Study of Parameters Dominating Electromechanical and Sensing Response in Ionic Electroactive Polymer (IEAP) Transducers

NASA Astrophysics Data System (ADS)

Almomani, Abdallah Mohammad

Ionic electroactive polymer (IEAP) transducers are a class of smart structures based on polymers that can be designed as soft actuators or sensors. IEAP actuators exhibit a high mechanical response to an external electrical stimulus. Conversely, they produce electrical signals when subjected to mechanical force. IEAP transducers are mainly composed of four different components: The ionomeric membrane (usually Nafion) is an ion permeable polymer that acts as the backbone of the transducer. Two conductive network composite (CNC) layer on both sides of the ionomeric membrane that enhance the surface conductivity and serve as an extra reservoir to the electrolytes. The electrolytes, (usually ionic liquids (IL)), which provides the mobile ions. And two outer electrodes on both sides of the transducer to either provide a distributed applied potential across the actuators (usually gold leaves) or to collect the generated signals from the sensors (usually copper electrodes). Any variation in any of these components or the operating conditions will directly affect the performance of the IEAP transduces. In this dissertation, we studied some of the parameters dominating the performance of the IEAP transducers by varying some of the transducers components or the transducers operating conditions in order to enhance their performance. The first study was conducted to understand the influence of ionic liquid concentration on the electromechanical performance of IEAP actuators. The IL weight percentage (wt%) was varied from 10% to 30% and both the electromechanical (induced strain) and the electrochemical (the current flow across the actuators) were studied. The results from this study showed an enhanced electrochemical performance (current flow is higher for higher IL wt%) and a maximum electromechanical strain of approximately 1.4% at 22 wt% IL content. A lower induced strain was noticed for IL wt% lower or higher than 22%. The second study was to investigate the effect of changing the morphology of the CNC on the sensing performance of IEAP stress sensors. In this study, small salt molecules were added to the CNC layers. Salt molecules directly affected the morphology of the CNC layers resulting in a thicker, more porous, and high conductive CNCs. As a result, the ionic conductivity increased through the CNC layers and sensing performance was enhanced significantly. In the third study, a non-linear angular deformation (limb-like motion) was achieved by varying the CNC layers of the IEAP actuators by adding some conjugated polymers (CP) patterns during the fabrication of the actuators. It was found that the segments with the CP layers will only expand and never contract during the actuation process. Depending on the direction of motion and the location of the CP layers, different actuation shapes such as square or triangular shapes were achieved rather than the typical circular bending. In the fourth study, the influence of temperature on the electromechanical properties of the IEAP actuators was examined. In this study, both electromechanical and electrochemical studies were conducted for actuators that were operated at temperatures ranging from 25 °C to 90 °C. The electromechanical results showed a lower cationic curvature with increasing temperature up to 70 °C. On the other hand, a maximum anionic curvature was achieved at 50 °C with a sudden decrease after 50 °C. Actuators started to lose functionality and showed unpredictable performance at temperatures higher than 70 °C. Electrochemically, an enhancement of the ionic conductivity was resulted from increasing temperature up to 80 °C. A sudden increase in current flow was recorded at 90 °C indicating a shorted circuit and actuator failure. Finally, in the fifth study, protons in Nafion membranes were exchanged with other counterions of different Van der Waals volumes. The ionic conductivity was measured for IEAP membranes with different counterions at different temperatures. The results showed higher ionic conductivities across membranes with larger Van der Waals volume counterions and higher temperatures. A different ionic conductivity behavior was also noticed for temperatures ranging from 30 °C to 55 °C than temperatures between 55 °C and 70 °C after fitting the data with the Arrhenius conductivity equation.

Electrokinetic mixing at high zeta potentials: ionic size effects on cross stream diffusion.

PubMed

Ahmadian Yazdi, Alireza; Sadeghi, Arman; Saidi, Mohammad Hassan

2015-03-15

The electrokinetic phenomena at high zeta potentials may show several unique features which are not normally observed. One of these features is the ionic size (steric) effect associated with the solutions of high ionic concentration. In the present work, attention is given to the influences of finite ionic size on the cross stream diffusion process in an electrokinetically actuated Y-shaped micromixer. The method consists of a finite difference based numerical approach for non-uniform grid which is applied to the dimensionless form of the governing equations, including the modified Poisson-Boltzmann equation. The results reveal that, neglecting the ionic size at high zeta potentials gives rise to the overestimation of the mixing length, because the steric effects retard liquid flow, thereby enhancing the mixing efficiency. The importance of steric effects is found to be more intense for channels of smaller width to height ratio. It is also observed that, in sharp contrast to the conditions that the ions are treated as point charges, increasing the zeta potential improves the cross stream diffusion when incorporating the ionic size. Moreover, increasing the EDL thickness decreases the mixing length, whereas the opposite is true for the channel aspect ratio. Copyright © 2014 Elsevier Inc. All rights reserved.

Carbon-, sulfur-, and phosphorus-based charge transfer reactions in inductively coupled plasma-atomic emission spectrometry

NASA Astrophysics Data System (ADS)

Grindlay, Guillermo; Gras, Luis; Mora, Juan; de Loos-Vollebregt, Margaretha T. C.

2016-01-01

In this work, the influence of carbon-, sulfur-, and phosphorus-based charge transfer reactions on the emission signal of 34 elements (Ag, Al, As, Au, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Ga, Hg, I, In, Ir, K, Li, Mg, Mn, Na, Ni, P, Pb, Pd, Pt, S, Sb, Se, Sr, Te, and Zn) in axially viewed inductively coupled plasma-atomic emission spectrometry has been investigated. To this end, atomic and ionic emission signals for diluted glycerol, sulfuric acid, and phosphoric acid solutions were registered and results were compared to those obtained for a 1% w w- 1 nitric acid solution. Experimental results show that the emission intensities of As, Se, and Te atomic lines are enhanced by charge transfer from carbon, sulfur, and phosphorus ions. Iodine and P atomic emission is enhanced by carbon- and sulfur-based charge transfer whereas the Hg atomic emission signal is enhanced only by carbon. Though signal enhancement due to charge transfer reactions is also expected for ionic emission lines of the above-mentioned elements, no experimental evidence has been found with the exception of Hg ionic lines operating carbon solutions. The effect of carbon, sulfur, and phosphorus charge transfer reactions on atomic emission depends on (i) wavelength characteristics. In general, signal enhancement is more pronounced for electronic transitions involving the highest upper energy levels; (ii) plasma experimental conditions. The use of robust conditions (i.e. high r.f. power and lower nebulizer gas flow rates) improves carbon, sulfur, and phosphorus ionization in the plasma and, hence, signal enhancement; and (iii) the presence of other concomitants (e.g. K or Ca). Easily ionizable elements reduce ionization in the plasma and consequently reduce signal enhancement due to charge transfer reactions.

Modeling electrokinetics in ionic liquids: General

DOE PAGES

Wang, Chao; Bao, Jie; Pan, Wenxiao; ...

2017-04-01

Using direct numerical simulations, we provide a thorough study regarding the electrokinetics of ionic liquids. In particular, modified Poisson–Nernst–Planck equations are solved to capture the crowding and overscreening effects characteristic of an ionic liquid. For modeling electrokinetic flows in an ionic liquid, the modified Poisson-Nernst-Planck equations are coupled with Navier–Stokes equations to study the coupling of ion transport, hydrodynamics, and electrostatic forces. Specifically, we consider the ion transport between two parallel charged surfaces, charging dynamics in a nanopore, capacitance of electric double-layer capacitors, electroosmotic flow in a nanochannel, electroconvective instability on a plane ion-selective surface, and electroconvective flow on amore » curved ionselective surface. Lastly, we also discuss how crowding and overscreening and their interplay affect the electrokinetic behaviors of ionic liquids in these application problems.« less

The molecular assembly of the ionic liquid/aliphatic carboxylic acid/aliphatic amine as effective and safety transdermal permeation enhancers.

PubMed

Kubota, Koji; Shibata, Akira; Yamaguchi, Toshikazu

2016-04-30

In spite of numerous advantages, transdermal drug delivery systems are unfeasible for most drugs because of the barrier effect of the stratum corneum. Ionic liquids were recently used to enhance transdermal drug delivery by improving drug solubility. In the present study, safe and effective ionic liquids for transdermal absorption were obtained as salts generated by a neutralization reaction between highly biocompatible aliphatic carboxylic acids (octanoic acid or isostearic acid) and aliphatic amines (diisopropanolamine or triisopropanolamine) (Medrx Co., Ltd., 2009). The mechanism of skin permeability enhancement by ionic liquids was investigated by hydrophilic phenol red and hydrophobic tulobuterol. Further, the skin permeation enhancing effect was remarkably superior in the acid excess state rather than the neutralization state. Infrared absorption spectrum analysis confirmed that ionic liquids/aliphatic carboxylic acid/aliphatic amine are coexisting at all mixing states. In the acid excess state, ionic liquids interact with aliphatic carboxylic acids via hydrogen bonds. Thus, the skin permeation enhancing effect is not caused by the ionic liquid alone. The "liquid salt mixture," referred to as a complex of ingredients coexisting with ionic liquids, forms a molecular assembly incorporating hydrophilic drug. This molecular assembly was considered an effective and safety enhancer of transdermal drug permeation. Copyright © 2016. Published by Elsevier B.V.

The confined [Bmim][BF4] ionic liquid flow through graphene oxide nanochannels: a molecular dynamics study.

PubMed

Wang, Yanlei; Huo, Feng; He, Hongyan; Zhang, Suojiang

2018-06-20

Ionic liquid (IL) flow in graphene oxide (GO) nanochannels plays a key role in the performance of IL- and GO-based fluidics devices and other chemical separator techniques. Here, we investigate the flow behavior of ILs in GO nanochannels via molecular dynamics simulations. The quantitative relation between slip velocity and shear stress has been identified, showing that the interfacial friction coefficient can be enhanced by almost sixty times, while the slip length is reduced by about three orders of magnitude, with the fraction of hydroxylation in graphene ranging from 0% to 15%. The great change in interfacial properties can be attributed to the structural changes of IL layers near GO, which is proved by the detailed analysis of density distribution, charge distribution and radial distribution function. Besides, the viscosity will increase as a fraction of hydroxylation because of the partial breaking of coulombic ordering of confined ILs. Meanwhile, the hydroxyls have more significant effects on IL flow than water flow in GO nanochannels due to the stronger interaction networks in IL/GO interfaces. In summary, hydroxylation can be a convincing method to regulate the IL flow in nanochannels. The quantitative properties of confined ILs in GO nanochannels and their relation to the fraction of hydroxylation could deepen the understanding of ILs and benefit the applications of ILs and GO in the fields of chemical engineering and various other nanofluidic devices.

Catalytic Decomposition of Hydroxylammonium Nitrate Ionic Liquid: Enhancement of NO Formation

DTIC Science & Technology

2017-04-24

Nitrate Ionic Liquid : Enhancement of NO Formation Steven D. Chambreau, Denisia M. Popolan-Vaida, Ghanshyam L. Vaghjiani, and Stephen R. Leone Air Force...Hydroxylammonium Nitrate Ionic Liquid : Enhancement of NO Formation Steven D. Chambreau,† Denisia M. Popolan-Vaida,‡,§ Ghanshyam L. Vaghjiani,*,∥ and Stephen R...nitrate (HAN)ionic liquid as a replacement for hydrazine as a spacecraft monopropellant has been of great interest recently due to the reduced toxicity

Nanoparticle transport in water-unsaturated porous media: effects of solution ionic strength and flow rate

NASA Astrophysics Data System (ADS)

Prédélus, Dieuseul; Lassabatere, Laurent; Louis, Cédric; Gehan, Hélène; Brichart, Thomas; Winiarski, Thierry; Angulo-Jaramillo, Rafael

2017-03-01

This paper presents the influence of ionic strength and flow on nanoparticle (NP) retention rate in an unsaturated calcareous medium, originating from a heterogeneous glaciofluvial deposit of the region of Lyon (France). Laboratory columns 10 cm in diameter and 30 cm in length were used. Silica nanoparticles (Au-SiO2-FluoNPs), with hydrodynamic diameter ranging from 50 to 60 nm and labeled with fluorescein derivatives, were used to simulate particle transport, and bromide was used to characterize flow. Three flow rates and five different ionic strengths were tested. The transfer model based on fractionation of water into mobile and immobile fractions was coupled with the attachment/detachment model to fit NPs breakthrough curves. The results show that increasing flow velocity induces a decrease in nanoparticle retention, probably as the result of several physical but also geochemical factors. The results show that NPs retention increases with ionic strength. However, an inversion of retention occurs for ionic strength >5.10-2 M, which has been scarcely observed in previous studies. The measure of zeta potential and DLVO calculations show that NPs may sorb on both solid-water and air-water interfaces. NPs size distribution shows the potential for nanoparticle agglomeration mostly at low pH, leading to entrapment in the soil pores. These mechanisms are highly sensitive to both hydrodynamic and geochemical conditions, which explains their high sensitivity to flow rates and ionic strength.

An Investigation of Ionic Flows in a Sphere-Plate Electrode Gap

NASA Astrophysics Data System (ADS)

Z. Alisoy, H.; Alagoz, S.; T. Alisoy, G.; B. Alagoz, B.

2013-10-01

This paper presents analyses of ion flow characteristics and ion discharge pulses in a sphere-ground plate electrode system. As a result of variation in electric field intensity in the electrode gap, the ion flows towards electrodes generate non-uniform discharging pulses. Inspection of these pulses provides useful information on ionic stream kinetics, the effective thickness of ion cover around electrodes, and the timing of ion clouds discharge pulse sequences. A finite difference time domain (FDTD) based space-charge motion simulation is used for the numerical analysis of the spatio-temporal development of ionic flows following the first Townsend avalanche, and the simulation results demonstrate expansion of the positive ion flow and compression of the negative ion flow, which results in non-uniform discharge pulse characteristics.

Probing the interaction of ionic liquids with graphene using surface-enhanced Raman spectroscopy

DOE PAGES

Mahurin, Shannon Mark; Dai, Sheng; Surwade, Sumedh P.; ...

2015-12-17

We report an in situ measurement of the interaction of an imidazolium-based room temperature ionic liquid with both pure silver and a graphene-over-silver electrode under an applied electrochemical potential. At a negative applied potential, overall signal intensity increased indicating enhanced ionic liquid concentration at both silver and graphene electrodes. Vibrational modes associated with the imidazolium ring exhibited greater intensity enhancements and larger peak shifts compared with the anion indicating that the cation adsorbs with the ring and alkyl chain parallel to the electrode surface for both silver and graphene. In contrast to the silver, the surface enhanced Raman spectra ofmore » the ionic liquid near graphene showed shifts in the cation peaks even at no applied potential because of the strong π–π interaction between the ionic liquid and the graphene. Furthermore, the intensity of the graphene peak decreased in the presence of ionic liquid possibly due to the interaction between the ionic liquid and graphene. In conclusion, these results illustrate the effectiveness of surface-enhanced Raman spectroscopy to investigate electrolyte interactions with graphene at the liquid/electrode interface.« less

Characterization of aggregates of surface modified fullerenes by asymmetrical flow field-flow fractionation with multi-angle light scattering detection.

PubMed

Astefanei, Alina; Kok, Wim Th; Bäuerlein, Patrick; Núñez, Oscar; Galceran, Maria Teresa; de Voogt, Pim; Schoenmakers, Peter J

2015-08-21

Fullerenes are carbon nanoparticles with widespread biomedical, commercial and industrial applications. Attributes such as their tendency to aggregate and aggregate size and shape impact their ability to be transported into and through the environment and living tissues. Knowledge of these properties is therefore valuable for their human and environmental risk assessment as well as to control their synthesis and manufacture. In this work, asymmetrical flow-field flow fractionation (AF4) coupled to multi-angle light scattering (MALS) was used for the first time to study the size distribution of surface modified fullerenes with both polyhydroxyl and carboxyl functional groups in aqueous solutions having different pH (6.5-11) and ionic strength values (0-200mM) of environmental relevance. Fractionation key parameters such as flow rates, flow programming, and membrane material were optimized for the selected fullerenes. The aggregation of the compounds studied appeared to be indifferent to changes in solution pH, but was affected by changes in the ionic strength. Polyhydroxy-fullerenes were found to be present mostly as 4nm aggregates in water without added salt, but showed more aggregation at high ionic strength, with an up to 10-fold increase in their mean hydrodynamic radii (200mM), due to a decrease in the electrostatic repulsion between the nanoparticles. Carboxy-fullerenes showed a much stronger aggregation degree in water (50-100nm). Their average size and recoveries decreased with the increase in the salt concentration. This behavior can be due to enhanced adsorption of the large particles to the membrane at high ionic strength, because of their higher hydrophobicity and much larger particle sizes compared to polyhydroxy-fullerenes. The method performance was evaluated by calculating the run-to-run precision of the retention time (hydrodynamic radii), and the obtained RSD values were lower than 1%. MALS measurements showed aggregate sizes that were in good agreement with the AF4 data. A comparison of the scattering radii from the MALS with the hydrodynamic radii obtained from the retention times in AF4 indicated that the aggregate shapes are far from spherical. TEM images of the fullerenes in the dry state also showed branched and irregular clusters. Copyright © 2015 Elsevier B.V. All rights reserved.

Effect of chitosan ethers on fresh state properties of lime mortars

NASA Astrophysics Data System (ADS)

Vyšvařil, M.; Žižlavský, T.

2017-10-01

The fresh state properties of mortars are eminently important since determine the material workability and also have a great influence on its hardened state characteristics. In this paper, the behaviour of fresh lime mortars modified by etherified derivatives of chitosan (hydroxypropylchitosan (HPCH) and carboxymethylchitosan (CMCH)) is assessed with the purpose of exploring a new application of such derivatives as lime mortar admixtures. The rheological parameters (relative yield stress, consistency coefficient and fluidity index) and viscoelastic properties were correlated with flow table tests, relative density measurements, water retention abilities of mortars and air content in mortars. Results were seen to be strongly dependent on substituents of the chitosan. Non-ionic derivative (HPCH) had a plasticizing influence on the mortars; the ionic CMCH showed the thickening effect. The effect of chitosan ethers was found to be dosage-dependent. CMCH had low impact on water retention, while HPCH displayed high water retention capability. It was concluded, that the ionic derivative (CMCH) is very similar by its viscosity enhancing effect to starch ether.

Hydrodynamic model of temperature change in open ionic channels.

PubMed Central

Chen, D P; Eisenberg, R S; Jerome, J W; Shu, C W

1995-01-01

Most theories of open ionic channels ignore heat generated by current flow, but that heat is known to be significant when analogous currents flow in semiconductors, so a generalization of the Poisson-Nernst-Planck theory of channels, called the hydrodynamic model, is needed. The hydrodynamic theory is a combination of the Poisson and Euler field equations of electrostatics and fluid dynamics, conservation laws that describe diffusive and convective flow of mass, heat, and charge (i.e., current), and their coupling. That is to say, it is a kinetic theory of solute and solvent flow, allowing heat and current flow as well, taking into account density changes, temperature changes, and electrical potential gradients. We integrate the equations with an essentially nonoscillatory shock-capturing numerical scheme previously shown to be stable and accurate. Our calculations show that 1) a significant amount of electrical energy is exchanged with the permeating ions; 2) the local temperature of the ions rises some tens of degrees, and this temperature rise significantly alters for ionic flux in a channel 25 A long, such as gramicidin-A; and 3) a critical parameter, called the saturation velocity, determines whether ionic motion is overdamped (Poisson-Nernst-Planck theory), is an intermediate regime (called the adiabatic approximation in semiconductor theory), or is altogether unrestricted (requiring the full hydrodynamic model). It seems that significant temperature changes are likely to accompany current flow in the open ionic channel. PMID:8599638

Electrokinetic remediation of contaminated soil with waste-lubricant oils and zinc.

PubMed

Park, Sung-Woo; Lee, Jae-Young; Yang, Jung-Seok; Kim, Kyoung-Jo; Baek, Kitae

2009-09-30

The feasibility of electrokinetic technology on the remediation of mixed-waste-contaminated railroad soil, contaminated by lubricant oil and zinc, was investigated. To enhance the removal efficiency, catholyte purging with 0.1M HNO(3) and a supply of non-ionic surfactant, secondary alcohol ethoxylate, was applied to the anode to remove Zn and to solubilize the lubricant oil. The catholyte purging maintained the soil pH as acidic and enhanced desorption of zinc from the soil, where the zeta potential of the acidic soil became positive. Thereafter, the direction of electro-osmotic flow was changed from the cathode to anode and the flow rate was reduced. The lesser in magnitude reverse electro-osmotic flow inhibited the migration of zinc and the lubricant oil was removed by the electro-osmotic flow. The removal of zinc and lubricant oil was enhanced with an increase in voltage gradient; however, a higher voltage gradient resulted in higher energy expenditure. After electrokinetic operation over 17 days, the removal efficiency of zinc was 22.1-24.3%, and that of lubricant oil was 45.1-55.0%. Although the removal of lubricant oil was quite high, the residual concentration did not meet Korean regulation levels.

