market waste (VMW) fraction of municipal solid waste (MSW) by two-phase anaerobic digestion system should be preferred over the single-stage reactors. This is because VMW undergoes rapid acidification leading to accumulation of volatile fatty acids and consequent low pH resulting in frequent failure of digesters. The weakest part in the two-phase anaerobic reactors was the techniques applied for solid-liquid phase separation of digestate in the first reactor where solubilization, hydrolysis and acidogenesis of solid organic waste occur. In this study, a two-phase reactor which consisted of a solid-phase reactor and a methane reactor was designed, built and operated with VMW fraction of Indian MSW. A robust type filter, which is unique in its implementation method, was developed and incorporated in the solid-phase reactor to separate the process liquid produced in the first reactor. Experiments were carried out to assess the long term performance of the two-phase reactor with respect to biogas production, volatile solids reduction, pH and number of occurrence of clogging in the filtering system or choking in the process liquid transfer line. The system performed well and was operated successfully without the occurrence of clogging or any other disruptions throughout. Biogas production of 0.86-0.889m 3 kg -1 VS, at OLR of 1.11-1.585kgm -3 d -1 , were obtained from vegetable market waste, which were higher than the results reported for similar substrates digested in two-phase reactors. The VS reduction was 82-86%. The two-phase anaerobic digestion system was demonstrated to be stable and suitable for the treatment of VMW fraction of MSW for energy generation. Copyright © 2016 Elsevier Ltd. All rights reserved.
Mechanism and microstructures in Ga2O3 pseudomartensitic solid phase transition.

PubMed

Zhu, Sheng-Cai; Guan, Shu-Hui; Liu, Zhi-Pan

2016-07-21

Solid-to-solid phase transition, although widely exploited in making new materials, challenges persistently our current theory for predicting its complex kinetics and rich microstructures in transition. The Ga2O3α-β phase transformation represents such a common but complex reaction with marked change in cation coordination and crystal density, which was known to yield either amorphous or crystalline products under different synthetic conditions. Here we, via recently developed stochastic surface walking (SSW) method, resolve for the first time the atomistic mechanism of Ga2O3α-β phase transformation, the pathway of which turns out to be the first reaction pathway ever determined for a new type of diffusionless solid phase transition, namely, pseudomartensitic phase transition. We demonstrate that the sensitivity of product crystallinity is caused by its multi-step, multi-type reaction pathway, which bypasses seven intermediate phases and involves all types of elementary solid phase transition steps, i.e. the shearing of O layers (martensitic type), the local diffusion of Ga atoms (reconstructive type) and the significant lattice dilation (dilation type). While the migration of Ga atoms across the close-packed O layers is the rate-determining step and yields "amorphous-like" high energy intermediates, the shearing of O layers contributes to the formation of coherent biphase junctions and the presence of a crystallographic orientation relation, (001)α//(201[combining macron])β + [120]α//[13[combining macron]2]β. Our experiment using high-resolution transmission electron microscopy further confirms the theoretical predictions on the atomic structure of biphase junction and the formation of (201[combining macron])β twin, and also discovers the late occurrence of lattice expansion in the nascent β phase that grows out from the parent α phase. By distinguishing pseudomartensitic transition from other types of mechanisms, we propose general rules to predict the product crystallinity of solid phase transition. The new knowledge on the kinetics of pseudomartensitic transition complements the theory of diffusionless solid phase transition.
Entropic Anomaly Observed in Lipid Polymorphisms Induced by Surfactant Peptide SP-B(1-25).