Spectacular Rate Enhancement of the Diels-Alder Reaction at the Ionic Liquid/n-Hexane Interface.

PubMed

Beniwal, Vijay; Manna, Arpan; Kumar, Anil

2016-07-04

The use of the ionic liquid/n-hexane interface as a new class of reaction medium for the Diels-Alder reaction gives large rate enhancements of the order of 10(6) to 10(8) times and high stereoselectivity, as compared to homogeneous media. The rate enhancement is attributed to the H-bonding abilities and polarities of the ionic liquids, whereas the hydrophobicity of ionic liquids was considered to be the factor in controlling stereoselectivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of ionic concentration gradient on electroosmotic flow mixing in a microchannel.

PubMed

Peng, Ran; Li, Dongqing

2015-02-15

Effects of ionic concentration gradient on electroosmotic flow (EOF) mixing of one stream of a high concentration electrolyte solution with a stream of a low concentration electrolyte solution in a microchannel are investigated numerically. The concentration field, flow field and electric field are strongly coupled via concentration dependent zeta potential, dielectric constant and electric conductivity. The results show that the electric field and the flow velocity are non-uniform when the concentration dependence of these parameters is taken into consideration. It is also found that when the ionic concentration of the electrolyte solution is higher than 1M, the electrolyte solution essentially cannot enter the channel due to the extremely low electroosmotic flow mobility. The effects of the concentration dependence of zeta potential, dielectric constant and electric conductivity on electroosmotic flow mixing are studied. Copyright © 2014 Elsevier Inc. All rights reserved.

Transport processes in magnetically confined plasmas in the nonlinear regime.

PubMed

Sonnino, Giorgio

2006-06-01

A field theory approach to transport phenomena in magnetically confined plasmas is presented. The thermodynamic field theory (TFT), previously developed for treating the generic thermodynamic system out of equilibrium, is applied to plasmas physics. Transport phenomena are treated here as the effect of the field linking the thermodynamic forces with their conjugate flows combined with statistical mechanics. In particular, the Classical and the Pfirsch-Schluter regimes are analyzed by solving the thermodynamic field equations of the TFT in the weak-field approximation. We found that, the TFT does not correct the expressions of the ionic heat fluxes evaluated by the neoclassical theory in these two regimes. On the other hand, the fluxes of matter and electronic energy (heat flow) is further enhanced in the nonlinear Classical and Pfirsch-Schluter regimes. These results seem to be in line with the experimental observations. The complete set of the electronic and ionic transport equations in the nonlinear Banana regime, is also reported. A paper showing the comparison between our theoretic results and the experimental observations in the JET machine is currently in preparation.

Dynamics of two interacting active Janus particles.

PubMed

Bayati, Parvin; Najafi, Ali

2016-04-07

Starting from a microscopic model for a spherically symmetric active Janus particle, we study the interactions between two such active motors. The ambient fluid mediates a long range hydrodynamic interaction between two motors. This interaction has both direct and indirect hydrodynamic contributions. The direct contribution is due to the propagation of fluid flow that originated from a moving motor and affects the motion of the other motor. The indirect contribution emerges from the re-distribution of the ionic concentrations in the presence of both motors. Electric force exerted on the fluid from this ionic solution enhances the flow pattern and subsequently changes the motion of both motors. By formulating a perturbation method for very far separated motors, we derive analytic results for the translation and rotational dynamics of the motors. We show that the overall interaction at the leading order modifies the translational and rotational speeds of motors which scale as O[1/D](3) and O[1/D](4) with their separation, respectively. Our findings open up the way for studying the collective dynamics of synthetic micro-motors.

Enhanced desalination performance of membrane capacitive deionization cells by packing the flow chamber with granular activated carbon.

PubMed

Bian, Yanhong; Yang, Xufei; Liang, Peng; Jiang, Yong; Zhang, Changyong; Huang, Xia

2015-11-15

A new design of membrane capacitive deionization (MCDI) cell was constructed by packing the cell's flow chamber with granular activated carbon (GAC). The GAC packed-MCDI (GAC-MCDI) delivered higher (1.2-2.5 times) desalination rates than the regular MCDI at all test NaCl concentrations (∼ 100-1000 mg/L). The greatest performance enhancement by packed GAC was observed when treating saline water with an initial NaCl concentration of 100 mg/L. Several different GAC materials were tested and they all exhibited similar enhancement effects. Comparatively, packing the MCDI's flow chamber with glass beads (GB; non-conductive) and graphite granules (GG; conductive but with lower specific surface area than GAC) resulted in inferior desalination performance. Electrochemical impedance spectroscopy (EIS) analysis showed that the GAC-MCDI had considerably smaller internal resistance than the regular MCDI (∼ 19.2 ± 1.2 Ω versus ∼ 1222 ± 15 Ω at 100 mg/L NaCl). The packed GAC also decreased the ionic resistance across the flow chamber (∼ 1.49 ± 0.05 Ω versus ∼ 1130 ± 12 Ω at 100 mg/L NaCl). The electric double layer (EDL) formed on the GAC surface was considered to store salt ions during electrosorption, and facilitate the ion transport in the flow chamber because of the higher ion conductivity in the EDLs than in the bulk solution, thereby enhancing the MCDI's desalination rate. Copyright © 2015 Elsevier Ltd. All rights reserved.

Enhancement of thermal transport in Gel Polymer Electrolytes with embedded BN/Al2O3 nano- and micro-particles

NASA Astrophysics Data System (ADS)

Vishwakarma, Vivek; Jain, Ankur

2017-09-01

While Gel Polymer Electrolytes (GPEs) have been widely investigated for use in next-generation Li-ion cells due to the potential for improved thermal safety, thermal transport within a GPE is still poorly understood. Among all materials in a Li-ion cell, the GPE has the lowest thermal conductivity, and hence determines the overall rate of heat flow in a Li-ion cell. This makes it critical to measure and understand thermal transport in a GPE and investigate trade-offs between thermal and ionic transport. This paper presents measurements of thermal and ionic conductivities in a PVdF-based GPE. The effect of incorporating BN/Al2O3 ceramic nano/microparticles in the GPE on thermal and ionic transport is characterized. Measurements indicate up to 2.5X improvement in thermal conductivity of activated GPE membranes, with relatively minor effect on electrochemical performance of GPE-based single-layer cells. The measured enhancement in thermal conductivity is in very good agreement with theoretical calculations based on the effective medium theory that accounts for thermal transport in a dispersed, two-phase medium such as a GPE. The fundamental insights gained in this work on thermal transport in a GPE and the role of nano/microparticle inclusions may facilitate thermal-electrochemical optimization and design of GPEs for safe, high-performance Li-ion cells.

Enhancing grain boundary ionic conductivity in mixed ionic-electronic conductors.

PubMed

Lin, Ye; Fang, Shumin; Su, Dong; Brinkman, Kyle S; Chen, Fanglin

2015-04-10

Mixed ionic-electronic conductors are widely used in devices for energy conversion and storage. Grain boundaries in these materials have nanoscale spatial dimensions, which can generate substantial resistance to ionic transport due to dopant segregation. Here, we report the concept of targeted phase formation in a Ce0.8Gd0.2O2-δ-CoFe2O4 composite that serves to enhance the grain boundary ionic conductivity. Using transmission electron microscopy and spectroscopy approaches, we probe the grain boundary charge distribution and chemical environments altered by the phase reaction between the two constituents. The formation of an emergent phase successfully avoids segregation of the Gd dopant and depletion of oxygen vacancies at the Ce0.8Gd0.2O2-δ-Ce0.8Gd0.2O2-δ grain boundary. This results in superior grain boundary ionic conductivity as demonstrated by the enhanced oxygen permeation flux. This work illustrates the control of mesoscale level transport properties in mixed ionic-electronic conductor composites through processing induced modifications of the grain boundary defect distribution.

Metal-air cell with performance enhancing additive

DOEpatents

Friesen, Cody A; Buttry, Daniel

2015-11-10

Systems and methods drawn to an electrochemical cell comprising a low temperature ionic liquid comprising positive ions and negative ions and a performance enhancing additive added to the low temperature ionic liquid. The additive dissolves in the ionic liquid to form cations, which are coordinated with one or more negative ions forming ion complexes. The electrochemical cell also includes an air electrode configured to absorb and reduce oxygen. The ion complexes improve oxygen reduction thermodynamics and/or kinetics relative to the ionic liquid without the additive.

Synergistic Interaction within Bifunctional Ruthenium Nanoparticle/SILP Catalysts for the Selective Hydrodeoxygenation of Phenols.

PubMed

Luska, Kylie L; Migowski, Pedro; El Sayed, Sami; Leitner, Walter

2015-12-21

Ruthenium nanoparticles immobilized on acid-functionalized supported ionic liquid phases (Ru NPs@SILPs) act as efficient bifunctional catalysts in the hydrodeoxygenation of phenolic substrates under batch and continuous flow conditions. A synergistic interaction between the metal sites and acid groups within the bifunctional catalyst leads to enhanced catalytic activities for the overall transformation as compared to the individual steps catalyzed by the separate catalytic functionalities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ionic liquid and nanoparticle hybrid systems: Emerging applications.

PubMed

He, Zhiqi; Alexandridis, Paschalis

2017-06-01

Having novel electronic and optical properties that emanate from their nano-scale dimensions, nanoparticles are central to numerous applications. Ionic liquids can confer to nanoparticle chemical protection and physicochemical property enhancement through intermolecular interactions and can consequently improve the stability and reusability of nanoparticle for various operations. With an aim to combine the novel properties of nanoparticles and ionic liquids, different structures have been generated, based on a balance of several intermolecular interactions. Such ionic liquid and nanoparticle hybrids are showing great potential in diverse applications. In this review, we first introduce various types of ionic liquid and nanoparticle hybrids, including nanoparticle colloidal dispersions in ionic liquids, ionic liquid-grafted nanoparticles, and nanoparticle-stabilized ionic liquid-based emulsions. Such hybrid materials exhibit interesting synergisms. We then highlight representative applications of ionic liquid and nanoparticle hybrids in the catalysis, electrochemistry and separations fields. Such hybrids can attain better stability and higher efficiency under a broad range of conditions. Novel and enhanced performance can be achieved in these applications by combining desired properties of ionic liquids and of nanoparticles within an appropriate hybrid nanostructure. Copyright © 2016 Elsevier B.V. All rights reserved.

Electric tempest in a teacup: The tea leaf analogy to microfluidic blood plasma separation

NASA Astrophysics Data System (ADS)

Yeo, Leslie Y.; Friend, James R.; Arifin, Dian R.

2006-09-01

In a similar fashion to Einstein's tea leaf paradox, the rotational liquid flow induced by ionic wind above a liquid surface can trap suspended microparticles by a helical motion, spinning them down towards a bottom stagnation point. The motion is similar to Batchelor [Q. J. Mech. Appl. Math. 4, 29 (1951)] flows occurring between stationary and rotating disks and arises due to a combination of the primary azimuthal and secondary bulk meridional recirculation that produces a centrifugal and enhanced inward radial force near the chamber bottom. The technology is thus useful for microfluidic particle trapping/concentration; the authors demonstrate its potential for rapid erythrocyte/blood plasma separation for miniaturized medical diagnostic kits.

High-Speed Lateral Flow Strategy for a Fast Biosensing with an Improved Selectivity and Binding Affinity.

PubMed

Cho, Dong Guk; Yoo, Haneul; Lee, Haein; Choi, Yeol Kyo; Lee, Minju; Ahn, Dong June; Hong, Seunghun

2018-05-10

We report a high-speed lateral flow strategy for a fast biosensing with an improved selectivity and binding affinity even under harsh conditions. In this strategy, biosensors were fixed at a location away from the center of a round shape disk, and the disk was rotated to create the lateral flow of a target solution on the biosensors during the sensing measurements. Experimental results using the strategy showed high reaction speeds, high binding affinity, and low nonspecific adsorptions of target molecules to biosensors. Furthermore, binding affinity between target molecules and sensing molecules was enhanced even in harsh conditions such as low pH and low ionic strength conditions. These results show that the strategy can improve the performance of conventional biosensors by generating high-speed lateral flows on a biosensor surface. Therefore, our strategy can be utilized as a simple but powerful tool for versatile bio and medical applications.

Microfluidic Fabrication of Cell Adhesive Chitosan Microtubes

PubMed Central

Oh, Jonghyun; Kim, Keekyoung; Won, Sung Wook; Cha, Chaenyung; Gaharwar, Akhilesh; Selimović, Šeila; Bae, Hojae; Lee, Kwang Ho; Lee, Dong Hwan; Lee, Sang-Hoon; Khademhosseini, Ali

2013-01-01

Chitosan has been used as a scaffolding material in tissue engineering due to its mechanical properties and biocompatibility. With increased appreciation of the effect of micro- and nanoscale environments on cellular behavior, there is increased emphasis on generating microfabricated chitosan structures. Here we employed a microfluidic coaxial flow-focusing system to generate cell adhesive chitosan microtubes of controlled sizes by modifying the flow rates of a chitosan pre-polymer solution and phosphate buffered saline (PBS). The microtubes were extruded from a glass capillary with a 300 μm inner diameter. After ionic crosslinking with sodium tripolyphosphate (TPP), fabricated microtubes had inner and outer diameter ranges of 70-150 μm and 120-185 μm. Computational simulation validated the controlled size of microtubes and cell attachment. To enhance cell adhesiveness on the microtubes, we mixed gelatin with the chitosan pre-polymer solution and adjusted the pH values of the chitosan pre-polymer solution with gelatin and TPP. During the fabrication of microtubes, fibroblasts suspended in core PBS flow adhered to the inner surface of chitosan-gelatin microtubes. To achieve physiological pH values, we adjusted pH values of chiotsan pre-polymer solution and TPP. In particular, we were able to improve cell viability to 92% with pH values of 5.8 and 7.4 for chitosan and TPP solution respectively. Cell culturing for three days showed that the addition of the gelatin enhanced cell spreading and proliferation inside the chitosan-gelatin microtubes. The microfluidic fabrication method for ionically crosslinked chitosan microtubes at physiological pH can be compatible with a variety of cells and used as a versatile platform for microengineered tissue engineering. PMID:23355068

Cobalt-Bridged Ionic Liquid Polymer on a Carbon Nanotube for Enhanced Oxygen Evolution Reaction Activity.

PubMed

Ding, Yuxiao; Klyushin, Alexander; Huang, Xing; Jones, Travis; Teschner, Detre; Girgsdies, Frank; Rodenas, Tania; Schlögl, Robert; Heumann, Saskia

2018-03-19

By taking inspiration from the catalytic properties of single-site catalysts and the enhancement of performance through ionic liquids on metal catalysts, we exploited a scalable way to place single cobalt ions on a carbon-nanotube surface bridged by polymerized ionic liquid. Single dispersed cobalt ions coordinated by ionic liquid are used as heterogeneous catalysts for the oxygen evolution reaction (OER). Performance data reveals high activity and stable operation without chemical instability. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Chemical composition and variability of the waters of the Edwards Plateau, central Texas

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

Groeger, A.W.; Gustafson, J.J.

1994-12-31

The surface waters of the karstic Edwards Plateau, southcentral Texas, are quite similar in many of their chemical characteristics. The ionic composition of the water was dominated by calcium and alkalinity (mostly bicarbonate) acquired through limestone weathering, and the ionic composition (in equivalents) was Ca>Mg>Na>K and alkalinity >Cl and SO{sub 4}. The median specific conductance and total dissolved solids ranged from 394 to 535 {mu}S cm{sup {minus}1} and 220 and 327 mg L{sup {minus}1}, respectively. The streams were always near or at supersaturation with respect to calcium carbonate, and the dynamics of calcium carbonate dissolution and precipitation tended to maintainmore » the dissolved substances at a fairly constant level. This may have been enhanced by the intimate contact of water and bedrock characteristic of karst drainages. Specific conductance, Ca, and alkalinity all decreased at higher summer temperatures. Many of the streams on the plateau maintained a constant level or actually increased concentrations of total dissolved substances at increased flow rates. These waters acquired significant quantities of solute as they flow through the confine Edwards Aquifer, including alkalinity, Ca, Mg, Na, Cl, and NO{sub 3}.« less

Interconnected ionic domains enhance conductivity in microphase separated block copolymer electrolytes

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

Arges, Christopher G.; Kambe, Yu; Dolejsi, Moshe

Block copolymer electrolytes (BCEs) represent an attractive choice as solid-state ionic conductors for electrochemical technologies used in energy storage and conversion, water treatment, sensors, and data storage and processing. Unlocking the maximum ionic conductivity of BCEs requires an intimate understanding as to how the microphase separated structure influences transport properties. However, elucidating such knowledge remains elusive due to the challenging task of precisely engineering BCEs with a defined structure in bulk materials. In this work, we examined BCEs in a thin film format because it was amenable to attaining BCEs with a desired nanostructure. Specifically, we systematically investigated anion-conducting BCEsmore » with different degrees of connectivity of the ionic domains. For the first time, we demonstrate that increasing terminal defects in the ionic domain from 1 terminal defect per mu m(2) to 20 terminal defects per mu m(2) ( a relatively small amount of defects) decreased ionic conductivity by 67% compared to the maximum value attained. Conversely, maximizing ionic domain connectivity increased the ionic conductivity by two-fold over a non-ordered BCE film. These experiments highlight that microphase separation alone was insufficient for ameliorating ionic conductivity in BCEs. Rather, microphase separation coupled with complete ionic domain connectivity realized BCEs with significantly enhanced ionic conductivity.« less

Colloidal Mechanisms of Gold Nanoparticle Loss in Asymmetric Flow Field-Flow Fractionation.

PubMed

Jochem, Aljosha-Rakim; Ankah, Genesis Ngwa; Meyer, Lars-Arne; Elsenberg, Stephan; Johann, Christoph; Kraus, Tobias

2016-10-07

Flow field-flow fractionation is a powerful method for the analysis of nanoparticle size distributions, but its widespread use has been hampered by large analyte losses, especially of metal nanoparticles. Here, we report on the colloidal mechanisms underlying the losses. We systematically studied gold nanoparticles (AuNPs) during asymmetrical flow field-flow fractionation (AF4) by systematic variation of the particle properties and the eluent composition. Recoveries of AuNPs (core diameter 12 nm) stabilized by citrate or polyethylene glycol (PEG) at different ionic strengths were determined. We used online UV-vis detection and off-line elementary analysis to follow particle losses during full analysis runs, runs without cross-flow, and runs with parts of the instrument bypassed. The combination allowed us to calculate relative and absolute analyte losses at different stages of the analytic protocol. We found different loss mechanisms depending on the ligand. Citrate-stabilized particles degraded during analysis and suffered large losses (up to 74%). PEG-stabilized particles had smaller relative losses at moderate ionic strengths (1-20%) that depended on PEG length. Long PEGs at higher ionic strengths (≥5 mM) caused particle loss due to bridging adsorption at the membrane. Bulk agglomeration was not a relevant loss mechanism at low ionic strengths ≤5 mM for any of the studied particles. An unexpectedly large fraction of particles was lost at tubing and other internal surfaces. We propose that the colloidal mechanisms observed here are relevant loss mechanisms in many particle analysis protocols and discuss strategies to avoid them.

On the relationship between the specific heat enhancement of salt-based nanofluids and the ionic exchange capacity of nanoparticles.

PubMed

Mondragón, Rosa; Juliá, J Enrique; Cabedo, Luis; Navarrete, Nuria

2018-05-14

Nanoparticles have been used in thermal applications to increase the specific heat of the molten salts used in Concentrated Solar Power plants for thermal energy storage. Although several mechanisms for abnormal enhancement have been proposed, they are still being investigated and more research is necessary. However, this nanoparticle-salt interaction can also be found in chemical applications in which nanoparticles have proved suitable to be used as an adsorbent for nitrate removal given their high specific surface, reactivity and ionic exchange capacity. In this work, the ionic exchange capacity mechanism for the nanoparticles functionalization phenomenon was evaluated. The ionic exchange capacity of silica and alumina nanoparticles dispersed in lithium, sodium and potassium nitrates was measured. Fourier-transform infrared spectroscopy tests confirmed the adsorption of nitrate ions on the nanoparticle surface. A relationship between the ionic exchange capacity of nanoparticles and the specific heat enhancement of doped molten salts was proposed for the first time.

Sequential injection ionic liquid dispersive liquid-liquid microextraction for thallium preconcentration and determination with flame atomic absorption spectrometry.

PubMed

Anthemidis, Aristidis N; Ioannou, Kallirroy-Ioanna G

2012-08-01

A novel, automatic on-line sequential injection dispersive liquid-liquid microextraction (SI-DLLME) method, based on 1-hexyl-3-methylimidazolium hexafluorophosphate ([Hmim][PF(6)]) ionic liquid as an extractant solvent was developed and demonstrated for trace thallium determination by flame atomic absorption spectrometry. The ionic liquid was on-line fully dispersed into the aqueous solution in a continuous flow format while the TlBr(4)(-) complex was easily migrated into the fine droplets of the extractant due to the huge contact area of them with the aqueous phase. Furthermore, the extractant was simply retained onto the surface of polyurethane foam packed into a microcolumn. No specific conditions like low temperature are required for extractant isolation. All analytical parameters of the proposed method were investigated and optimized. For 15 mL of sample solution, an enhancement factor of 290, a detection limit of 0.86 μg L(-1) and a precision (RSD) of 2.7% at 20.0 μg L(-1) Tl(I) concentration level, was obtained. The developed method was evaluated by analyzing certified reference materials while good recoveries from environmental and biological samples proved that present method was competitive in practical applications.

Indoor air purification by dielectric barrier discharge combined with ionic wind: physical and microbiological investigations

NASA Astrophysics Data System (ADS)

Timmermann, E.; Prehn, F.; Schmidt, M.; Höft, H.; Brandenburg, R.; Kettlitz, M.

2018-04-01

A non-thermal plasma source based on a surface dielectric barrier discharge (DBD) is developed for purification of recirculating air in operating theatres in hospitals. This is a challenging application due to high flow rates, short treatment times and the low threshold for ozone in the ventilated air. Therefore, the surface DBD was enhanced in order to generate an ionic wind, which can deflect and thus, filter out airborne microorganisms. Electrical and gas diagnostics as well as microbiological experiments were performed in a downscaled plasma source under variation of various electrical parameters, but application-oriented airflow velocity and humidity. The dependence of electrical power and ozone concentration as well as charged particles in the plasma treated air on frequency, voltage and relative humidity is presented and discussed. The presence of humidity causes a more conductive dielectric surface and thus a weaker plasma formation, especially at low frequency. The airborne test bacteria, Escherichia coli, showed significant effect to plasma treatment (up to 20% reduction) and to plasma with ionic wind (up to 90% removal); especially a configuration with 70% removal and an accompanying ozone concentration of only 360 ppb is promising for future application.

A self-consistent model of ionic wind generation by negative corona discharges in air with experimental validation

NASA Astrophysics Data System (ADS)

Chen, She; Nobelen, J. C. P. Y.; Nijdam, S.

2017-09-01

Ionic wind is produced by a corona discharge when gaseous ions are accelerated in the electric field and transfer their momentum to neutral molecules by collisions. This technique is promising because a gas flow can be generated without the need for moving parts and can be easily miniaturized. The basic theory of ionic wind sounds simple but the details are far from clear. In our experiment, a negative DC voltage is applied to a needle-cylinder electrode geometry. Hot wire anemometry is used to measure the flow velocity at the downstream exit of the cylinder. The flow velocity fluctuates but the average velocity increases with the voltage. The current consists of a regular train of pulses with short rise time, the well-known Trichel pulses. To reveal the ionic wind mechanism in the Trichel pulse stage, a three-species corona model coupled with gas dynamics is built. The drift-diffusion equations of the plasma together with the Navier-Stokes equations of the flow are solved in COMSOL Multiphysics. The electric field, net number density of charged species, electrohydrodynamic (EHD) body force and flow velocity are calculated in detail by a self-consistent model. Multiple time scales are employed: hundreds of microseconds for the plasma characteristics and longer time scales (˜1 s) for the flow behavior. We found that the flow velocity as well as the EHD body force have opposite directions in the ionization region close to the tip and the ion drift region further away from the tip. The calculated mean current, Trichel pulse frequency and flow velocity are very close to our experimental results. Furthermore, in our simulations we were able to reproduce the mushroom-like minijets observed in experiments.

Incorporation of ionic liquid into porous polymer monoliths to enhance the separation of small molecules in reversed-phase high-performance liquid chromatography.

PubMed

Wang, Jiafei; Bai, Ligai; Wei, Zhen; Qin, Junxiao; Ma, Yamin; Liu, Haiyan

2015-06-01

An ionic liquid was incorporated into the porous polymer monoliths to afford stationary phases with enhanced chromatographic performance for small molecules in reversed-phase high-performance liquid chromatography. The effect of the ionic liquid in the polymerization mixture on the performance of the monoliths was studied in detail. While monoliths without ionic liquid exhibited poor resolution and low efficiency, the addition of ionic liquid to the polymerization mixture provides highly increased resolution and high efficiency. The chromatographic performances of the monoliths were demonstrated by the separations of various small molecules including aromatic hydrocarbons, isomers, and homologues using a binary polar mobile phase. The present column efficiency reached 27 000 plates/m, which showed that the ionic liquid monoliths are alternative stationary phases in the separation of small molecules by high-performance liquid chromatography. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced nonlinear optical responses in donor-acceptor ionic complexes via photo induced energy transfer.

PubMed

Mamidala, Venkatesh; Polavarapu, Lakshminarayana; Balapanuru, Janardhan; Loh, Kian Ping; Xu, Qing-Hua; Ji, Wei

2010-12-06

By complexion of donor and acceptor using ionic interactions, the enhanced nonlinear optical responses of donor-acceptor ionic complexes in aqueous solution were studied with 7-ns laser pulses at 532 nm. The optical limiting performance of negatively charged gold nanoparticles or graphene oxide (Acceptor) was shown to be improved significantly when they were mixed with water-soluble, positively-charged porphyrin (Donor) derivative. In contrast, no enhancement was observed when mixing with negatively-charged porphyrin. Transient absorption studies of the donor-acceptor complexes confirmed that the addition of energy transfer pathway were responsible for excited-state deactivation, which results in the observed enhancement. Fluence, angle-dependent scattering and time correlated single photon counting measurements suggested that the enhanced nonlinear scattering due to faster nonradiative decay should play a major role in the enhanced optical limiting responses.

Geometry effect on electrokinetic flow and ionic conductance in pH-regulated nanochannels

NASA Astrophysics Data System (ADS)

Sadeghi, Morteza; Saidi, Mohammad Hassan; Moosavi, Ali; Sadeghi, Arman

2017-12-01

Semi-analytical solutions are obtained for the electrical potential, electroosmotic velocity, ionic conductance, and surface physicochemical properties associated with long pH-regulated nanochannels of arbitrary but constant cross-sectional area. The effects of electric double layer overlap, multiple ionic species, and surface association/dissociation reactions are all taken into account, assuming low surface potentials. The method of analysis includes series solutions which the pertinent coefficients are obtained by applying the wall boundary conditions using either of the least-squares or point matching techniques. Although the procedure is general enough to be applied to almost any arbitrary cross section, nine nanogeometries including polygonal, trapezoidal, double-trapezoidal, rectangular, elliptical, semi-elliptical, isosceles triangular, rhombic, and isotropically etched profiles are selected for presentation. For the special case of an elliptic cross section, full analytical solutions are also obtained utilizing the Mathieu functions. We show that the geometrical configuration plays a key role in determination of the ionic conductance, surface charge density, electrical potential and velocity fields, and proton enhancement. In this respect, the net electric charge and convective ionic conductance are higher for channels of larger perimeter to area ratio, whereas the opposite is true for the average surface charge density and mean velocity; the geometry impact on the two latest ones, however, vanishes if the background salt concentration is high enough. Moreover, we demonstrate that considering a constant surface potential equal to the average charge-regulated potential provides sufficiently accurate results for smooth geometries such as an ellipse at medium-high aspect ratios but leads to significant errors for geometries having narrow corners such as a triangle.

Microcontact Printing of Thiol-Functionalized Ionic Liquid Microarrays for "Membrane-less" and "Spill-less" Gas Sensors.

PubMed

Gondosiswanto, Richard; Gunawan, Christian A; Hibbert, David B; Harper, Jason B; Zhao, Chuan

2016-11-16

Lab-on-a-chip systems have gained significant interest for both chemical synthesis and assays at the micro-to-nanoscale with a unique set of benefits. However, solvent volatility represents one of the major hurdles to the reliability and reproducibility of the lab-on-a-chip devices for large-scale applications. Here we demonstrate a strategy of combining nonvolatile and functionalized ionic liquids with microcontact printing for fabrication of "wall-less" microreactors and microfluidics with high reproducibility and high throughput. A range of thiol-functionalized ionic liquids have been synthesized and used as inks for microcontact printing of ionic liquid microdroplet arrays onto gold chips. The covalent bonds formed between the thiol-functionalized ionic liquids and the gold substrate offer enhanced stability of the ionic liquid microdroplets, compared to conventional nonfunctionalized ionic liquids, and these microdroplets remain stable in a range of nonpolar and polar solvents, including water. We further demonstrate the use of these open ionic liquid microarrays for fabrication of "membrane-less" and "spill-less" gas sensors with enhanced reproducibility and robustness. Ionic-liquid-based microarray and microfluidics fabricated using the described microcontact printing may provide a versatile platform for a diverse number of applications at scale.

Explicit role of ionic strength in retention behavior of polystyrene latex particles in sedimentation field-flow fractionation: Slip boundary model.

PubMed

Rah, Kyunil; Han, Sujeong; Choi, Jaeyeong; Eum, Chul Hun; Lee, Seungho

2017-12-15

We investigate an explicit role of the ionic strength in the retention behaviors of polystyrene (PS) latex particles in sedimentation field-flow fractionation (SdFFF) by hinging upon the retention theory recently developed [1] asR=(R o +v b * )/(1+v b * ). Here R is an experimental retention ratio, and R o is the analytical expression of the standard retention theory based on the parabolic flow velocity. The reduced boundary velocityv b * is expressed in terms of the ionic strength I of the carrier liquid as v b * =v b,o * /(1+εI), where v b,o * =0.070and ε=60 mM -1 for all the PS latex systems under investigation. We then apply this to study the explicit ionic strength effect on the retention behaviors of PS beads of 200, 300, 400, and 500nm, respectively. As a primary result, the strong dependence of the retention ratio on the ionic strength can be quantitatively accounted for in an excellent accuracy: The slip effect at the channel surface is significant, particularly when I≲0.5mM, without showing any distinguishable dependence on the specific additives to control I, such as FL-70, SDS, NaNO 3 , and NaN 3 . Based on the present study, we put forward an experimental means to estimate the ionic strength of an aqueous solution using an FFF technique. Copyright © 2017. Published by Elsevier B.V.

Enhanced Electro-Static Modulation of Ionic Diffusion through Carbon Nanotube Membranes by Diazonium Grafting Chemistry

PubMed Central

Majumder, Mainak; Keis, Karin; Zhan, Xin; Meadows, Corey; Cole, Jeggan

2013-01-01

A membrane structure consisting of an aligned array of open ended carbon nanotubes (~ 7 nm i.d.) spanning across an inert polymer matrix allows the diffusive transport of aqueous ionic species through CNT cores. The plasma oxidation process that opens CNTs tips inherently introduces carboxylic acid groups at the CNT tips, which allows for a limited amount of chemical functional at the CNT pore entrance. However for numerous applications, it is important to increase the density of carboxylic acid groups at the pore entrance for effective separation processes. Aqueous diazonium based electro-chemistry significantly increases the functional density of carboxylic acid groups. pH dependent dye adsorption-desorption and interfacial capacitance measurements indicate ~ 5–6 times increase in functional density. To further control the spatial location of the functional chemistry, a fast flowing inert liquid column inside the CNT core is found to restrict the diazonium grafting to the CNT tips only. This is confirmed by the increased flux of positively charged Ru(bi-py)3+2 with anionic functionality. The electrostatic enhancement of ion diffusion is readily screened in 0.1(M) electrolyte solution consistent with the membrane pore geometry and increased functional density. PMID:25132719

Characterisation of cationic potato starch by asymmetrical flow field-flow fractionation. Influence of ionic strength and degree of substitution.

PubMed

Santacruz, Stalin

2014-06-15

The properties of a paper sheet depend on the absorption together with the physico-chemical properties of additives used in the paper processing. The effect of ionic strength and degree of substitution of cationic potato starch on the elution pattern of asymmetrical flow field-flow fractionation was analysed. The effect of starch derivatisation, in either dry or wet phase, was also investigated. Average molar mass showed no difference between the starches obtained from the two derivatisation processes. Apparent densities showed that dry cationic starch had higher density than wet cationic starch for a hydrodynamic radius between 50 and 100 nm. Elution times of native and three cationic starches increased when the ionic strength increased from 50 to 100mM. No differences in the molar mass among cationic starches with different degree of substitution suggested no degradation due to a derivatisation process. Large sample loads can be used at 100mM without overloading. Copyright © 2014 Elsevier Ltd. All rights reserved.

Water Contaminant Mitigation in Ionic Liquid Propellant

NASA Technical Reports Server (NTRS)

Conroy, David; Ziemer, John

2009-01-01

Appropriate system and operational requirements are needed in order to ensure mission success without unnecessary cost. Purity requirements applied to thruster propellants may flow down to materials and operations as well as the propellant preparation itself. Colloid electrospray thrusters function by applying a large potential to a room temperature liquid propellant (such as an ionic liquid), inducing formation of a Taylor cone. Ions and droplets are ejected from the Taylor cone and accelerated through a strong electric field. Electrospray thrusters are highly efficient, precise, scaleable, and demonstrate low thrust noise. Ionic liquid propellants have excellent properties for use as electrospray propellants, but can be hampered by impurities, owing to their solvent capabilities. Of foremost concern is the water content, which can result from exposure to atmosphere. Even hydrophobic ionic liquids have been shown to absorb water from the air. In order to mitigate the risks of bubble formation in feed systems caused by water content of the ionic liquid propellant, physical properties of the ionic liquid EMI-Im are analyzed. The effects of surface tension, material wetting, physisorption, and geometric details of the flow manifold and electrospray emitters are explored. Results are compared to laboratory test data.

Methods for forming small-volume electrical contacts and material manipulations with fluid microchannels

DOEpatents

Jacobson, Stephen C [Knoxville, TN; Ramsey, J Michael [Knoxville, TN; Culbertson, Christopher T [Oak Ridge, TN; Whitten, William B [Lancing, TN; Foote, Robert S [Oak Ridge, TN

2011-12-27

A microfabricated device employing a bridging membrane and methods for electrokinetic transport of a liquid phase biological or chemical material using the same are described. The bridging membrane is deployed in or adjacent to a microchannel and permits either ionic current flow or the transport of gas species, while inhibiting the bulk flow of material. The use of bridging membranes in accordance with this invention is applicable to a variety of processes, including electrokinetically induced pressure flow in a region of a microchannel that is not influenced by an electric field, sample concentration enhancement and injection, as well as improving the analysis of materials where it is desired to eliminate electrophoretic bias. Other applications of the bridging membranes according to this invention include the separation of species from a sample material, valving of fluids in a microchannel network, mixing of different materials in a microchannel, and the pumping of fluids.

Methods for forming small-volume electrical contacts and material manipulations with fluidic microchannels

DOEpatents

Jacobson, Stephen C [Knoxville, TN; Ramsey, J Michael [Knoxville, TN; Culbertson, Christopher T [Oak Ridge, TN; Whitten, William B [Lancing, TN; Foote, Robert S [Oak Ridge, TN

2011-04-26

A microfabricated device employing a bridging membrane and methods for electrokinetic transport of a liquid phase biological or chemical material using the same are described. The bridging membrane is deployed in or adjacent to a microchannel and permits either ionic current flow or the transport of gas species, while inhibiting the bulk flow of material. The use of bridging membranes in accordance with this invention is applicable to a variety of processes, including electrokinetically induced pressure flow in a region of a microehannel that is not influenced by an electric field, sample concentration enhancement and injection, as well as improving the analysis of materials where it is desired to eliminate electrophoretic bias. Other applications of the bridging membranes according to this invention include the separation of species from a sample material, valving of fluids in a microchannel network, mixing of different materials in a microchannel, and the pumping of fluids.

Methods for forming small-volume electrical contacts and material manipulations with fluidic microchannels

DOEpatents

Jacobson, Stephen C [Knoxville, TN; Ramsey, J Michael [Knoxville, TN; Culbertson, Christopher T [Oak Ridge, TN; Whitten, William B [Lancing, TN; Foote, Robert S [Oak Ridge, TN

2011-03-22

A microfabricated device employing a bridging membrane and methods for electrokinetic transport of a liquid phase biological or chemical material using the same are described. The bridging membrane is deployed in or adjacent to a microchannel and permits either ionic current flow or the transport of gas species, while inhibiting the bulk flow of material. The use of bridging membranes in accordance with this invention is applicable to a variety of processes, including electrokinetically induced pressure flow in a region of a microchannel that is not influenced by an electric field, sample concentration enhancement and injection, as well as improving the analysis of materials where it is desired to eliminate electrophoretic bias. Other applications of the bridging membranes according to this invention include the separation of species from a sample material, valving of fluids in a microchannel network, mixing of different materials in a microchannel, and the pumping of fluids.

Methods for forming small-volume electrical contacts and material manipulations with fluidic microchannels

DOEpatents

Jacobson, Stephen C.; Ramsey, J. Michael

2007-11-20

A microfabricated device employing a bridging membrane and methods for electrokinetic transport of a liquid phase biological or chemical material using the same are described. The bridging membrane is deployed in or adjacent to a microchannel and permits either ionic current flow or the transport of gas species, while inhibiting the bulk flow of material. The use of bridging membranes in accordance with this invention is applicable to a variety of processes, including electrokinetically induced pressure flow in a region of a microchannel that is not influenced by an electric field, sample concentration enhancement and injection, as well as improving the analysis of materials where it is desired to eliminate electrophoretic bias. Other applications of the bridging membranes according to this invention include the separation of species from a sample material, valving of fluids in a microchannel network, mixing of different materials in a microchannel, and the pumping of fluids.

Methods for forming small-volume electrical contacts and material manipulations with fluidic microchannels

DOEpatents

Jacobson, Stephen C.; Ramsey, J. Michael; Culbertson, Christopher T.; Whitten, William B.; Foote, Robert S.

2004-02-03

A microfabricated device employing a bridging membrane and methods for electrokinetic transport of a liquid phase biological or chemical material using the same are described. The bridging membrane is deployed in or adjacent to a microchannel and permits either ionic current flow or the transport of gas species, while inhibiting the bulk flow of material. The use of bridging membranes in accordance with this invention is applicable to a variety of processes, including electrokinetically induced pressure flow in a region of a microchannel that is not influenced by an electric field, sample concentration enhancement and injection, as well as improving the analysis of materials where it is desired to eliminate electrophoretic bias. Other applications of the bridging membranes according to this invention include the separation of species from a sample material, valving of fluids in a microchannel network, mixing of different materials in a microchannel, and the pumping of fluids.

The effect of DC voltage polarity on ionic wind in ambient air for cooling purposes

NASA Astrophysics Data System (ADS)

Chen, She; van den Berg, R. G. W.; Nijdam, S.

2018-05-01

Gas flows can be induced by gas discharges like DC coronas because neutral molecules gain momentum by ion-neutral collisions. This can be used for active cooling and has advantages over mechanical fans. We investigate ionic wind by a DC corona discharge under different conditions with an emphasis on the effects of voltage polarity and the transition between different discharge regimes. We also consider the gas temperature of a DC corona which is important when it is to be used for cooling purposes. Although DC coronas are usually characterized as low temperature plasmas, gas heating can have a significant impact on flow generation, especially at higher operating voltages. In this paper, a 5–20 kV DC voltage of positive and negative polarity is applied to a needle–cylinder electrode. The ionic wind velocity at the exit of the cylinder electrode is measured by hot wire anemometry and the emission spectrum is used to study the gas temperature. It is found that the flow velocity induced by positive coronas is higher than that by negative coronas for voltages above 10–15 kV, which is also demonstrated by a phenomenological EHD force model. Furthermore, a heated column is observed by Schlieren technique for both voltage polarities. An improved self-consistent ionic wind model considering heat transfer is built to study the temperature distribution. The simulation results indicate that the gas flow velocity is lower on the symmetry axis when the temperature gradient is taken into account, something which is usually ignored in ionic wind simulations.