PubMed

Tran, Nhi; Kurian, Justin; Bhatt, Avni; McKenna, Robert; Long, Joanna R

2017-10-05

The N-terminal 25 amino-acid residues of pulmonary surfactant protein B (SP-B 1-25 ) induces unusual lipid polymorphisms in a model lipid system, 4:1 DPPC/POPG, mirroring the lipid composition of native pulmonary surfactant. It is widely suggested that SP-B 1-25 -induced lipid polymorphisms within the alveolar aqueous subphase provide a structural platform for rapid lipid adsorption to the air-water interface. Here, we characterize in detail the phase behavior of DPPC and POPG in hydrated lipid assemblies containing therapeutic levels of SP-B 1-25 using 2 H and 31 P solid state NMR spectroscopy. The appearance of a previously observed isotropic lipid phase is found to be highly dependent on the thermal cycling of the samples. Slow heating of frozen samples leads to phase separation of DPPC into a lamellar phase whereas POPG lipids interact with the peptide to form an isotropic phase at physiologic temperature. Rapid heating of frozen samples to room temperature leads to strongly isotropic phase behavior for both DPPC and POPG lipids, with DPPC in exchange between isotropic and interdigitated phases. 31 P T 2 relaxation times confirm the isotropic phase to be consistent with a lipid cubic phase. The observed phases exhibit thermal stability up to physiologic temperature (37 °C) and are consistent with the formation of a ripple phase containing a large number of peptide-induced membrane structural defects enabling rapid transit of lipids between lipid lamellae. The coexistance of a lipid cubic phase with interdigitated lipids suggests a specific role for the highly conserved N-terminus of SP-B in stabilizing this unusual lipid polymorphism.
Thermodynamic Investigation of the Effect of Interface Curvature on the Solid-Liquid Equilibrium and Eutectic Point of Binary Mixtures.

PubMed

Liu, Fanghui; Zargarzadeh, Leila; Chung, Hyun-Joong; Elliott, Janet A W

2017-10-12

Thermodynamic phase behavior is affected by curved interfaces in micro- and nanoscale systems. For example, capillary freezing point depression is associated with the pressure difference between the solid and liquid phases caused by interface curvature. In this study, the thermal, mechanical, and chemical equilibrium conditions are derived for binary solid-liquid equilibrium with a curved solid-liquid interface due to confinement in a capillary. This derivation shows the equivalence of the most general forms of the Gibbs-Thomson and Ostwald-Freundlich equations. As an example, the effect of curvature on solid-liquid equilibrium is explained quantitatively for the water/glycerol system. Considering the effect of a curved solid-liquid interface, a complete solid-liquid phase diagram is developed over a range of concentrations for the water/glycerol system (including the freezing of pure water or precipitation of pure glycerol depending on the concentration of the solution). This phase diagram is compared with the traditional phase diagram in which the assumption of a flat solid-liquid interface is made. We show the extent to which nanoscale interface curvature can affect the composition-dependent freezing and precipitating processes, as well as the change in the eutectic point temperature and concentration with interface curvature. Understanding the effect of curvature on solid-liquid equilibrium in nanoscale capillaries has applications in the food industry, soil science, cryobiology, nanoporous materials, and various nanoscience fields.
Suppressing the cellular breakdown in silicon supersaturated with titanium

NASA Astrophysics Data System (ADS)

Liu, Fang; Prucnal, S.; Hübner, R.; Yuan, Ye; Skorupa, W.; Helm, M.; Zhou, Shengqiang

2016-06-01

Hyper doping Si with up to 6 at.% Ti in solid solution was performed by ion implantation followed by pulsed laser annealing and flash lamp annealing. In both cases, the implanted Si layer can be well recrystallized by liquid phase epitaxy and solid phase epitaxy, respectively. Cross-sectional transmission electron microscopy of Ti-implanted Si after liquid phase epitaxy shows the so-called growth interface breakdown or cellular breakdown owing to the occurrence of constitutional supercooling in the melt. The appearance of cellular breakdown prevents further recrystallization. However, the out-diffusion and cellular breakdown can be effectively suppressed by solid phase epitaxy during flash lamp annealing due to the high velocity of amorphous-crystalline interface and the low diffusion velocity for Ti in the solid phase.
Experimental investigation of hydrodynamics and heat exchange in the ring channel with heat exchangers in the modes of single-phase convection and bubble boiling

NASA Astrophysics Data System (ADS)

Agishev, B. Y.; Boltenko, E. A.; Varava, A. N.; Dedov, A. V.; Zakharenkov, A. V.; Komov, A. T.; Smorchova, Y. V.