Impact of multicomponent ionic transport on pH fronts propagation in saturated porous media

NASA Astrophysics Data System (ADS)

Muniruzzaman, Muhammad; Rolle, Massimo

2016-04-01

Multicomponent ionic interactions have been increasingly recognized as important factors for the displacement of charged species in porous media under both diffusion- [1,2] and advection-dominated flow regimes [3,4]. In this study we investigate the propagation of pH fronts during multicomponent ionic transport in saturated porous media under flow-through conditions. By performing laboratory bench-scale experiments combined with numerical modeling we show the important influence of Coulombic effects on proton transport in the presence of ionic admixtures. The experiments were performed in a quasi two-dimensional flow-through setup under steady-state flow and transport conditions. Dilute solutions of hydrochloric acid with MgCl2 (1:2 strong electrolyte) were used as tracer solutions to experimentally test the effect of electrochemical cross-coupling on the migration of diffusive/dispersive pH fronts. We focus on two experimental scenarios, with different composition of tracer solutions, causing remarkably different effects on the propagation of the acidic fronts with relative differences in the penetration depth of pH fronts of 36% between the two scenarios and of 25% and 15% for each scenario with respect to the transport of ions at liberated state (i.e., without considering the charge effects). Also significant differences in the dilution of the distinct ionic plumes, quantified using the flux-related dilution index at the laboratory bench scale [5], were measured at the outflow of the flow-through system. The dilution of the pH plumes also changed considerably (26% relative difference) in the two flow-through experiments only due to the different composition of the pore water solution and to the electrostatic coupling of the ions in the flow-through setups. Numerical transport simulations were performed to interpret the laboratory experiments. The simulations were based on a multicomponent ionic formulation accurately capturing the Coulombic interactions between the transported ions in the flow-through system. The results of purely forward simulations show a very good agreement with the high-resolution measurements performed at the outlet of the flow-through setup and illustrate the importance of charge effects on pH fronts propagation in porous media. [1] Giambalvo, E. R., C. I. Steefel, A. T. Fisher, N. D. Rosenberg, and C. G. Wheat (2002), Effect of fluid-sediment reaction on hydrothermal fluxes of major elements, eastern flank of the Juan de Fuca Ridge, Geochim. Cosmochim. Acta, 66, 1739-1757. [2] Appelo, C. A. J., and P. Wersin (2007), Multicomponent diffusion modeling in clay systems with application to the diffusion of tritium, iodide, and sodium in opalinus clay, Environ. Sci. Technol., 41, 5002-5007. [3] Rolle, M., M. Muniruzzaman, C. M. Haberer, and P. Grathwohl (2013), Coulombic effects in advection-dominated transport of electrolytes in porous media: Multicomponent ionic dispersion, Geochim. Cosmochim. Acta, 120, 195-205. [4] Muniruzzaman, M., C. M. Haberer, P. Grathwohl, and M. Rolle (2014), Multicomponent ionic dispersion during transport of electrolytes in heterogeneous porous media: Experiments and model-based interpretation, Geochim. Cosmochim. Acta, 141, 656-669. [5] Rolle, M., G. Chiogna, D. L. Hochstetler, and P. K. Kitanidis (2013), On the importance of diffusion and compound-specific mixing for groundwater transport: An investigation from pore to field scale, J. Contam. Hydrol., 153, 51-68.

Double-membrane triple-electrolyte redox flow battery design

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

Yushan, Yan; Gu, Shuang; Gong, Ke

A redox flow battery is provided having a double-membrane (one cation exchange membrane and one anion exchange membrane), triple-electrolyte (one electrolyte in contact with the negative electrode, one electrolyte in contact with the positive electrode, and one electrolyte positioned between and in contact with the two membranes). The cation exchange membrane is used to separate the negative or positive electrolyte and the middle electrolyte, and the anion exchange membrane is used to separate the middle electrolyte and the positive or negative electrolyte. This design physically isolates, but ionically connects, the negative electrolyte and positive electrolyte. The physical isolation offers greatmore » freedom in choosing redox pairs in the negative electrolyte and positive electrolyte, making high voltage of redox flow batteries possible. The ionic conduction drastically reduces the overall ionic crossover between negative electrolyte and positive one, leading to high columbic efficiency.« less

Continuous Flow Polymer Synthesis toward Reproducible Large-Scale Production for Efficient Bulk Heterojunction Organic Solar Cells.

PubMed

Pirotte, Geert; Kesters, Jurgen; Verstappen, Pieter; Govaerts, Sanne; Manca, Jean; Lutsen, Laurence; Vanderzande, Dirk; Maes, Wouter

2015-10-12

Organic photovoltaics (OPV) have attracted great interest as a solar cell technology with appealing mechanical, aesthetical, and economies-of-scale features. To drive OPV toward economic viability, low-cost, large-scale module production has to be realized in combination with increased top-quality material availability and minimal batch-to-batch variation. To this extent, continuous flow chemistry can serve as a powerful tool. In this contribution, a flow protocol is optimized for the high performance benzodithiophene-thienopyrroledione copolymer PBDTTPD and the material quality is probed through systematic solar-cell evaluation. A stepwise approach is adopted to turn the batch process into a reproducible and scalable continuous flow procedure. Solar cell devices fabricated using the obtained polymer batches deliver an average power conversion efficiency of 7.2 %. Upon incorporation of an ionic polythiophene-based cathodic interlayer, the photovoltaic performance could be enhanced to a maximum efficiency of 9.1 %. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redox active polymers and colloidal particles for flow batteries

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

Gavvalapalli, Nagarjuna; Moore, Jeffrey S.; Rodriguez-Lopez, Joaquin

The invention provides a redox flow battery comprising a microporous or nanoporous size-exclusion membrane, wherein one cell of the battery contains a redox-active polymer dissolved in the non-aqueous solvent or a redox-active colloidal particle dispersed in the non-aqueous solvent. The redox flow battery provides enhanced ionic conductivity across the electrolyte separator and reduced redox-active species crossover, thereby improving the performance and enabling widespread utilization. Redox active poly(vinylbenzyl ethylviologen) (RAPs) and redox active colloidal particles (RACs) were prepared and were found to be highly effective redox species. Controlled potential bulk electrolysis indicates that 94-99% of the nominal charge on different RAPsmore » is accessible and the electrolysis products are stable upon cycling. The high concentration attainable (>2.0 M) for RAPs in common non-aqueous battery solvents, their electrochemical and chemical reversibility, and their hindered transport across porous separators make them attractive materials for non-aqueous redox flow batteries based on size-selectivity.« less

Synergistic Impacts of Electrolyte Adsorption on the Thermoelectric Properties of Single-Walled Carbon Nanotubes.

PubMed

Nakano, Motohiro; Nakashima, Takuya; Kawai, Tsuyoshi; Nonoguchi, Yoshiyuki

2017-08-01

Single-walled carbon nanotubes are promising candidates for light-weight and flexible energy materials. Recently, the thermoelectric properties of single-walled carbon nanotubes have been dramatically improved by ionic liquid addition; however, controlling factors remain unsolved. Here the thermoelectric properties of single-walled carbon nanotubes enhanced by electrolytes are investigated. Complementary characterization with absorption, Raman, and X-ray photoelectron spectroscopy reveals that shallow hole doping plays a partial role in the enhanced electrical conductivity. The molecular factors controlling the thermoelectric properties of carbon nanotubes are systematically investigated in terms of the ionic functionalities of ionic liquids. It is revealed that appropriate ionic liquids show a synergistic enhancement in conductivity and the Seebeck coefficient. The discovery of significantly precise doping enables the generation of thermoelectric power factor exceeding 460 µW m - 1 K -2 . © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Retention of neodymium by dolomite at variable ionic strength as probed by batch and column experiments.

PubMed

Emerson, H P; Zengotita, F; Richmann, M; Katsenovich, Y; Reed, D T; Dittrich, T M

2018-10-01

The results presented in this paper highlight the complexity of adsorption and incorporation processes of Nd with dolomite and significantly improve upon previous work investigating trivalent actinide and lanthanide interactions with dolomite. Both batch and mini column experiments were conducted at variable ionic strength. These data highlight the strong chemisorption of Nd to the dolomite surface (equilibrium K d 's > 3000 mL/g) and suggest that equilibrium adsorption processes may not be affected by ionic strength based on similar results at 0.1 and 5.0 M ionic strength in column breakthrough and equilibrium batch (>5 days) results. Mini column experiments conducted over approximately one year also represent a significant development in measurement of sorption of Nd in the presence of flow as previous large-scale column experiments did not achieve breakthrough likely due to the high loading capacity of dolomite for Nd (up to 240 μg/g). Batch experiments in the absence of flow show that the rate of Nd removal increases with increasing ionic strength (up to 5.0 M) with greater removal at greater ionic strength for a 24 h sampling point. We suggest that the increasing ionic strength induces increased mineral dissolution and re-precipitation caused by changes in activity with ionic strength that lead to increased removal of Nd through co-precipitation processes. Copyright © 2018 Elsevier Ltd. All rights reserved.

Nanoparticle enhanced ionic liquid heat transfer fluids

DOEpatents

Fox, Elise B.; Visser, Ann E.; Bridges, Nicholas J.; Gray, Joshua R.; Garcia-Diaz, Brenda L.

2014-08-12

A heat transfer fluid created from nanoparticles that are dispersed into an ionic liquid is provided. Small volumes of nanoparticles are created from e.g., metals or metal oxides and/or alloys of such materials are dispersed into ionic liquids to create a heat transfer fluid. The nanoparticles can be dispersed directly into the ionic liquid during nanoparticle formation or the nanoparticles can be formed and then, in a subsequent step, dispersed into the ionic liquid using e.g., agitation.

Flow-induced voltage generation in non-ionic liquids over monolayer graphene

NASA Astrophysics Data System (ADS)

Ho Lee, Seung; Jung, Yousung; Kim, Soohyun; Han, Chang-Soo

2013-02-01

To clarify the origin of the flow-induced voltage generation in graphene, we prepared a new experimental device whose electrodes were aligned perpendicular to the flow with a non-ionic liquid. We found that significant voltage in our device was generated with increasing flow velocity, thereby confirming that voltage was due to an intrinsic interaction between graphene and the flowing liquid. To understand the mechanism of the observed flow-induced voltage generation, we systematically varied several important experimental parameters: flow velocity, electrode alignment, liquid polarity, and liquid viscosity. Based on these measurements, we suggest that polarity of the fluid is a significant factor in determining the extent of the voltage generated, and the major mechanism can be attributed to instantaneous potential differences induced in the graphene due to an interaction with polar liquids and to the momentum transferred from the flowing liquid to the graphene.

Ionic Liquid Droplet Microreactor for Catalysis Reactions Not at Equilibrium.

PubMed

Zhang, Ming; Ettelaie, Rammile; Yan, Tao; Zhang, Suojiang; Cheng, Fangqin; Binks, Bernard P; Yang, Hengquan

2017-12-06

We develop a novel strategy to more effectively and controllably process continuous enzymatic or homogeneous catalysis reactions based on nonaqueous Pickering emulsions. A key element of this strategy is "bottom-up" construction of a macroscale continuous flow reaction system through packing catalyst-containing micron-sized ionic liquid (IL) droplet in oil in a column reactor. Due to the continuous influx of reactants into the droplet microreactors and the continuous release of products from the droplet microreactors, catalysis reactions in such a system can take place without limitations arising from establishment of the reaction equilibrium and catalyst separation, inherent in conventional batch reactions. As proof of the concept, enzymatic enantioselective trans-esterification and CuI-catalyzed cycloaddition reactions using this IL droplet-based flow system both exhibit 8 to 25-fold enhancement in catalysis efficiency compared to their batch counterparts, and a durability of at least 4000 h for the enantioselective trans-esterification of 1-phenylethyl alcohol, otherwise unattainable in their batch counterparts. We further establish a theoretical model for such a catalysis system working under nonequilibrium conditions, which not only supports the experimental results but also helps to predict reaction progress at a microscale level. Being operationally simple, efficient, and adaptive, this strategy provides an unprecedented platform for practical applications of enzymes and homogeneous catalysts even at a controllable level.

Adsorption removal of tannic acid from aqueous solution by polyaniline: Analysis of operating parameters and mechanism.

PubMed

Sun, Chencheng; Xiong, Bowen; Pan, Yang; Cui, Hao

2017-02-01

Polyaniline (PANI) prepared by chemical oxidation was studied for adsorption removal of tannic acid (TA) from aqueous solution. Batch adsorption studies were carried out under different adsorbent dosages, pH, ionic strength, initial TA concentration and coexisting anions. Solution pH had an important impact on TA adsorption onto PANI with optimal removal in the pH range of 8-11. TA adsorption on PANI at three ionic strength levels (0.02, 0.2 and 2molL -1 NaCl) could be well described by Langmuir model (monolayer adsorption process) and the maximum adsorption capacity was 230, 223 and 1023mgg -1 , respectively. Kinetic data showed that TA adsorption on PANI fitted well with pseudo-second-order model (controlled by chemical process). Among the coexisting anions tested, PO 4 3- significantly inhibited TA adsorption due to the enhancement of repulsive interaction. Continuous flow adsorption studies indicated good flexibility and adaptability of the PANI adsorbent under different flow rates and influent TA concentrations. The mechanism controlling TA adsorption onto PANI under different operating conditions was analyzed with the combination of electrostatic interactions, hydrogen bonding, π-π interactions and Van der Waals interactions. Copyright © 2016 Elsevier Inc. All rights reserved.

An extended model based on the modified Nernst-Planck equation for describing transdermal iontophoresis of weak electrolytes.

PubMed

Imanidis, Georgios; Luetolf, Peter

2006-07-01

An extended model for iontophoretic enhancement of transdermal drug permeation under constant voltage is described based on the previously modified Nernst-Planck equation, which included the effect of convective solvent flow. This model resulted in an analytical expression for the enhancement factor as a function of applied voltage, convective flow velocity due to electroosmosis, ratio of lipid to aqueous pathway passive permeability, and weighted average net ionic valence of the permeant in the aqueous epidermis domain. The shift of pH in the epidermis compared to bulk caused by the electrical double layer at the lipid-aqueous domain interface was evaluated using the Poisson-Boltzmann equation. This was solved numerically for representative surface charge densities and yielded pH differences between bulk and epidermal aqueous domain between 0.05 and 0.4 pH units. The developed model was used to analyze the experimental enhancement of an amphoteric weak electrolyte measured in vitro using human cadaver epidermis and a voltage of 250 mV at different pH values. Parameter values characterizing the involved factors were determined that yielded the experimental enhancement factors and passive permeability coefficients at all pH values. The model provided a very good agreement between experimental and calculated enhancement and passive permeability. The deduced parameters showed (i) that the pH shift in the aqueous permeation pathway had a notable effect on the ionic valence and the partitioning of the drug in this domain for a high surface charge density and depending on the pK(a) and pI of the drug in relation to the bulk pH; (ii) the magnitude and the direction of convective transport due to electroosmosis typically reflected the density and sign, respectively, of surface charge of the tissue and its effect on enhancement was substantial for bulk pH values differing from the pI of epidermal tissue; (iii) the aqueous pathway predominantly determined passive permeability of the studied compound despite its measurable lipophilicity and therefore the lipid pathway did not notably affect enhancement. Hence, the proposed model can provide a good quantitative insight into the interplay between different phenomena and permeant properties influencing iontophoresis and can potentially be used as a predictive tool of the process.

Generation and detection of the cyclohexadienyl radical in phosphonium ionic liquids.

PubMed

Lauzon, J M; Arseneau, D J; Brodovitch, J C; Clyburne, J A C; Cormier, P; McCollum, B; Ghandi, K

2008-10-21

The formation of the cyclohexadienyl radical, C(6)H(6)Mu, in ionic and molecular solvents has been compared. This is the first time that a muoniated free radical is reported in an ionic liquid. In marked contrast to molecular liquids, free radical generation in ionic liquids is significantly enhanced. Comparison of the hyperfine interactions in the ionic liquid and in molecular solvents and with theoretical calculations, suggests significant and unforeseen solvent interaction with the cyclohexadienyl radical.

Synthesis and Properties of Highly Dispersed Ionic Silica–Poly(ethylene oxide) Nanohybrids

PubMed Central

2013-01-01

We report an ionic hybrid based on silica nanoparticles as the anion and amine-terminated poly(ethylene oxide) (PEO) as a cation. The charge on the nanoparticle anion is carried by the surface hydroxyls. SAXS and TEM reveal an exceptional degree of dispersion of the silica in the polymer and high degree of order in both thin film and bulk forms. In addition to better dispersion, the ionic hybrid shows improved flow characteristics compared to silica/PEO mixtures in which the ionic interactions are absent. PMID:23351113

Effects of Solution Chemistry on Nano-Bubbles Transport in Saturated Porous Media

NASA Astrophysics Data System (ADS)

Hamamoto, S.; Takemura, T.; Suzuki, K.; Nihei, N.; Nishimura, T.

2017-12-01

Nano-bubbles (NBs) have a considerable potential for the remediation of soil and groundwater contaminated by organic compounds, especially when used in conjunction with bioremediation technologies. Understanding the transport mechanisms of NBs in soils is essential to optimize NB-based remediation techniques. In this study, one-dimensional column transport experiments using glass beads with 0.1 mm size were conducted, where NBs created by oxygen gas at different pH and ionic strength were injected to the column at the constant flow rate. The NBs concentration in the effluent was quantified using a resonant mass measurement technique. Effects of solution chemistry of the NBs water on NB transport in the porous media were investigated. The results showed that attachment of NBs was enhanced under higher ionic strength and lower pH conditions, caused by the reduced repulsive force between NBs and glass beads. In addition, bubble size distributions in the effluents showed that relatively larger NBs were retained in the column. This trend was more significant at lower pH condition.

A novel electrochemical biosensor based on dynamic polymerase-extending hybridization for E. coli O157:H7 DNA detection.

PubMed

Wang, Lijiang; Liu, Qingjun; Hu, Zhaoying; Zhang, Yuanfan; Wu, Chunsheng; Yang, Mo; Wang, Ping

2009-05-15

A novel biosensor based on single-stranded DNA (ssDNA) probe functionalized aluminum anodized oxide (AAO) nanopore membranes was demonstrated for Escherichia coli O157:H7 DNA detection. An original and dynamic polymerase-extending (PE) DNA hybridization procedure is proposed, where hybridization happens in the existence of Taq DNA polymerase and dNTPs under controlled reaction temperature. The probe strand would be extended as long as the target DNA strand, then the capability to block the ionic flow in the pores has been prominently enhanced by the double strand complex. We have investigated the variation of ionic conductivity during the fabrication of the film and the hybridization using cyclic voltammetry and impedance spectroscopy. The present approach provides low detection limit for DNA (a few hundreds of pmol), rapid label-free and easy-to-use bacteria detection, which holds the potential for future use in various ss-DNA analyses by integrated into a self-contained biochip.

A microfluidic fuel cell with flow-through porous electrodes.

PubMed

Kjeang, Erik; Michel, Raphaelle; Harrington, David A; Djilali, Ned; Sinton, David

2008-03-26

A microfluidic fuel cell architecture incorporating flow-through porous electrodes is demonstrated. The design is based on cross-flow of aqueous vanadium redox species through the electrodes into an orthogonally arranged co-laminar exit channel, where the waste solutions provide ionic charge transfer in a membraneless configuration. This flow-through architecture enables improved utilization of the three-dimensional active area inside the porous electrodes and provides enhanced rates of convective/diffusive transport without increasing the parasitic loss required to drive the flow. Prototype fuel cells are fabricated by rapid prototyping with total material cost estimated at 2 USD/unit. Improved performance as compared to previous microfluidic fuel cells is demonstrated, including power densities at room temperature up to 131 mW cm-2. In addition, high overall energy conversion efficiency is obtained through a combination of relatively high levels of fuel utilization and cell voltage. When operated at 1 microL min-1 flow rate, the fuel cell produced 20 mW cm-2 at 0.8 V combined with an active fuel utilization of 94%. Finally, we demonstrate in situ fuel and oxidant regeneration by running the flow-through architecture fuel cell in reverse.

Enhanced ionic liquid mobility induced by confinement in 1D CNT membranes

NASA Astrophysics Data System (ADS)

Berrod, Q.; Ferdeghini, F.; Judeinstein, P.; Genevaz, N.; Ramos, R.; Fournier, A.; Dijon, J.; Ollivier, J.; Rols, S.; Yu, D.; Mole, R. A.; Zanotti, J.-M.

2016-04-01

Water confined within carbon nanotubes (CNT) exhibits tremendous enhanced transport properties. Here, we extend this result to ionic liquids (IL) confined in vertically aligned CNT membranes. Under confinement, the IL self-diffusion coefficient is increased by a factor 3 compared to its bulk reference. This could lead to high power battery separators.Water confined within carbon nanotubes (CNT) exhibits tremendous enhanced transport properties. Here, we extend this result to ionic liquids (IL) confined in vertically aligned CNT membranes. Under confinement, the IL self-diffusion coefficient is increased by a factor 3 compared to its bulk reference. This could lead to high power battery separators. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01445c

Experimental Studies of Hydrocarbon Flame Phenomena: Enabling Combustion Control

DTIC Science & Technology

2016-07-30

early discussions on the “ionic or electric wind ’ was a term used to describe a fluid flow driven only from the difference in electric potentials at two...locations, Chattock [2] and Robinson [11]. 4 To produce ionic wind , a high potential combined with a favorable electrode geometry, forms an...the secondary electrode. Beyond the formation of the ionic wind , it has been observed that high potentials in ambient air can produce ozone

Elucidating the correlation between morphology and ion dynamics in polymerized ionic liquids.

NASA Astrophysics Data System (ADS)

Heres, Maximilian; Cosby, Tyler; Iacob, Ciprian; Runt, James; Benson, Roberto; Liu, Hongjun; Paddison, Stephen; Sangoro, Joshua

Charge transport and dynamics are investigated for a series of poly-ammonium and poly-imidazolium-based polymerized ionic liquids (polyIL) with a common bis(trifluoromethylsulfonyl)imide anion using broadband dielectric spectroscopy and temperature modulated differential scanning calorimetry. A significant enhancement of the Tg independent ionic conductivity is observed for ammonium based polyIL with shorter pendant groups, in comparison to imidazolium based systems. These results emphasize the importance of polymer backbone spacing as well as counter-ion size on ionic conductivity in polymerized ionic liquids. NSF DMR 1508394.

Transport and retention of surfactant- and polymer-stabilized engineered silver nanoparticles in silicate-dominated aquifer material.

PubMed

Adrian, Yorck F; Schneidewind, Uwe; Bradford, Scott A; Simunek, Jirka; Fernandez-Steeger, Tomas M; Azzam, Rafig

2018-05-01

Packed column experiments were conducted to investigate the transport and blocking behavior of surfactant- and polymer-stabilized engineered silver nanoparticles (Ag-ENPs) in saturated natural aquifer media with varying content of material < 0.063 mm in diameter (silt and clay fraction), background solution chemistry, and flow velocity. Breakthrough curves for Ag-ENPs exhibited blocking behavior that frequently produced a delay in arrival time in comparison to a conservative tracer that was dependent on the physicochemical conditions, and then a rapid increase in the effluent concentration of Ag-ENPs. This breakthrough behavior was accurately described using one or two irreversible retention sites that accounted for Langmuirian blocking on one site. Simulated values for the total retention rate coefficient and the maximum solid phase concentration of Ag-ENPs increased with increasing solution ionic strength, cation valence, clay and silt content, decreasing flow velocity, and for polymer-instead of surfactant-stabilized Ag-ENPs. Increased Ag-ENP retention with ionic strength occurred because of compression of the double layer and lower magnitudes in the zeta potential, whereas lower velocities increased the residence time and decreased the hydrodynamics forces. Enhanced Ag-ENP interactions with cation valence and clay were attributed to the creation of cation bridging in the presence of Ca 2+ . The delay in breakthrough was always more pronounced for polymer-than surfactant-stabilized Ag-ENPs, because of differences in the properties of the stabilizing agents and the magnitude of their zeta-potential was lower. Our results clearly indicate that the long-term transport behavior of Ag-ENPs in natural, silicate dominated aquifer material will be strongly dependent on blocking behavior that changes with the physicochemical conditions and enhanced Ag-ENP transport may occur when retention sites are filled. Copyright © 2018 Elsevier Ltd. All rights reserved.

Electrical double layer modulation of hybrid room temperature ionic liquid/aqueous buffer interface for enhanced sweat based biosensing.

PubMed

Jagannath, Badrinath; Muthukumar, Sriram; Prasad, Shalini

2018-08-03

We have investigated the role of kosmotropic anionic moieties and chaotropic cationic moieties of room temperature hydrophilic ionic liquids in enhancing the biosensing performance of affinity based immunochemical biosensors in human sweat. Two ionic liquids, 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM[BF 4 ]) and choline dihydrogen phosphate (Choline[DHP]) were investigated in this study with Choline[DHP] being more kosmotropic in nature having a more protein stabilizing effect based on the hofmeister series. Non-faradaic interfacial charge transfer has been employed as the mechanism for evaluating the formation and the biosensing of capture probe antibodies in room temperature ionic liquids (RTILs)/aqueous human sweat interface. The charge of the ionic moieties were utilized to form compact electrical double layers around the antibodies for enhancing the stability of the antibody capture probes, which was evaluated through zeta potential measurements. The zeta potential measurements indicated stability of antibodies due to electrostatic repulsion of the RTIL charged moieties encompassing the antibodies, thus preventing any aggregation. Here, we report for the first time of non-faradaic electrochemical impedance spectroscopy equivalent circuit model analysis for analyzing and interpreting affinity based biosensing at hybrid electrode/ionic liquid-aqueous sweat buffer interface guided by the choice of the ionic liquid. Interleukin-6 (IL-6) and cortisol two commonly occurring biomarkers in human sweat were evaluated using this method. The limit of detection (LOD) obtained using both ionic liquids for IL-6 was 0.2 pg mL -1 with cross-reactivity studies indicating better performance of IL-6 detection using Choline[DHP] and no response to cross-reactive molecule. The LOD of 0.1 ng/mL was achieved for cortisol and the cross-reactivity studies indicated that cortisol antibody in BMIM[BF 4 ] did not show any signal response to cross-reactive molecules. Furthermore, improved sensitivity and LOD was achieved using ionic liquids as compared to capture probes in aqueous buffer. Copyright © 2018 Elsevier B.V. All rights reserved.

ESM of ionic and electrochemical phenomena on the nanoscale

DOE PAGES

Kalinin, Sergei V.; Kumar, Amit; Balke, Nina; ...

2011-01-01

Operation of energy storage and conversion devices is ultimately controlled by series of intertwined ionic and electronic transport processes and electrochemical reactions at surfaces and interfaces, strongly mediated by strain and mechanical processes. In a typical fuel cell, these include chemical species transport in porous cathode and anode materials, gas-solid electrochemical reactions at grains and triple-phase boundaries (TPBs), ionic and electronic flows in multicomponent electrodes, and chemical and electronic potential drops at internal interfaces in electrodes and electrolytes. Furthermore, all these phenomena are sensitively affected by the microstructure of materials from device level to the atomic scales. Similar spectrum ofmore » length scales and phenomena underpin operation of other energy systems including primary and secondary batteries, as well as hybrid systems such flow and metal-air/water batteries.« less

Through-plane conductivities of membranes for nonaqueous redox flow batteries

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

Anderson, Travis Mark; Small, Leo J.; Pratt, III, Harry D.

In this study, nonaqueous redox flow batteries (RFB) leverage nonaqueous solvents to enable higher operating voltages compared to their aqueous counterparts. Most commercial components for flow batteries, however, are designed for aqueous use. One critical component, the ion-selective membrane, provides ionic conductance between electrodes while preventing crossover of electroactive species. Here we evaluate the area-specific conductances and through-plane conductivities of commercially available microporous separators (Celgard 2400, 2500) and anion exchange membranes (Neosepta AFX, Neosepta AHA, Fumasep FAP-450, Fumasep FAP-PK) soaked in acetonitrile, propylene carbonate, or two imidazolium-based ionic liquids. Fumasep membranes combined with acetonitrile-based electrolyte solutions provided the highest conductancemore » values and conductivities by far. When tested in ionic liquids, all anion exchange membranes displayed conductivities greater than those of the Celgard microporous separators, though the separators’ decreased thickness-enabled conductances on par with the most conductive anion exchange membranes. Ionic conductivity is not the only consideration when choosing an anion exchange membrane; testing of FAP-450 and FAP-PK membranes in a nonaqueous RFB demonstrated that the increased mechanical stability of PEEK-supported FAP-PK minimized swelling, in turn decreasing solvent mediated crossover and enabling greater electrochemical yields (40% vs. 4%) and Coulombic efficiencies (94% vs. 90%) compared to the unsupported, higher conductance FAP-450.« less

Through-plane conductivities of membranes for nonaqueous redox flow batteries

DOE PAGES

Anderson, Travis Mark; Small, Leo J.; Pratt, III, Harry D.; ...

2015-08-13

In this study, nonaqueous redox flow batteries (RFB) leverage nonaqueous solvents to enable higher operating voltages compared to their aqueous counterparts. Most commercial components for flow batteries, however, are designed for aqueous use. One critical component, the ion-selective membrane, provides ionic conductance between electrodes while preventing crossover of electroactive species. Here we evaluate the area-specific conductances and through-plane conductivities of commercially available microporous separators (Celgard 2400, 2500) and anion exchange membranes (Neosepta AFX, Neosepta AHA, Fumasep FAP-450, Fumasep FAP-PK) soaked in acetonitrile, propylene carbonate, or two imidazolium-based ionic liquids. Fumasep membranes combined with acetonitrile-based electrolyte solutions provided the highest conductancemore » values and conductivities by far. When tested in ionic liquids, all anion exchange membranes displayed conductivities greater than those of the Celgard microporous separators, though the separators’ decreased thickness-enabled conductances on par with the most conductive anion exchange membranes. Ionic conductivity is not the only consideration when choosing an anion exchange membrane; testing of FAP-450 and FAP-PK membranes in a nonaqueous RFB demonstrated that the increased mechanical stability of PEEK-supported FAP-PK minimized swelling, in turn decreasing solvent mediated crossover and enabling greater electrochemical yields (40% vs. 4%) and Coulombic efficiencies (94% vs. 90%) compared to the unsupported, higher conductance FAP-450.« less

In situ colloid mobilization in Hanford sediments under unsaturated transient flow conditions: effect of irrigation pattern.

PubMed

Zhuang, Jie; McCarthy, John F; Tyner, John S; Perfect, Edmund; Flury, Markus

2007-05-01

Colloid transport may facilitate off-site transport of radioactive wastes at the Hanford site, Washington State. In this study, column experiments were conducted to examine the effect of irrigation schedule on releases of in situ colloids from two Hanford sediments during saturated and unsaturated transientflow and its dependence on solution ionic strength, irrigation rate, and sediment texture. Results show that transient flow mobilized more colloids than steady-state flow. The number of short-term hydrological pulses was more important than total irrigation volume for increasing the amount of mobilized colloids. This effect increased with decreasing ionic strength. At an irrigation rate equal to 5% of the saturated hydraulic conductivity, a transient multipulse flow in 100 mM NaNO3 was equivalent to a 50-fold reduction of ionic strength (from 100 mM to 2 mM) with a single-pulse flow in terms of their positive effects on colloid mobilization. Irrigation rate was more important for the initial release of colloids. In addition to water velocity, mechanical straining of colloids was partly responsible for the smaller colloid mobilization in the fine than in the coarse sands, although the fine sand contained much larger concentrations of colloids than the coarse sand.

Enhancement of the ionic conductivity of olivine by the water incorporation based on the Mg diffusivity

NASA Astrophysics Data System (ADS)

Katsura, T.; Fei, H.; Koizumi, S.; Sakamoto, N.; Yurimoto, H.

2016-12-01

Although the water corporation has been considered to enhance the electrical conductivity of olivine by the proton conduction, the magnitude of the proton conduction is relatively small at asthenospheric temperatures because of its smaller activation energy than those of the small polaron and ionic conductions. However, the water incorporation could enhance the ionic conduction, because it should increase the defect density in the Mg sites. Since the ionic conductivity is proportional to the diffusivity, we have measured the self-diffusion coefficients of Mg in forsterite as a function of pressure, temperature and water content. We annealed fine-grained polycrystalline aggregates of forsterite with water contents up to 300 ppm, on whose polished plane a 25Mg-enriched Mg2SiO4 thin film was made, at pressures of 1 to 13 GPa and temperatures of 1100 to 1300 K. The lattice and grain-boundary diffusion coefficients were calculated simultaneously using profiles obtained by the depth analysis of SIMS. Experimental results gave the activation energy of 280 ± 30 and 360 ± 30 kJ/mol, activation volumes of 4.3 ± 0.3 and 3.9 ± 0.7 cm3/mol, and water content exponents of 1.2 ± 0.2 and 1.0 ± 0.1 for the lattice and grain-boundary diffusions, respectively. Using the ionic conduction data by Constable [2006] and Yoshino et al. [2009], and the water and pressure effects on Mg diffusivity in this study, the ionic conduction is found by 2 orders of magnitude higher than the small polaron and proton conductions under oceanic-asthenosphere conditions. Thus, the high conductivity of the oceanic asthenosphere will be governed by the water-enhanced ionic conduction. The negative pressure dependence of the Mg diffusivity and the gradual temperature increase in the asthenosphere will produce a conductivity maximum at the top of the asthenosphere. The high-conductivity layer at the top of the asthenosphere observed under very young oceanic plates can be attributed to this ionic conduction maximum.

Vertically Aligned and Continuous Nanoscale Ceramic-Polymer Interfaces in Composite Solid Polymer Electrolytes for Enhanced Ionic Conductivity.

PubMed

Zhang, Xiaokun; Xie, Jin; Shi, Feifei; Lin, Dingchang; Liu, Yayuan; Liu, Wei; Pei, Allen; Gong, Yongji; Wang, Hongxia; Liu, Kai; Xiang, Yong; Cui, Yi

2018-06-13

Among all solid electrolytes, composite solid polymer electrolytes, comprised of polymer matrix and ceramic fillers, garner great interest due to the enhancement of ionic conductivity and mechanical properties derived from ceramic-polymer interactions. Here, we report a composite electrolyte with densely packed, vertically aligned, and continuous nanoscale ceramic-polymer interfaces, using surface-modified anodized aluminum oxide as the ceramic scaffold and poly(ethylene oxide) as the polymer matrix. The fast Li + transport along the ceramic-polymer interfaces was proven experimentally for the first time, and an interfacial ionic conductivity higher than 10 -3 S/cm at 0 °C was predicted. The presented composite solid electrolyte achieved an ionic conductivity as high as 5.82 × 10 -4 S/cm at the electrode level. The vertically aligned interfacial structure in the composite electrolytes enables the viable application of the composite solid electrolyte with superior ionic conductivity and high hardness, allowing Li-Li cells to be cycled at a small polarization without Li dendrite penetration.

Non-Aqueous Primary Li-Air Flow Battery and Optimization of its Cathode through Experiment and Modeling.

PubMed

Kim, Byoungsu; Takechi, Kensuke; Ma, Sichao; Verma, Sumit; Fu, Shiqi; Desai, Amit; Pawate, Ashtamurthy S; Mizuno, Fuminori; Kenis, Paul J A

2017-09-22

A primary Li-air battery has been developed with a flowing Li-ion free ionic liquid as the recyclable electrolyte, boosting power capability by promoting superoxide diffusion and enhancing discharge capacity through separately stored discharge products. Experimental and computational tools are used to analyze the cathode properties, leading to a set of parameters that improve the discharge current density of the non-aqueous Li-air flow battery. The structure and configuration of the cathode gas diffusion layers (GDLs) are systematically modified by using different levels of hot pressing and the presence or absence of a microporous layer (MPL). These experiments reveal that the use of thinner but denser MPLs is key for performance optimization; indeed, this leads to an improvement in discharge current density. Also, computational results indicate that the extent of electrolyte immersion and porosity of the cathode can be optimized to achieve higher current density. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

DFT-based ab initio MD simulation of the ionic conduction in doped ZrO₂ systems under epitaxial strain.

PubMed

Oka, M; Kamisaka, H; Fukumura, T; Hasegawa, T

2015-11-21

The oxygen ionic conduction in ZrO2 systems under tensile epitaxial strain was investigated by performing ab initio molecular dynamics (MD) calculations based on density functional theory (DFT) to elucidate the essential factors in the colossal ionic conductivity observed in the yttria stabilized ZrO2 (YSZ)/SrTiO3 heterostructure. Three factors were evaluated: lattice strain, oxygen vacancies, and dopants. Phonon calculations based on density functional perturbation theory (DFPT) were used to obtain the most stable structure for nondoped ZrO2 under 7% tensile strain along the a- and b-axes. This structure has the space group Pbcn, which is entirely different from that of cubic ZrO2, suggesting that previous ab initio MD calculations assuming cubic ZrO2 may have overestimated the ionic conductivity due to relaxation from the initial structure to the stable structure (Pbcn). Our MD calculations revealed that the ionic conductivity is enhanced only when tensile strain and oxygen vacancies are incorporated, although the presently obtained diffusion constant is far below the range for the colossal ionic conduction experimentally observed. The enhanced ionic conductivity is due to the combined effects of oxygen sublattice formation induced by strain and deformation of this sublattice by oxygen vacancies.

Anisotropic amplification of proton transport in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Thimmappa, Ravikumar; Fawaz, Mohammed; Devendrachari, Mruthyunjayachari Chattanahalli; Gautam, Manu; Kottaichamy, Alagar Raja; Shafi, Shahid Pottachola; Thotiyl, Musthafa Ottakam

2017-07-01

Though graphene oxide (GO) membrane shuttles protons under humid conditions, it suffer severe disintegration and anhydrous conditions lead to abysmal ionic conductivity. The trade-off between mechanical integrity and ionic conductivity challenge the amplification of GO's ionic transport under anhydrous conditions. We show anisotropic amplification of GO's ionic transport with a selective amplification of in plane contribution under anhydrous conditions by doping it with a plant extract, phytic acid (PA). The hygroscopic nature of PA stabilized interlayer water molecules and peculiar geometry of sbnd OH functionalities around saturated hydrocarbon ring anisotropically enhanced ionic transport amplifying the fuel cell performance metrics.

Metal-chelating active packaging film enhances lysozyme inhibition of Listeria monocytogenes.

PubMed

Roman, Maxine J; Decker, Eric A; Goddard, Julie M

2014-07-01

Several studies have demonstrated that metal chelators enhance the antimicrobial activity of lysozyme. This study examined the effect of metal-chelating active packaging film on the antimicrobial activity of lysozyme against Listeria monocytogenes. Polypropylene films were surface modified by photoinitiated graft polymerization of acrylic acid (PP-g-PAA) from the food contact surface of the films to impart chelating activity based on electrostatic interactions. PP-g-PAA exhibited a carboxylic acid density of 113 ± 5.4 nmol cm(-2) and an iron chelating activity of 53.7 ± 9.8 nmol cm(-2). The antimicrobial interaction of lysozyme and PP-g-PAA depended on growth media composition. PP-g-PAA hindered lysozyme activity at low ionic strength (2.48-log increase at 64.4 mM total ionic strength) and enhanced lysozyme activity at moderate ionic strength (5.22-log reduction at 120 mM total ionic strength). These data support the hypothesis that at neutral pH, synergy between carboxylate metal-chelating films (pKa(bulk) 6.45) and lysozyme (pI 11.35) is optimal in solutions of moderate to high ionic strength to minimize undesirable charge interactions, such as lysozyme absorption onto film. These findings suggest that active packaging, which chelates metal ions based on ligand-specific interactions, in contrast to electrostatic interactions, may improve antimicrobial synergy. This work demonstrates the potential application of metal-chelating active packaging films to enhance the antimicrobial activity of membrane-disrupting antimicrobials, such as lysozyme.

Ternary mixtures of ionic liquids for better salt solubility, conductivity and cation transference number improvement

PubMed Central

Karpierz, E.; Niedzicki, L.; Trzeciak, T.; Zawadzki, M.; Dranka, M.; Zachara, J.; Żukowska, G. Z.; Bitner-Michalska, A.; Wieczorek, W.

2016-01-01

We hereby present the new class of ionic liquid systems in which lithium salt is introduced into the solution as a lithium cation−glyme solvate. This modification leads to the reorganisation of solution structure, which entails release of free mobile lithium cation solvate and hence leads to the significant enhancement of ionic conductivity and lithium cation transference numbers. This new approach in composing electrolytes also enables even three-fold increase of salt concentration in ionic liquids. PMID:27767069

POSS Ionic Liquid.

PubMed

Tanaka, Kazuo; Ishiguro, Fumiyasu; Chujo, Yoshiki

2010-12-22

We report the synthesis of a stable room-temperature ionic liquid consisting of an octacarboxy polyhedral oligomeric silsesquioxane (POSS) anion and an imidazolium cation. The introduction of the POSS moiety enhances the thermal stability and reduces the melting temperature. From an evaluation of the thermodynamic parameters during the melting, it was found that the rigidity and cubic structure of POSS can contribute to the enhancement of these thermal properties.

Desorption of hydrocarbon chains by association with ionic and nonionic surfactants under flow as a mechanism for enhanced oil recovery.

PubMed

Terrón-Mejía, Ketzasmin A; López-Rendón, Roberto; Goicochea, Armando Gama

2017-08-29

The need to extract oil from wells where it is embedded on the surfaces of rocks has led to the development of new and improved enhanced oil recovery techniques. One of those is the injection of surfactants with water vapor, which promotes desorption of oil that can then be extracted using pumps, as the surfactants encapsulate the oil in foams. However, the mechanisms that lead to the optimal desorption of oil and the best type of surfactants to carry out desorption are not well known yet, which warrants the need to carry out basic research on this topic. In this work, we report non equilibrium dissipative particle dynamics simulations of model surfactants and oil molecules adsorbed on surfaces, with the purpose of studying the efficiency of the surfactants to desorb hydrocarbon chains, that are found adsorbed over flat surfaces. The model surfactants studied correspond to nonionic and cationic surfactants, and the hydrocarbon desorption is studied as a function of surfactant concentration under increasing Poiseuille flow. We obtain various hydrocarbon desorption isotherms for every model of surfactant proposed, under flow. Nonionic surfactants are found to be the most effective to desorb oil and the mechanisms that lead to this phenomenon are presented and discussed.