2018-03-01

The effectiveness of the heat exchange intensifier “rib-twisted wire” is considered in this paper. The main goal is to study the influence of the wire coiling step t on heat transfer and hydraulic resistance for different values Ḣ of the dimensionless height of the edge Ḣ, as well as some results on heat exchange during bubbly boiling in an annular channel. Show: • a brief description and an image of the heat exchange intensifier “rib-twisted wire” • generalized results of studies of heat exchange and hydraulic resistance in the annular channel in the single-phase convection with different geometric characteristics of the intensifier; • empirical correlations of the generalized experimental results that allow to calculating the coefficient of hydraulic resistance and heat transfer in the range of regime parameters in the single-phase convection that is being studied. • some results of experiments in bubbly boiling regimes and near-critical thermal loads.
Comparing the catalytic oxidation of ethanol at the solid-gas and solid-liquid interfaces over size-controlled Pt nanoparticles: striking differences in kinetics and mechanism.

PubMed

Sapi, Andras; Liu, Fudong; Cai, Xiaojun; Thompson, Christopher M; Wang, Hailiang; An, Kwangjin; Krier, James M; Somorjai, Gabor A

2014-11-12

Pt nanoparticles with controlled size (2, 4, and 6 nm) are synthesized and tested in ethanol oxidation by molecular oxygen at 60 °C to acetaldehyde and carbon dioxide both in the gas and liquid phases. The turnover frequency of the reaction is ∼80 times faster, and the activation energy is ∼5 times higher at the gas-solid interface compared to the liquid-solid interface. The catalytic activity is highly dependent on the size of the Pt nanoparticles; however, the selectivity is not size sensitive. Acetaldehyde is the main product in both media, while twice as much carbon dioxide was observed in the gas phase compared to the liquid phase. Added water boosts the reaction in the liquid phase; however, it acts as an inhibitor in the gas phase. The more water vapor was added, the more carbon dioxide was formed in the gas phase, while the selectivity was not affected by the concentration of the water in the liquid phase. The differences in the reaction kinetics of the solid-gas and solid-liquid interfaces can be attributed to the molecular orientation deviation of the ethanol molecules on the Pt surface in the gas and liquid phases as evidenced by sum frequency generation vibrational spectroscopy.
Calorimetric Study of Alkali Metal Ion (K +, Na +, Li +) Exchange in a Clay-Like MXene

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

Sharma, Geetu; Muthuswamy, Elayaraja; Naguib, Michael

Intercalation of ions in layered materials has been explored to improve the rate capability in Li-ion batteries and supercapacitors. This work investigates the energetics of alkali ion exchange in a clay-like MXene, Ti 3C 2T x, where T x stands for anionic surface moieties, by immersion calorimetry in aqueous solutions. The measured immersion enthalpies of clay-like Ti 3C 2T x, ΔH imm, at 25 °C in 1 M KCl, 1 M NaCl, 1 M LiCl, and nanopure water are -9.19 (±0.56), -5.90 (±0.31), -1.31 (±0.20), and -1.29 (±0.13) kJ/mol of MXene, respectively. Inductively coupled plasma mass spectrometry is used tomore » obtain the concentrations of alkali ions in the solid and aqueous phases. Using these concentrations, the enthalpies of exchange of alkali metal ions (Li+, Na+, and K+) are calculated; ΔHex in 1 M KCl, 1 M NaCl, 1 M LiCl, and nanopure water are -9.3 (±2.2), 21.0 (±0.9), -1.3 (±0.2), and 302.4 (±0.6) kJ/mol of MXene, respectively. Both immersion and exchange enthalpies are most exothermic for potassium. This suggests that K+ ions interact more strongly with anions present in the interlayers of this MXene than Na + and Li + ions. Water vapor adsorption calorimetry indicates very weak interaction of water with the MXene, while immersion calorimetry suggests a weakly hydrophilic nature of the MXene surface.« less
Calorimetric Study of Alkali Metal Ion (K +, Na +, Li +) Exchange in a Clay-Like MXene

DOE PAGES

Sharma, Geetu; Muthuswamy, Elayaraja; Naguib, Michael; ...