Disinfection of Spacecraft Potable Water Systems by Passivation with Ionic Silver

NASA Technical Reports Server (NTRS)

Birmele, Michele N.; McCoy, LaShelle e.; Roberts, Michael S.

2011-01-01

Microbial growth is common on wetted surfaces in spacecraft environmental control and life support systems despite the use of chemical and physical disinfection methods. Advanced control technologies are needed to limit microorganisms and increase the reliability of life support systems required for long-duration human missions. Silver ions and compounds are widely used as antimicrobial agents for medical applications and continue to be used as a residual biocide in some spacecraft water systems. The National Aeronautics and Space Administration (NASA) has identified silver fluoride for use in the potable water system on the next generation spacecraft. Due to ionic interactions between silver fluoride in solution and wetted metallic surfaces, ionic silver is rapidly depleted from solution and loses its antimicrobial efficacy over time. This report describes research to prolong the antimicrobial efficacy of ionic silver by maintaining its solubility. Three types of metal coupons (lnconel 718, Stainless Steel 316, and Titanium 6AI-4V) used in spacecraft potable water systems were exposed to either a continuous flow of water amended with 0.4 mg/L ionic silver fluoride or to a static, pre-treatment passivation in 50 mg/L ionic silver fluoride with or without a surface oxidation pre-treatment. Coupons were then challenged in a high-shear, CDC bioreactor (BioSurface Technologies) by exposure to six bacteria previously isolated from spacecraft potable water systems. Continuous exposure to 0.4 mg/L ionic silver over the course of 24 hours during the flow phase resulted in a >7-log reduction. The residual effect of a 24-hour passivation treatment in 50 mg/L of ionic silver resulted in a >3-log reduction, whereas a two-week treatment resulted in a >4-log reduction. Results indicate that 0.4 mg/L ionic silver is an effective biocide against many bacteria and that a prepassivation of metal surfaces with silver can provide additional microbial control.

Remarkable enhancement of charge carrier mobility of conjugated polymer field-effect transistors upon incorporating an ionic additive

PubMed Central

Luo, Hewei; Yu, Chenmin; Liu, Zitong; Zhang, Guanxin; Geng, Hua; Yi, Yuanping; Broch, Katharina; Hu, Yuanyuan; Sadhanala, Aditya; Jiang, Lang; Qi, Penglin; Cai, Zhengxu; Sirringhaus, Henning; Zhang, Deqing

2016-01-01

Organic semiconductors with high charge carrier mobilities are crucial for flexible electronic applications. Apart from designing new conjugated frameworks, different strategies have been explored to increase charge carrier mobilities. We report a new and simple approach to enhancing the charge carrier mobility of DPP-thieno[3,2-b]thiophene–conjugated polymer by incorporating an ionic additive, tetramethylammonium iodide, without extra treatments into the polymer. The resulting thin films exhibit a very high hole mobility, which is higher by a factor of 24 than that of thin films without the ionic additive under the same conditions. On the basis of spectroscopic grazing incidence wide-angle x-ray scattering and atomic force microscopy studies as well as theoretical calculations, the remarkable enhancement of charge mobility upon addition of tetramethylammonium iodide is attributed primarily to an inhibition of the torsion of the alkyl side chains by the presence of the ionic species, facilitating a more ordered lamellar packing of the alkyl side chains and interchain π-π interactions. PMID:27386541

Enhancing grain boundary ionic conductivity in mixed ionic–electronic conductors

DOE PAGES

Lin, Ye; Fang, Shumin; Su, Dong; ...

2015-04-10

Mixed ionic–electronic conductors are widely used in devices for energy conversion and storage. Grain boundaries in these materials have nanoscale spatial dimensions, which can generate substantial resistance to ionic transport due to dopant segregation. Here, we report the concept of targeted phase formation in a Ce 0.8Gd 0.2O 2₋δ–CoFe 2O 4 composite that serves to enhance the grain boundary ionic conductivity. Using transmission electron microscopy and spectroscopy approaches, we probe the grain boundary charge distribution and chemical environments altered by the phase reaction between the two constituents. The formation of an emergent phase successfully avoids segregation of the Gd dopantmore » and depletion of oxygen vacancies at the Ce 0.8Gd 0.2O 2₋δ–Ce 0.8Gd 0.2O 2₋δ grain boundary. This results in superior grain boundary ionic conductivity as demonstrated by the enhanced oxygen permeation flux. Lastly, this work illustrates the control of mesoscale level transport properties in mixed ionic–electronic conductor composites through processing induced modifications of the grain boundary defect distribution.« less

Enhancement in ionic conductivity on solid polymer electrolytes containing large conducting species

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

Praveen, D.; Damle, Ramakrishna

2016-05-23

Solid Polymer Electrolytes (SPEs) lack better conducting properties at ambient temperatures. Various methods to enhance their ionic conductivity like irradiation with swift heavy ions, γ-rays, swift electrons and quenching at low temperature etc., have been explored in the literature. Among these, one of the oldest methods is incorporation of different conducting species into the polymer matrix and/or addition of nano-sized inert particles into SPEs. Various new salts like LiBr, Mg(ClO{sub 4}){sub 2}, NH{sub 4}I etc., have already been tried in the past with some success. Also various nanoparticles like Al{sub 2}O{sub 3}, TiO{sub 2} etc., have been tried in themore » past. In this article, we have investigated an SPE containing Rubidium as a conducting species. Rubidium has a larger ionic size compared to lithium and sodium ions which have been investigated in the recent past. In the present article, we have investigated the conductivity of large sized conducting species and shown the enhancement in the ionic conductivity by addition of nano-sized inert particles.« less

Enhancing grain boundary ionic conductivity in mixed ionic–electronic conductors

PubMed Central

Lin, Ye; Fang, Shumin; Su, Dong; Brinkman, Kyle S; Chen, Fanglin

2015-01-01

Mixed ionic–electronic conductors are widely used in devices for energy conversion and storage. Grain boundaries in these materials have nanoscale spatial dimensions, which can generate substantial resistance to ionic transport due to dopant segregation. Here, we report the concept of targeted phase formation in a Ce0.8Gd0.2O2−δ–CoFe2O4 composite that serves to enhance the grain boundary ionic conductivity. Using transmission electron microscopy and spectroscopy approaches, we probe the grain boundary charge distribution and chemical environments altered by the phase reaction between the two constituents. The formation of an emergent phase successfully avoids segregation of the Gd dopant and depletion of oxygen vacancies at the Ce0.8Gd0.2O2−δ–Ce0.8Gd0.2O2−δ grain boundary. This results in superior grain boundary ionic conductivity as demonstrated by the enhanced oxygen permeation flux. This work illustrates the control of mesoscale level transport properties in mixed ionic–electronic conductor composites through processing induced modifications of the grain boundary defect distribution. PMID:25857355

Enhancing grain boundary ionic conductivity in mixed ionic–electronic conductors

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

Lin, Ye; Fang, Shumin; Su, Dong

Mixed ionic–electronic conductors are widely used in devices for energy conversion and storage. Grain boundaries in these materials have nanoscale spatial dimensions, which can generate substantial resistance to ionic transport due to dopant segregation. Here, we report the concept of targeted phase formation in a Ce 0.8Gd 0.2O 2₋δ–CoFe 2O 4 composite that serves to enhance the grain boundary ionic conductivity. Using transmission electron microscopy and spectroscopy approaches, we probe the grain boundary charge distribution and chemical environments altered by the phase reaction between the two constituents. The formation of an emergent phase successfully avoids segregation of the Gd dopantmore » and depletion of oxygen vacancies at the Ce 0.8Gd 0.2O 2₋δ–Ce 0.8Gd 0.2O 2₋δ grain boundary. This results in superior grain boundary ionic conductivity as demonstrated by the enhanced oxygen permeation flux. Lastly, this work illustrates the control of mesoscale level transport properties in mixed ionic–electronic conductor composites through processing induced modifications of the grain boundary defect distribution.« less

The magic of aqueous solutions of ionic liquids: ionic liquids as a powerful class of catanionic hydrotropes†

PubMed Central

Cláudio, Ana Filipa M.; Neves, Márcia C.; Shimizu, Karina; Canongia Lopes, José N.; Freire, Mara G.; Coutinho, João A. P.

2015-01-01

Hydrotropes are compounds able to enhance the solubility of hydrophobic substances in aqueous media and therefore are widely used in the formulation of drugs, cleaning and personal care products. In this work, it is shown that ionic liquids are a new class of powerful catanionic hydrotropes where both the cation and the anion synergistically contribute to increase the solubility of biomolecules in water. The effects of the ionic liquid chemical structures, their concentration and the temperature on the solubility of two model biomolecules, vanillin and gallic acid were evaluated and compared with the performance of conventional hydrotropes. The solubility of these two biomolecules was studied in the entire composition range, from pure water to pure ionic liquids, and an increase in the solubility of up to 40-fold was observed, confirming the potential of ionic liquids to act as hydrotropes. Using dynamic light scattering, NMR and molecular dynamics simulations, it was possible to infer that the enhanced solubility of the biomolecule in the IL aqueous solutions is related to the formation of ionic-liquid–biomolecules aggregates. Finally, it was demonstrated that hydrotropy induced by ionic liquids can be used to recover solutes from aqueous media by precipitation, simply by using water as an anti-solvent. The results reported here have a significant impact on the understanding of the role of ionic liquid aqueous solutions in the extraction of value-added compounds from biomass as well as in the design of novel processes for their recovery from aqueous media. PMID:26379471

Natural terpene derivatives as new structural task-specific ionic liquids to enhance the enantiorecognition of acidic enantiomers on teicoplanin-based stationary phase by high-performance liquid chromatography.

PubMed

Flieger, Jolanta; Feder-Kubis, Joanna; Tatarczak-Michalewska, Małgorzata; Płazińska, Anita; Madejska, Anna; Swatko-Ossor, Marta

2017-06-01

We present the specific cooperative effect of a semisynthetic glycopeptide antibiotic teicoplanin and chiral ionic liquids containing the (1R,2S,5R)-(-)-menthol moiety on the chiral recognition of enantiomers of mandelic acid, vanilmandelic acid, and phenyllactic acid. Experiments were performed chromatographically on an Astec Chirobiotic T chiral stationary phase applying the mobile phase with the addition of the chiral ionic liquids. The stereoselective binding of enantiomers to teicoplanin in presence of new chiral ionic liquids were evaluated applying thermodynamic measurements and the docking simulations. Both the experimental and theoretical methods revealed that the chiral recognition of enantiomers in the presence of new chiral ionic liquids was enthalpy driven. The changes of the teicoplanin conformation occurring upon binding of the chiral ionic liquids are responsible for the differences in the standard changes in Gibbs energy (ΔG 0 ) values obtained for complexes formed by the R and S enantiomers and teicoplanin. Docking simulations revealed the steric adjustment between the chiral ionic liquids cyclohexane ring (chair conformation) and the β-d-glucosamine ring of teicoplanin and additionally hydrophobic interactions between the decanoic aliphatic chain of teicoplanin and the alkyl group of the tested salts. The obtained terpene derivatives can be considered as "structural task-specific ionic liquids" responsible for enhancing the chiral resolution in synergistic systems with two chiral selectors. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Diels Alder polyphenylene anion exchange membrane for nonaqueous redox flow batteries

DOE PAGES

Small, Leo J.; Pratt, III, Harry D.; Fujimoto, Cy H.; ...

2015-10-23

Here highly conductive, solvent-resistant anionic Diels Alder polyphenylene (DAPP) membranes were synthesized with three different ionic contents and tested in an ionic liquid-based nonaqueous redox flow battery (RFB). These membranes display 3–10× increase in conductivity in propylene carbonate compared to some commercially available (aqueous) anion exchange membranes. The membrane with an ion content of 1.5 meq/g (DAPP1.5) proved too brittle for operation in a RFB, while the membrane with an ion content of 2.5 meq/g (DAPP2.5) allowed excessive movement of solvent and poor electrochemical yields (capacity fade). Despite having lower voltage efficiencies compared to DAPP2.5, the membrane with an intermediatemore » ion content of 2.0 meq/g (DAPP2.0) exhibited higher coulombic efficiencies (96.4% vs. 89.1%) and electrochemical yields (21.6% vs. 10.9%) after 50 cycles. Crossover of the electroactive species was the primary reason for decreased electrochemical yields. Analysis of the anolyte and catholyte revealed degradation of the electroactive species and formation of a film at the membrane-solution interface. Increases in membrane resistance were attributed to mechanical and thermal aging of the membrane; no chemical change was observed. As a result, improvements in the ionic selectivity and ionic conductivity of the membrane will increase the electrochemical yield and voltage efficiency of future nonaqueous redox flow batteries.« less

Feasibility of a Supporting-Salt-Free Nonaqueous Redox Flow Battery Utilizing Ionic Active Materials.

PubMed

Milshtein, Jarrod D; Fisher, Sydney L; Breault, Tanya M; Thompson, Levi T; Brushett, Fikile R

2017-05-09

Nonaqueous redox flow batteries (NAqRFBs) are promising devices for grid-scale energy storage, but high projected prices could limit commercial prospects. One route to reduced prices is to minimize or eliminate the expensive supporting salts typically employed in NAqRFBs. Herein, the feasibility of a flow cell operating in the absence of supporting salt by utilizing ionic active species is demonstrated. These ionic species have high conductivities in acetonitrile (12-19 mS cm -1 ) and cycle at 20 mA cm -2 with energy efficiencies (>75 %) comparable to those of state-of-the-art NAqRFBs employing high concentrations of supporting salt. A chemistry-agnostic techno-economic analysis highlights the possible cost savings of minimizing salt content in a NAqRFB. This work offers the first demonstration of a NAqRFB operating without supporting salt. The associated design principles can guide the development of future active species and could make NAqRFBs competitive with their aqueous counterparts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrafast preparation of a polyhedral oligomeric silsesquioxane-based ionic liquid hybrid monolith via photoinitiated polymerization, and its application to capillary electrochromatography of aromatic compounds.

PubMed

Zhang, Bingyu; Lei, Xiaoyun; Deng, Lijun; Li, Minsheng; Yao, Sicong; Wu, Xiaoping

2018-06-06

An ionic liquid hybrid monolithic capillary column was prepared within 7 min via photoinitiated free-radical polymerization of an ionic liquid monomer (1-butyl-3-vinylimidazolium-bis[(trifluoromethyl)sulfonyl]imide); VBIMNTF 2 ) and a methacryl substituted polyhedral oligomeric silsesquioxane (POSS-MA) acting as a cross-linker. The effects of composition of prepolymerization solution and initiation time on the porous structure and electroosmotic flow (EOF) of monolithic column were investigated. The hybrid monolith was characterized by scanning electron microscopy and FTIR. Owing to the introduction of a rigid nanosized POSS silica core and ionic liquids with multiple interaction sites, the monolithic column has a well-defined 3D skeleton morphology, good mechanical stability, and a stable anodic electroosmotic flow. The hybrid monolithic stationary phase was applied to the capillary electrochromatographic separation of various alkylbenzenes, phenols, anilines and polycyclic aromatic hydrocarbons (PAHs). The column efficiency is highest (98,000 plates/m) in case of alkylbenzenes. Mixed-mode retention mechanisms including hydrophobic interactions, π-π stacking, electrostatic interaction and electrophoretic mobility can be observed. This indicates the potential of this material in terms of efficient separation of analytes of different structural type. Graphical Abstract Preparation of a mixed-mode ionic liquid hybrid monolithic column via photoinitiated polymerization of methacryl substituted polyhedral oligomeric silsesquioxane (POSS-MA) and 1-butyl-3-vinylimidazolium-bis[(trifluoromethyl)sulfonyl]imide (VBIMNTF 2 ) ionic liquid for use in capillary electrochromatography.

Electrodialytic in-line preconcentration for ionic solute analysis.

PubMed

Ohira, Shin-Ichi; Yamasaki, Takayuki; Koda, Takumi; Kodama, Yuko; Toda, Kei

2018-04-01

Preconcentration is an effective way to improve analytical sensitivity. Many types of methods are used for enrichment of ionic solute analytes. However, current methods are batchwise and include procedures such as trapping and elution. In this manuscript, we propose in-line electrodialytic enrichment of ionic solutes. The method can enrich ionic solutes within seconds by quantitative transfer of analytes from the sample solution to the acceptor solution under an electric field. Because of quantitative ion transfer, the enrichment factor (the ratio of the concentration in the sample and to that in the obtained acceptor solution) only depends on the flow rate ratio of the sample solution to the acceptor solution. The ratios of the concentrations and flow rates are equal for ratios up to 70, 20, and 70 for the tested ionic solutes of inorganic cations, inorganic anions, and heavy metal ions, respectively. The sensitivity of ionic solute determinations is also improved based on the enrichment factor. The method can also simultaneously achieve matrix isolation and enrichment. The method was successively applied to determine the concentrations of trace amounts of chloroacetic acids in tap water. The regulated concentration levels cannot be determined by conventional high-performance liquid chromatography with ultraviolet detection (HPLC-UV) without enrichment. However, enrichment with the present method is effective for determination of tap water quality by improving the limits of detection of HPLC-UV. The standard addition test with real tap water samples shows good recoveries (94.9-109.6%). Copyright © 2017 Elsevier B.V. All rights reserved.

Refinement of current monitoring methodology for electroosmotic flow assessment under low ionic strength conditions

PubMed Central

Saucedo-Espinosa, Mario A.; Lapizco-Encinas, Blanca H.

2016-01-01

Current monitoring is a well-established technique for the characterization of electroosmotic (EO) flow in microfluidic devices. This method relies on monitoring the time response of the electric current when a test buffer solution is displaced by an auxiliary solution using EO flow. In this scheme, each solution has a different ionic concentration (and electric conductivity). The difference in the ionic concentration of the two solutions defines the dynamic time response of the electric current and, hence, the current signal to be measured: larger concentration differences result in larger measurable signals. A small concentration difference is needed, however, to avoid dispersion at the interface between the two solutions, which can result in undesired pressure-driven flow that conflicts with the EO flow. Additional challenges arise as the conductivity of the test solution decreases, leading to a reduced electric current signal that may be masked by noise during the measuring process, making for a difficult estimation of an accurate EO mobility. This contribution presents a new scheme for current monitoring that employs multiple channels arranged in parallel, producing an increase in the signal-to-noise ratio of the electric current to be measured and increasing the estimation accuracy. The use of this parallel approach is particularly useful in the estimation of the EO mobility in systems where low conductivity mediums are required, such as insulator based dielectrophoresis devices. PMID:27375813

Facile fabrication of palladium-ionic liquids-nitrogen-doped graphene nanocomposites as enhanced electro-catalyst for ethanol oxidation

NASA Astrophysics Data System (ADS)

Li, Shuwen; Yang, Honglei; Ren, Ren; Ma, Jianxin; Jin, Jun; Ma, Jiantai

2015-10-01

The palladium-ionic liquids-nitrogen-doped graphene nanocomposites are facile fabricated as enhanced electro-catalyst for ethanol oxidation. First, the ionic liquids functionalized nitrogen-doping graphene nanosheets (PDIL-NGS) with few layers is synthesized through a facile and effective one-pot hydrothermal method with graphene oxide as raw material, urea as reducing-doping agents and ionic liquids (ILs) derived from 3,4,9,10-perylene tetracarboxylic acid as functional molecules. The results of systematic characterization reveal that the PDIL molecules not only can functionalize NGS by π-π stacking with no affecting the nitrogen doping but also prevent the agglomeration of NGS. More importantly, the processing performance and the property of electron transfer are remarkably enhanced duo to introducing a large number of ILs groups. Then, the enhanced electrocatalytic Pd nanoparticles are successfully anchored on PDIL-NGS by a facile and surfactant-free synthetic technique. As an anode catalyst, the novel catalyst exhibits better kinetics, more superior electrocatalytic performance, higher tolerance and electrochemical stability than the other catalysts toward ethanol electrooxidation, owing to the role of PDIL molecules. Therefore, the new catalyst is believed to have the potential use for direct alcohol fuel cells in the future and the functionalized NGS is promising useful materials applied in other fields.

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

Ruegg, Thomas Lawrence; Thelen, Michael P.

The present invention provides for a method of genetically modifying microorganisms to enhance resistance to ionic liquids, host cells genetically modified in accordance with the methods, and methods of using the host cells in a reaction comprising biomass that has been pretreated with ionic liquids.

Ionic strength-induced formation of smectite quasicrystals enhances nitroaromatic compound sorption.

PubMed

Li, Hui; Pereira, Tanya R; Teppen, Brian J; Laird, David A; Johnston, Cliff T; Boyd, Stephen A

2007-02-15

Sorption of organic contaminants by soils is a determinant controlling their transport and fate in the environment. The influence of ionic strength on nitroaromatic compound sorption by K+- and Ca2+ -saturated smectite was examined. Sorption of 1,3-dinitrobenzene by K-smectite increased as KCl ionic strength increased from 0.01 to 0.30 M. In contrast, sorption by Ca-smectite at CaCl2 ionic strengths of 0.015 and 0.15 M remained essentially the same. The "salting-out" effect on the decrease of 1,3-dinitrobenzene aqueous solubility within this ionic strength range was <1.5% relative to the solubility in pure water. This decrease of solubility is insufficient to account for the observed increase of sorption by K-smectite with increasing KCl ionic strength. X-ray diffraction patterns and light absorbance of K-clay suspensions indicated the aggregation of clay particles and the formation of quasicrystal structures as KCI ionic strength increased. Sorption enhancement is attributed to the formation of better-ordered K-clay quasicrystals with reduced interlayer distances rather than to the salting-out effect. Dehydration of 1,3-dinitrobenzene is apparently a significant driving force for sorption, and we show for the first time that sorption of small, planar, neutral organic molecules, namely, 1,3-dinitrobenzene, causes previously expanded clay interlayers to dehydrate and collapse in aqueous suspension.

Impact of electrolyte composition on the reactivity of a redox active polymer studied through surface interrogation and ion-sensitive scanning electrochemical microscopy.

PubMed

Burgess, Mark; Hernández-Burgos, Kenneth; Cheng, Kevin J; Moore, Jeffrey S; Rodríguez-López, Joaquín

2016-06-21

Elucidating the impact of interactions between the electrolyte and electroactive species in redox active polymers is key to designing better-performing electrodes for electrochemical energy storage and conversion. Here, we present on the improvement of the electrochemical activity of poly(para-nitrostyrene) (PNS) in solution and as a film by exploiting the ionic interactions between reduced PNS and K(+), which showed increased reactivity when compared to tetrabutylammonium (TBA(+))- and Li(+)-containing electrolytes. While cyclic voltammetry enabled the study of the effects of cations on the electrochemical reversibility and the reduction potential of PNS, scanning electrochemical microscopy (SECM) provided new tools to probe the ionic and redox reactivity of this system. Using an ion-sensitive Hg SECM tip allowed to probe the ingress of ions into PNS redox active films, while surface interrogation SECM (SI-SECM) measured the specific kinetics of PNS and a solution phase mediator in the presence of the tested electrolytes. SI-SECM measurements illustrated that the interrogation kinetics of PNS in the presence of K(+) compared to TBA(+) and Li(+) are greatly enhanced under the same surface concentration of adsorbed radical anion, exhibiting up to a 40-fold change in redox kinetics. We foresee using this new application of SECM methods for elucidating optimal interactions that enhance polymer reactivity for applications in redox flow batteries.

SORPTION OF CU AND ZN TO KAOLINITE AND IRON OXIDE: EFFECTS OF HUMIC ACID AND IONIC STRENGTH AND IMPLICATIONS FOR STORMWATER RUNOFF

EPA Science Inventory

Heavy metals are common pollutants in wet weather flows and urban waterways. Changes in ionic strength, whether from mixing with saline waters, road salt, or from the large osmotic adjustment needed for the Microtox toxicity assay, affect the aqueous chemistry of stormwater runof...

Reactions of Ions with Ionic Liquid Vapors by Selected-Ion Flow Tube Mass Spectrometry

DTIC Science & Technology

2011-03-29

Emel’yanenko, V. N.; Verevkin, S. P.; Heintz, A.; Corfield, J.-A.; Deyko, A.; Lovelock , K. R. J.; Licence, P.; Jones, R. G. Pyrrolidinium- Based Ionic...112, 11734–11742. (2) Lovelock , K. R. J.; Deyko, A.; Licence, P.; Jones, R. G. Vaporisa- tion of an Ionic Liquid Near Room Temperature. Phys. Chem...Relevance of pKa from Aqueous Solutions. J. Am. Chem. Soc. 2003, 125, 15411–15419. (15) Armstrong, J. P.; Hurst, C.; Jones, R. G.; Licence, P.; Lovelock , K

Membranes for redox flow battery applications.

PubMed

Prifti, Helen; Parasuraman, Aishwarya; Winardi, Suminto; Lim, Tuti Mariana; Skyllas-Kazacos, Maria

2012-06-19

The need for large scale energy storage has become a priority to integrate renewable energy sources into the electricity grid. Redox flow batteries are considered the best option to store electricity from medium to large scale applications. However, the current high cost of redox flow batteries impedes the wide spread adoption of this technology. The membrane is a critical component of redox flow batteries as it determines the performance as well as the economic viability of the batteries. The membrane acts as a separator to prevent cross-mixing of the positive and negative electrolytes, while still allowing the transport of ions to complete the circuit during the passage of current. An ideal membrane should have high ionic conductivity, low water intake and excellent chemical and thermal stability as well as good ionic exchange capacity. Developing a low cost, chemically stable membrane for redox flow cell batteries has been a major focus for many groups around the world in recent years. This paper reviews the research work on membranes for redox flow batteries, in particular for the all-vanadium redox flow battery which has received the most attention.

Membranes for Redox Flow Battery Applications

PubMed Central

Prifti, Helen; Parasuraman, Aishwarya; Winardi, Suminto; Lim, Tuti Mariana; Skyllas-Kazacos, Maria

2012-01-01

The need for large scale energy storage has become a priority to integrate renewable energy sources into the electricity grid. Redox flow batteries are considered the best option to store electricity from medium to large scale applications. However, the current high cost of redox flow batteries impedes the wide spread adoption of this technology. The membrane is a critical component of redox flow batteries as it determines the performance as well as the economic viability of the batteries. The membrane acts as a separator to prevent cross-mixing of the positive and negative electrolytes, while still allowing the transport of ions to complete the circuit during the passage of current. An ideal membrane should have high ionic conductivity, low water intake and excellent chemical and thermal stability as well as good ionic exchange capacity. Developing a low cost, chemically stable membrane for redox flow cell batteries has been a major focus for many groups around the world in recent years. This paper reviews the research work on membranes for redox flow batteries, in particular for the all-vanadium redox flow battery which has received the most attention. PMID:24958177

Investigating Attachment Behaviors of Cryptosporidium Parvum Oocysts Using Collision Efficiency in Laboratory Column Experiments

NASA Astrophysics Data System (ADS)

Park, Y.; Hou, L.; Atwill, R.; Packman, A. I.; Harter, T.

2009-12-01

Cryptosporidium is one of the most common enteric parasites of humans and domestic animals, and a number of outbreaks of Cryprosporidiosis, a diarrheal disease caused by Cryptosporidium have been reported worldwide. Natural porous media has been demonstrated to be an effective filter for removing Cryptosporidium parvum from contaminated water and the amount of Cryptosporidium filtered is known to be highly dependent on physical and chemical conditions of the porous media and the water. Cryptosporidium deposition in saturated porous media involves two main steps: approach and attachment. In contrast to the approach mechanisms, attachment processes have not been systematically described to predict a priori because theories that represent attachment behavior (colloid stability) such as DLVO are insufficient to explain experimental data. For this reason, attachment efficiency is calculated based on empirical data, typically experimental breakthrough curves in laboratory columns or field experiments. In this study, collision (attachment) efficiencies (α) of C. parvum oocyst were calculated to test the effect of chemical property changes on the association of oocysts with sand grains. The breakthrough curve data obtained from twelve column experiments and three models were employed to calculate single collector efficiency (η) and α. The first ten experiments were conducted by changing ionic strength and pH, and mixing with natural sediments under the same physical properties (same η). Our experiment results show that iron coating or clay/suspended solids mixture drastically enhanced oocyst deposition. The experiments also showed that increase in ionic strength and decrease in pH enhanced the attachment efficiency. However, the experiment with 100mM NaCl resulted in low attachment efficiency and the experiment with pH 8.5 showed similar attachment efficiency to the one at pH 7. Based on the results from two additional experiments with different flow velocities, it appears that attachment efficiency changes when the flow velocity changes, which contradicts CFT. The results prove that predicting attachment efficiency of C. parvum oocyst using ionic strength or pH is inappropriate when non-DLVO interactions are involved. A review of our results and comparison to existing data shows that it is challenging to accurately predict the attachment efficiency using single peak value of breakthrough curve data from geochemical information of porous media.

Modeling electrokinetics in ionic liquids: General

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

Wang, Chao; Bao, Jie; Pan, Wenxiao

2017-04-07

Using direct numerical simulations we provide a thorough study on the electrokinetics of ionic liquids. In particular, the modfied Poisson-Nernst-Planck (MPNP) equations are solved to capture the crowding and overscreening effects that are the characteristics of an ionic liquid. For modeling electrokinetic flows in an ionic liquid, the MPNP equations are coupled with the Navier-Stokes equations to study the coupling of ion transport, hydrodynamics, and electrostatic forces. Specifically, we consider the ion transport between two parallel plates, charging dynamics in a 2D straight-walled pore, electro-osmotic ow in a nano-channel, electroconvective instability on a plane ion-selective surface, and electroconvective ow onmore » a curved ion-selective surface. We discuss how the crowding and overscreening effects and their interplay affect the electrokinetic behaviors of ionic liquids in these application problems.« less

Ionic thermoelectric gating organic transistors

PubMed Central

Zhao, Dan; Fabiano, Simone; Berggren, Magnus; Crispin, Xavier

2017-01-01

Temperature is one of the most important environmental stimuli to record and amplify. While traditional thermoelectric materials are attractive for temperature/heat flow sensing applications, their sensitivity is limited by their low Seebeck coefficient (∼100 μV K−1). Here we take advantage of the large ionic thermoelectric Seebeck coefficient found in polymer electrolytes (∼10,000 μV K−1) to introduce the concept of ionic thermoelectric gating a low-voltage organic transistor. The temperature sensing amplification of such ionic thermoelectric-gated devices is thousands of times superior to that of a single thermoelectric leg in traditional thermopiles. This suggests that ionic thermoelectric sensors offer a way to go beyond the limitations of traditional thermopiles and pyroelectric detectors. These findings pave the way for new infrared-gated electronic circuits with potential applications in photonics, thermography and electronic-skins. PMID:28139738

Peroxyoxalate chemiluminescence enhanced by oligophenylenevinylene fluorophores in the presence of various surfactants.

PubMed

Motoyoshiya, Jiro; Takigawa, Setsuko

2014-11-01

The effect of several surfactants on peroxyoxalate chemiluminescence (PO-CL) using oligophenylenevinylene fluorophores was investigated. Among several oligophenylenevinylenes consisting of stilbene units, linearly conjugated ones, such as distyrylbenzene and distyrylstilbene, effectively enhanced PO-CL efficiency. Various effects of anionic, cationic, amphoteric and non-ionic surfactants on the CL efficiency of PO-CL were determined using three oxalates and the distyrylbenzene fluorophore. Anionic and non-ionic surfactants effectively enhanced CL efficiency, in contrast to the negative effect of cationic and amphoteric surfactants. Non-ionic surfactants were also effective in CL reactions of oxalates bearing dodecyl ester groups by the hydrophobic interaction between their alkyl chains. Considering these results, the surfactants not only increase the concentrations of water-insoluble interacting species in the hydrophobic micelle cores, but also control rapid degradation of the oxalates by alkaline hydrolysis. Copyright © 2014 John Wiley & Sons, Ltd.

Fluid flow sensing with ionic polymer-metal composites

NASA Astrophysics Data System (ADS)

Stalbaum, Tyler; Trabia, Sarah; Shen, Qi; Kim, Kwang J.

2016-04-01

Ionic polymer-metal composite (IPMC) actuators and sensors have been developed and modeled over the last two decades for use as soft-robotic deformable actuators and sensors. IPMC devices have been suggested for application as underwater actuators, energy harvesting devices, and medical devices such as in guided catheter insertion. Another interesting application of IPMCs in flow sensing is presented in this study. IPMC interaction with fluid flow is of interest to investigate the use of IPMC actuators as flow control devices and IPMC sensors as flow sensing devices. An organized array of IPMCs acting as interchanging sensors and actuators could potentially be designed for both flow measurement and control, providing an unparalleled tool in maritime operations. The underlying physics for this system include the IPMC ion transport and charge fundamental framework along with fluid dynamics to describe the flow around IPMCs. An experimental setup for an individual rectangular IPMC sensor with an externally controlled fluid flow has been developed to investigate this phenomenon and provide further insight into the design and application of this type of device. The results from this portion of the study include recommendations for IPMC device designs in flow control.

Communication: Influence of nanophase segregation on ion transport in room temperature ionic liquids

DOE PAGES

Griffin, Philip J.; Wang, Yangyang; Holt, Adam P.; ...

2016-04-21

In this paper, we report measurements of the ionic conductivity, shear viscosity, and structural dynamics in a homologous series of quaternary ammonium ionic liquids (ILs) and a prototypical imidazolium-based IL over a wide range of temperatures down to the glass transition. We find that the ionic conductivity of these materials generally decreases, while the shear viscosity correspondingly increases, with increasing volume fraction of aliphatic side groups. Upon crossing an aliphatic volume fraction of ~0.40, we observe a sharp, order-of-magnitude decrease in ionic conductivity and enhancement of viscosity, which coincides with the presence of long-lived, nanometer-sized alkyl aggregates. These strong changesmore » in dynamics are not mirrored in the ionicity of these ILs, which decreases nearly linearly with aliphatic volume fraction. Finally, our results demonstrate that nanophase segregation in neat ILs strongly reduces ionic conductivity primarily due to an aggregation-induced suppression of dynamics.« less

Underwater energy harvesting from a turbine hosting ionic polymer metal composites

NASA Astrophysics Data System (ADS)

Cellini, Filippo; Pounds, Jason; Peterson, Sean D.; Porfiri, Maurizio

2014-08-01

In this study, we explore the possibility of energy harvesting from fluid flow through a turbine hosting ionic polymer metal composites (IPMCs). Specifically, IPMC harvesters are embedded in the blades of a small-scale vertical axis water turbine to convert flow kinetics into electrical power via low-frequency flow-induced IPMC deformations. An in-house fabricated Savonius-Darrieus hybrid active turbine with three IPMCs is tested in a laboratory water tunnel to estimate the energy harvesting capabilities of the device as a function of the shunting electrical load. The turbine is shown to harvest a few nanowatt from a mean flow of 0.43\\;m\\;{{s}^{-1}} for shunting resistances in the range 100-1000\\;\\Omega . To establish a first understanding of the energy harvesting device, we propose a quasi-static hydroelastic model for the bending of the IPMCs and we utilize a black-box model to study their electromechanical response.

STIMULI-RESPONSIVE POLYMERS WITH ENHANCED EFFICIENCY IN RESERVOIR RECOVERY PROCESSES

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

Charles McCormick; Roger Hester

This sixth and final progress report for DOE Award Number DE-FC26-01BC15317 describes research during the period March 01, 2004 through August 31, 2004 performed at the University of Southern Mississippi on ''Stimuli Responsive Polymers with Enhanced Efficiency in Reservoir Recovery'' processes. Significantly, terpolymers that are responsive to changes in pH and ionic strength have been synthesized, characterized, and their solution properties have been extensively examined. Terpolymers composed of acrylamide, a carboxylated acrylamido monomer (AMBA), and a quaternary ammonium monomer (AMBATAC) with balanced compositions of the latter two, exhibit increases in aqueous solution viscosity as NaCl concentration is increased. This increasemore » in polymer coil size can be expected upon injection of this type of polymer into oil reservoirs of moderate-to-high salinity, leading to better mobility control. The opposite effect (loss of viscosity) is observed for conventional polymer systems. Additionally polymer mobility characteristics have been conducted for a number of hydrophilic copolymers utilizing an extensional flow apparatus and size exclusion chromatography. This study reveled that oil recovery enhancement through use of polymers in a water flood is due to the polymer's resistance to deformation as it flows through the reservoir. Individual polymers when in aqueous solution form coils. The larger the polymer's coil size, the greater the polymer's resistance to extensional flow and the more effective the polymer is in enhancing oil recovery. Large coil sizes are obtained by increasing the polymer molecular weight and having macromolecular structures that favor greater swelling of the coil by the aqueous solvent conditions (temperature, pH and electrolyte concentration) existing in the reservoir.« less

The effect of varying the anion of an ionic liquid on the solvent effects on a nucleophilic aromatic substitution reaction.

PubMed

Hawker, Rebecca R; Haines, Ronald S; Harper, Jason B

2018-05-09

A variety of ionic liquids, each containing the same cation but a different anion, were examined as solvents for a nucleophilic aromatic substitution reaction. Varying the proportion of ionic liquid was found to increase the rate constant as the mole fraction of ionic liquid increased demonstrating that the reaction outcome could be controlled through varying the ionic liquid. The solvent effects were correlated with the hydrogen bond accepting ability (β) of the ionic liquid anion allowing for qualitative prediction of the effect of changing this component of the solute. To determine the microscopic origins of the solvent effects, activation parameters were determined through temperature-dependent kinetic analyses and shown to be consistent with previous studies. With the knowledge of the microscopic interactions in solution, an ionic liquid was rationally chosen to maximise rate enhancement demonstrating that an ionic solvent can be selected to control reaction outcome for this reaction type.

Theoretical and experimental studies on ionic currents in nanopore-based biosensors.

PubMed

Liu, Lei; Li, Chu; Ma, Jian; Wu, Yingdong; Ni, Zhonghua; Chen, Yunfei

2014-12-01

Novel generation of analytical technology based on nanopores has provided possibilities to fabricate nanofluidic devices for low-cost DNA sequencing or rapid biosensing. In this paper, a simplified model was suggested to describe DNA molecule's translocation through a nanopore, and the internal potential, ion concentration, ionic flowing speed and ionic current in nanopores with different sizes were theoretically calculated and discussed on the basis of Poisson-Boltzmann equation, Navier-Stokes equation and Nernst-Planck equation by considering several important parameters, such as the applied voltage, the thickness and the electric potential distributions in nanopores. In this way, the basic ionic currents, the modulated ionic currents and the current drops induced by translocation were obtained, and the size effects of the nanopores were carefully compared and discussed based on the calculated results and experimental data, which indicated that nanopores with a size of 10 nm or so are more advantageous to achieve high quality ionic current signals in DNA sensing.

Electrodeionization Using Microseparated Bipolar Membranes

NASA Technical Reports Server (NTRS)

Lyons, Donald; Jackson, George; Andrews, Craig C.; Tennakoon, Charles L, K.; Singh, Waheguru; Hitchens, G. Duncan; Jabs, Harry; Chepin, James F.; Archer, Shivaun; Gonzalez-Martinez, Anukia;

Stagnation point flow of wormlike micellar solutions in a microfluidic cross-slot device: effects of surfactant concentration and ionic environment.

PubMed

Haward, Simon J; McKinley, Gareth H

2012-03-01

We employ the techniques of microparticle image velocimetry and full-field birefringence microscopy combined with mechanical measurements of the pressure drop to perform a detailed characterization of the extensional rheology and elastic flow instabilities observed for a range of wormlike micellar solutions flowing through a microfluidic cross-slot device. As the flow rate through the device is increased, the flow first bifurcates from a steady symmetric to a steady asymmetric configuration characterized by a birefringent strand of highly aligned micellar chains oriented along the shear-free centerline of the flow field. At higher flow rates the flow becomes three dimensional and time dependent and is characterized by aperiodic spatiotemporal fluctuations of the birefringent strand. The extensional properties and critical conditions for the onset of flow instabilities in the fluids are highly dependent on the fluid formulation (surfactant concentration and ionic strength) and the resulting changes in the linear viscoelasticity and nonlinear shear rheology of the fluids. By combining the measurements of critical conditions for the flow transitions with the viscometric material properties and the degree of shear-thinning characterizing each test fluid, it is possible to construct a stability diagram for viscoelastic flow of complex fluids in the cross-slot geometry.

Electro-osmotic infusion for joule heating soil remediation techniques

DOEpatents

Carrigan, Charles R.; Nitao, John J.

1999-01-01

Electro-osmotic infusion of ground water or chemically tailored electrolyte is used to enhance, maintain, or recondition electrical conductivity for the joule heating remediation technique. Induced flows can be used to infuse electrolyte with enhanced ionic conductivity into the vicinity of the electrodes, maintain the local saturation of near-electrode regions and resaturate a partially dried out zone with groundwater. Electro-osmotic infusion can also tailor the conductivity throughout the target layer by infusing chemically modified and/or heated electrolyte to improve conductivity contrast of the interior. Periodic polarity reversals will prevent large pH changes at the electrodes. Electro-osmotic infusion can be used to condition the electrical conductivity of the soil, particularly low permeability soil, before and during the heating operation. Electro-osmotic infusion is carried out by locating one or more electrodes adjacent the heating electrodes and applying a dc potential between two or more electrodes. Depending on the polarities of the electrodes, the induced flow will be toward the heating electrodes or away from the heating electrodes. In addition, electrodes carrying a dc potential may be located throughout the target area to tailor the conductivity of the target area.