2017-06-21

Intercalation of ions in layered materials has been explored to improve the rate capability in Li-ion batteries and supercapacitors. This work investigates the energetics of alkali ion exchange in a clay-like MXene, Ti 3C 2T x, where T x stands for anionic surface moieties, by immersion calorimetry in aqueous solutions. The measured immersion enthalpies of clay-like Ti 3C 2T x, ΔH imm, at 25 °C in 1 M KCl, 1 M NaCl, 1 M LiCl, and nanopure water are -9.19 (±0.56), -5.90 (±0.31), -1.31 (±0.20), and -1.29 (±0.13) kJ/mol of MXene, respectively. Inductively coupled plasma mass spectrometry is used tomore » obtain the concentrations of alkali ions in the solid and aqueous phases. Using these concentrations, the enthalpies of exchange of alkali metal ions (Li+, Na+, and K+) are calculated; ΔHex in 1 M KCl, 1 M NaCl, 1 M LiCl, and nanopure water are -9.3 (±2.2), 21.0 (±0.9), -1.3 (±0.2), and 302.4 (±0.6) kJ/mol of MXene, respectively. Both immersion and exchange enthalpies are most exothermic for potassium. This suggests that K+ ions interact more strongly with anions present in the interlayers of this MXene than Na + and Li + ions. Water vapor adsorption calorimetry indicates very weak interaction of water with the MXene, while immersion calorimetry suggests a weakly hydrophilic nature of the MXene surface.« less
A High-Throughput Process for the Solid-Phase Purification of Synthetic DNA Sequences

PubMed Central

Grajkowski, Andrzej; Cieślak, Jacek; Beaucage, Serge L.

2017-01-01

An efficient process for the purification of synthetic phosphorothioate and native DNA sequences is presented. The process is based on the use of an aminopropylated silica gel support functionalized with aminooxyalkyl functions to enable capture of DNA sequences through an oximation reaction with the keto function of a linker conjugated to the 5′-terminus of DNA sequences. Deoxyribonucleoside phosphoramidites carrying this linker, as a 5′-hydroxyl protecting group, have been synthesized for incorporation into DNA sequences during the last coupling step of a standard solid-phase synthesis protocol executed on a controlled pore glass (CPG) support. Solid-phase capture of the nucleobase- and phosphate-deprotected DNA sequences released from the CPG support is demonstrated to proceed near quantitatively. Shorter than full-length DNA sequences are first washed away from the capture support; the solid-phase purified DNA sequences are then released from this support upon reaction with tetra-n-butylammonium fluoride in dry dimethylsulfoxide (DMSO) and precipitated in tetrahydrofuran (THF). The purity of solid-phase-purified DNA sequences exceeds 98%. The simulated high-throughput and scalability features of the solid-phase purification process are demonstrated without sacrificing purity of the DNA sequences. PMID:28628204
Nanostructured lipid carriers: effect of solid phase fraction and distribution on the release of encapsulated materials.

PubMed

Dan, Nily

2014-11-25

Emulsions, solid lipid nanoparticles (SLN), and nanostructured lipid carriers (NLC) containing a mix of liquid and solid domains are of interest as encapsulation vehicles for hydrophobic compounds. Studies of the release rate from these particles yield contradictory results: Some find that increasing the fraction of solid phase increases the rate of release and others the opposite. In this paper we study the release of encapsulated materials from lipid-based nanoparticles using Monte Carlo simulations. We find that, quite surprisingly, the release rate is largely insensitive to the size of solid domains or the fraction of solid phase. However, the distribution of the domains significantly affects the rate of release: Solid domains located at the interface with the surrounding solution inhibit transport, while nanoparticles where the solid domains are concentrated in the center enhance it. The latter can lead to release rates in NLCs that are faster than in the equivalent emulsions. We conclude that controlling the release rate from NLCs requires the ability to determine the location and distribution of the solid phase, which may be achieved through choice of the surfactants stabilizing the particles, incorporation of nucleation sites, and/or the cooling rates and temperatures.

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