Active chemisorption sites in functionalized ionic liquids for carbon capture.

PubMed

Cui, Guokai; Wang, Jianji; Zhang, Suojiang

2016-07-25

Development of novel technologies for the efficient and reversible capture of CO2 is highly desired. In the last decade, CO2 capture using ionic liquids has attracted intensive attention from both academia and industry, and has been recognized as a very promising technology. Recently, a new approach has been developed for highly efficient capture of CO2 by site-containing ionic liquids through chemical interaction. This perspective review focuses on the recent advances in the chemical absorption of CO2 using site-containing ionic liquids, such as amino-based ionic liquids, azolate ionic liquids, phenolate ionic liquids, dual-functionalized ionic liquids, pyridine-containing ionic liquids and so on. Other site-containing liquid absorbents such as amine-based solutions, switchable solvents, and functionalized ionic liquid-amine blends are also investigated. Strategies have been discussed for how to activate the existent reactive sites and develop novel reactive sites by physical and chemical methods to enhance CO2 absorption capacity and reduce absorption enthalpy. The carbon capture mechanisms of these site-containing liquid absorbents are also presented. Particular attention has been paid to the latest progress in CO2 capture in multiple-site interactions by amino-free anion-functionalized ionic liquids. In the last section, future directions and prospects for carbon capture by site-containing ionic liquids are outlined.

Clustering effects in ionic polymers: Molecular dynamics simulations.

PubMed

Agrawal, Anupriya; Perahia, Dvora; Grest, Gary S

2015-08-01

Ionic clusters control the structure, dynamics, and transport in soft matter. Incorporating a small fraction of ionizable groups in polymers substantially reduces the mobility of the macromolecules in melts. These ionic groups often associate into random clusters in melts, where the distribution and morphology of the clusters impact the transport in these materials. Here, using molecular dynamic simulations we demonstrate a clear correlation between cluster size and morphology with the polymer mobility in melts of sulfonated polystyrene. We show that in low dielectric media ladderlike clusters that are lower in energy compared with spherical assemblies are formed. Reducing the electrostatic interactions by enhancing the dielectric constant leads to morphological transformation from ladderlike clusters to globular assemblies. Decrease in electrostatic interaction significantly enhances the mobility of the polymer.

Predicting ion specific capacitances of supercapacitors due to quantum ionic interactions.

PubMed

Parsons, Drew F

2014-08-01

A new theoretical framework is now available to help explain ion specific (Hofmeister) effects. All measurements in physical chemistry show ion specificity, inexplicable by classical electrostatic theories. These ignore ionic dispersion forces that change ionic adsorption. We explored ion specificity in supercapacitors using a modified Poisson-Boltzmann approach that includes ionic dispersion energies. We have applied ab initio quantum chemical methods to determine required ion sizes and ion polarisabilities. Our model represents graphite electrodes through their optical dielectric spectra. The electrolyte was 1.2 M Li salt in propylene carbonate, using the common battery anions, PF6(-), BF4(-) and ClO4(-). We also investigated the perhalate series with BrO4(-) and IO4(-). The capacitance C=dσ/dψ was calculated from the predicted electrode surface charge σ of each electrode with potential ψ between electrodes. Compared to the purely electrostatic calculation, the capacitance of a positively charged graphite electrode was enhanced by more than 15%, with PF6(-) showing >50% increase in capacitance. IO4(-) provided minimal enhancement. The enhancement is due to adsorption of both anions and cations, driven by ionic dispersion forces. The Hofmeister series in the single-electrode capacitance was PF6(-)>BF4(-)>ClO4(-)>BrO4(-)>IO4(-) . When the graphite electrode was negatively charged, the perhalates provided almost no enhancement of capacitance, while PF6(-) and BF4(-) decreased capacitance by about 15%. Due to the asymmetric impact of nonelectrostatic ion interactions, the capacitances of positive and negative electrodes are not equal. The capacitance of a supercapacitor should therefore be reported as two values rather than one, similar to the matrix of mutual capacitances used in multielectrode devices. Copyright © 2014 Elsevier Inc. All rights reserved.

Viscoelasticity of nano-alumina dispersions

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

Rand, B.; Fries, R.

1996-06-01

The flow and viscoelastic properties of electrostatically stabilized nano-alumina dispersions have been studied as a function of ionic strength and volume fraction of solids. At low ionic strength the suspensions were deflocculated and showed a transition from viscous to elastic behavior as the solid content increased associated with the onset of double layer interpenetration. The phase transition was progressively shifted to higher solids fractions with increasing ionic strength. At higher ionic strength, above the critical coagulation concentration, the suspensions formed attractive networks characterized by high elasticity. Two independent methods of estimating the effective radius of electrostatically stabilized {open_quotes}soft{close_quotes} particles, a{submore » eff}, are presented based on phase angle data and a modified Dougherty-Krieger equation. The results suggest that a{sub eff} is not constant for a given system but changes with both solids fraction and ionic strength.« less

Atmospheric Pressure Method and Apparatus for Removal of Organic Matter with Atomic and Ionic Oxygen

NASA Technical Reports Server (NTRS)

Banks, Bruce A. (Inventor); Rutledge, Sharon K. (Inventor)

1996-01-01

A gas stream containing ionic and atomic oxygen in inert gas is used to remove organic matter from a substrate. The gas stream is formed by flowing a mixture of gaseous oxygen in an inert gas such as helium at atmospheric pressure past a high voltage, current limited, direct current arc which contacts the gas mixture and forms the ionic and atomic oxygen. The arc is curved at the cathode end and the ionic oxygen formed by the arc nearer to the anode end of the arc is accelerated in a direction towards the cathode by virtue of its charge. The relatively high mass to charge ratio of the ionic oxygen enables at least some of it to escape the arc before contacting the cathode and it is directed onto the substrate. This is useful for cleaning delicate substrates such as fine and historically important paintings and delicate equipment and the like.

Atmospheric Pressure Method and Apparatus for Removal of Organic Matter with Atomic and Ionic Oxygen

NASA Technical Reports Server (NTRS)

Banks, Bruce A. (Inventor); Rutledge, Sharon K. (Inventor)

1997-01-01

A gas stream containing ionic and atomic oxygen in inert gas is used to remove organic matter from a substrate. The gas stream is formed by flowing a mixture of gaseous oxygen in an inert gas such as helium at atmospheric pressure past a high voltage, current limited, direct current arc which contacts the gas mixture and forms the ionic and atomic oxygen. The arc is curved at the cathode end and the ionic oxygen formed by the arc nearer to the anode end of the arc is accelerated in a direction towards the cathode by virtue of its charge. The relatively high mass to charge ratio of the ionic oxygen enables at least some of it to escape the arc before contacting the cathode and it is directed onto the substrate. This is useful for cleaning delicate substrates such as fine and historically important paintings and delicate equipment and the like.

Multiscale modeling of electroosmotic flow: Effects of discrete ion, enhanced viscosity, and surface friction

NASA Astrophysics Data System (ADS)

Bhadauria, Ravi; Aluru, N. R.

2017-05-01

We propose an isothermal, one-dimensional, electroosmotic flow model for slit-shaped nanochannels. Nanoscale confinement effects are embedded into the transport model by incorporating the spatially varying solvent and ion concentration profiles that correspond to the electrochemical potential of mean force. The local viscosity is dependent on the solvent local density and is modeled using the local average density method. Excess contributions to the local viscosity are included using the Onsager-Fuoss expression that is dependent on the local ionic strength. A Dirichlet-type boundary condition is provided in the form of the slip velocity that is dependent on the macroscopic interfacial friction. This solvent-surface specific interfacial friction is estimated using a dynamical generalized Langevin equation based framework. The electroosmotic flow of Na+ and Cl- as single counterions and NaCl salt solvated in Extended Simple Point Charge (SPC/E) water confined between graphene and silicon slit-shaped nanochannels are considered as examples. The proposed model yields a good quantitative agreement with the solvent velocity profiles obtained from the non-equilibrium molecular dynamics simulations.

PALLADIUM-CATALYZED OXIDATION OF STYRENE AND ALKENES IN PRESENCE OF IONIC LIQUIDS (WACKER REACTION)

EPA Science Inventory

The use of ionic liquids in various synthetic transformations is gaining significance due to the enhanced reaction rates, potential for recycling and compatibility with various organic compounds and organometallic catalysts. Palladium-catalyzed oxidation of styrene and other alk...

Oxidized template-synthesized mesoporous carbon with pH-dependent adsorption activity: A promising adsorbent for removal of hydrophilic ionic liquid

NASA Astrophysics Data System (ADS)

Zhang, Ling; Cao, Wugang; Alvarez, Pedro J. J.; Qu, Xiaolei; Fu, Heyun; Zheng, Shourong; Xu, Zhaoyi; Zhu, Dongqiang

2018-05-01

Aiming to remove ionic liquid pollutants from water, an ordered mesoporous carbon CMK-3 (OMC) was prepared and modified by oxidation with nitric acid. A commercial microporous activated carbon adsorbent, Filtrasorb-300 (AC), was used as benchmark. Boehm titration showed that oxidized OMC had a substantially higher oxygen content than oxidized AC. Adsorption of the hydrophilic imidazolium-based ionic liquid 1-Butyl-3-methylimidazolium chloride ([Bmim]Cl) on OMC and AC was well-described by the Freundlich isotherm model. Surface oxidation markedly enhanced [Bmim]Cl adsorption by both OMC and AC. Nevertheless, [Bmim]Cl adsorption was much higher on oxidized OMC than on oxidized AC. Increasing pH had negligible influence on [Bmim]Cl adsorption on pristine OMC, but enhanced adsorption on oxidized OMC. Regeneration tests showed stable performance of oxidized OMC over five adsorption-desorption cycles. Thus, oxidized OMC can be a highly effective adsorbent for the removal of hydrophilic ionic liquids from water.

Effect of Aperture Field Variability, Flow Rate, and Ionic Strength on Colloid Transport in Single Fractures: Laboratory-Scale Experiments and Numerical Simulation

NASA Astrophysics Data System (ADS)

Zheng, Q.; Dickson, S.; Guo, Y.

2007-12-01

A good understanding of the physico-chemical processes (i.e., advection, dispersion, attachment/detachment, straining, sedimentation etc.) governing colloid transport in fractured media is imperative in order to develop appropriate bioremediation and/or bioaugmentation strategies for contaminated fractured aquifers, form management plans for groundwater resources to prevent pathogen contamination, and identify suitable radioactive waste disposal sites. However, research in this field is still in its infancy due to the complex heterogeneous nature of fractured media and the resulting difficulty in characterizing this media. The goal of this research is to investigate the effects of aperture field variability, flow rate and ionic strength on colloid transport processes in well characterized single fractures. A combination of laboratory-scale experiments, numerical simulations, and imaging techniques were employed to achieve this goal. Transparent replicas were cast from natural rock fractures, and a light transmission technique was employed to measure their aperture fields directly. The surface properties of the synthetic fractures were characterized by measuring the zeta-potential under different ionic strengths. A 33 (3 increased to the power of 3) factorial experiment was implemented to investigate the influence of aperture field variability, flow rate, and ionic strength on different colloid transport processes in the laboratory-scale fractures, specifically dispersion and attachment/detachment. A fluorescent stain technique was employed to photograph the colloid transport processes, and an analytical solution to the one-dimensional transport equation was fit to the colloid breakthrough curves to calculate the average transport velocity, dispersion coefficient, and attachment/detachment coefficient. The Reynolds equation was solved to obtain the flow field in the measured aperture fields, and the random walk particle tracking technique was employed to model the colloid transport experiments. The images clearly show the development of preferential pathways for colloid transport in the different aperture fields and under different flow conditions. Additionally, a correlation between colloid deposition and fracture wall topography was identified. This presentation will demonstrate (1) differential transport between colloid and solute in single fractures, and the relationship between differential transport and aperture field statistics; (2) the relationship between the colloid dispersion coefficient and aperture field statistics; and (3) the relationship between attachment/detachment, aperture field statistics, fracture wall topography, flow rate, and ionic strength. In addition, this presentation will provide insight into the application of the random walk particle tracking technique for modeling colloid transport in variable-aperture fractures.

Enhanced electrochemiluminescence sensor from tris(2,2'-bipyridyl)ruthenium(II) incorporated into MCM-41 and an ionic liquid-based carbon paste electrode.

PubMed

Li, Jing; Huang, Minghua; Liu, Xiaoqing; Wei, Hui; Xu, Yuanhong; Xu, Guobao; Wang, Erkang

2007-07-01

The electrochemiluminescence (ECL) of tris(2,2'-bipyridyl)ruthenium(II) [Ru(bpy)(3)(2+)] ion-exchanged in the sulfonic-functionalized MCM-41 silicas was developed with tripropylamine (TPrA) as a co-reactant in a carbon paste electrode (CPE) using a room temperature ionic liquid (IL) as a binder. The sulfonic-functionalized silicas MCM-41 were used for preparing an ECL sensor by the electrostatic interactions between Ru(bpy)(3)(2+) cations and sulfonic acid groups. We used the IL as a binder to construct the CPE (IL-CPE) to replace the traditional binder of the CPE (T-CPE)--silicone oil. The results indicated that the MCM-41-modified IL-CPE had more open structures to allow faster diffusion of Ru(bpy)(3)(2+) and that the ionic liquid also acted as a conducting bridge to connect TPrA with Ru(bpy)(3)(2+) sites immobilized in the electrode, resulting in a higher ECL intensity compared with the MCM-41-modified T-CPE. Herein, the detection limit for TPrA of the MCM-41-modified IL-CPE was 7.2 nM, which was two orders of magnitude lower than that observed at the T-CPE. When this new sensor was used in flow injection analysis (FIA), the MCM-41-modified IL-CPE ECL sensor also showed good reproducibility. Furthermore, the sensor could also be renewed easily by mechanical polishing whenever needed.

Activation of MEK/ERK signaling contributes to the PACAP-induced increase in guinea pig cardiac neuron excitability

PubMed Central

Tompkins, John D.; Clason, Todd A.; Hardwick, Jean C.; Girard, Beatrice M.; Merriam, Laura A.; May, Victor

2016-01-01

Pituitary adenylate cyclase (PAC)-activating polypeptide (PACAP) peptides (Adcyap1) signaling at the selective PAC1 receptor (Adcyap1r1) participate in multiple homeostatic and stress-related responses, yet the cellular mechanisms underlying PACAP actions remain to be completely elucidated. PACAP/PAC1 receptor signaling increases excitability of neurons within the guinea pig cardiac ganglia, and as these neurons are readily accessible, this neuronal system is particularly amenable to study of PACAP modulation of ionic conductances. The present study investigated how PACAP activation of MEK/ERK signaling contributed to the peptide-induced increase in cardiac neuron excitability. Treatment with the MEK inhibitor PD 98059 blocked PACAP-stimulated phosphorylated ERK and, in parallel, suppressed the increase in cardiac neuron excitability. However, PD 98059 did not blunt the ability of PACAP to enhance two inward ionic currents, one flowing through hyperpolarization-activated nonselective cationic channels (Ih) and another flowing through low-voltage-activated calcium channels (IT), which support the peptide-induced increase in excitability. Thus a PACAP- and MEK/ERK-sensitive, voltage-dependent conductance(s), in addition to Ih and IT, modulates neuronal excitability. Despite prior work implicating PACAP downregulation of the KV4.2 potassium channel in modulation of excitability in other cells, treatment with the KV4.2 current blocker 4-aminopyridine did not replicate the PACAP-induced increase in excitability in cardiac neurons. However, cardiac neurons express the ERK target, the NaV1.7 sodium channel, and treatment with the selective NaV1.7 channel inhibitor PF-04856264 decreased the PACAP modulation of excitability. From these results, PACAP/PAC1 activation of MEK/ERK signaling may phosphorylate the NaV1.7 channel, enhancing sodium currents near the threshold, an action contributing to repetitive firing of the cardiac neurons exposed to PACAP. PMID:27488668

Drag reducing properties of microalgal exopolymers.

PubMed

Ramus, J; Kenney, B E; Shaughnessy, E J

1989-01-25

Dilute aqueous solutions of polymers released by marine phytoplankton (microalgae) were shown to effectively reduce drag in capillary pipe flow. Tests were performed in a capillary turbulent flow viscometer which extruded small samples under high pressures. In all, 22 species were screened, and the products of one chlorophyte and four rhodophyte species proved especially effective. The viscoelastic polymers produced by these species delayed the transition from laminar to turbulent flow to significantly higher Re. In general, polymeric regime segments come off the maximum drag reduction asymptote at characteristic retro-onset points, and come to lie approximately parallel to, but displaced upwards from the Prandtl-von Karman line. The delay to transition was shown to be dependent on additive polymer concentration, capillary diameter, and temperature. Ionic concentration, ionic composition, or pH had little effect on drag reducing properties.

Microfluidic System Simulation Including the Electro-Viscous Effect

NASA Technical Reports Server (NTRS)

Rojas, Eileen; Chen, C. P.; Majumdar, Alok

2007-01-01

This paper describes a practical approach using a general purpose lumped-parameter computer program, GFSSP (Generalized Fluid System Simulation Program) for calculating flow distribution in a network of micro-channels including electro-viscous effects due to the existence of electrical double layer (EDL). In this study, an empirical formulation for calculating an effective viscosity of ionic solutions based on dimensional analysis is described to account for surface charge and bulk fluid conductivity, which give rise to electro-viscous effect in microfluidics network. Two dimensional slit micro flow data was used to determine the model coefficients. Geometry effect is then included through a Poiseuille number correlation in GFSSP. The bi-power model was used to calculate flow distribution of isotropically etched straight channel and T-junction microflows involving ionic solutions. Performance of the proposed model is assessed against experimental test data.

Potentiometric chip-based multipumping flow system for the simultaneous determination of fluoride, chloride, pH, and redox potential in water samples.

PubMed

Chango, Gabriela; Palacio, Edwin; Cerdà, Víctor

2018-08-15

A simple potentiometric chip-based multipumping flow system (MPFS) has been developed for the simultaneous determination of fluoride, chloride, pH, and redox potential in water samples. The proposed system was developed by using a poly(methyl methacrylate) chip microfluidic-conductor using the advantages of flow techniques with potentiometric detection. For this purpose, an automatic system has been designed and built by optimizing the variables involved in the process, such as: pH, ionic strength, stirring and sample volume. This system was applied successfully to water samples getting a versatile system with an analysis frequency of 12 samples per hour. Good correlation between chloride and fluoride concentration measured with ISE and ionic chromatography technique suggests satisfactory reliability of the system. Copyright © 2018 Elsevier B.V. All rights reserved.

Clustering effects in ionic polymers: Molecular dynamics simulations

DOE PAGES

Agrawal, Anupriya; Perahia, Dvora; Grest, Gary S.

2015-08-18

Ionic clusters control the structure, dynamics, and transport in soft matter. Incorporating a small fraction of ionizable groups in polymers substantially reduces the mobility of the macromolecules in melts. Furthermore, these ionic groups often associate into random clusters in melts, where the distribution and morphology of the clusters impact the transport in these materials. Here, using molecular dynamic simulations we demonstrate a clear correlation between cluster size and morphology with the polymer mobility in melts of sulfonated polystyrene. We show that in low dielectric media ladderlike clusters that are lower in energy compared with spherical assemblies are formed. Reducing themore » electrostatic interactions by enhancing the dielectric constant leads to morphological transformation from ladderlike clusters to globular assemblies. Finally, decrease in electrostatic interaction significantly enhances the mobility of the polymer.« less

Numerical modeling of ultrasonic cavitation in ionic liquids

NASA Astrophysics Data System (ADS)

Calvisi, Michael L.; Elder, Ross M.

2017-11-01

Ionic liquids have favorable properties for sonochemistry applications in which the high temperatures and pressures achieved by cavitation bubbles are important drivers of chemical processes. Two different numerical models are presented to simulate ultrasonic cavitation in ionic liquids, each with different capabilities and physical assumptions. A model based on a compressible form of the Rayleigh-Plesset equation (RPE) simulates ultrasonic cavitation of a spherical bubble with a homogeneous interior, incorporating evaporation and condensation at the bubble surface, and temperature-varying thermodynamic properties in the interior. A second, more computationally intensive model of a spherical bubble uses the finite element method (FEM) and accounts for spatial variations in pressure and temperature throughout the flow domain. This model provides insight into heat transfer across the bubble surface and throughout the bubble interior and exterior. Parametric studies are presented for sonochemistry applications involving ionic liquids as a solvent, examining a range of realistic ionic liquid properties and initial conditions to determine their effect on temperature and pressure. Results from the two models are presented for parametric variations including viscosity, thermal conductivity, water content of the ionic liquid solvent, acoustic frequency, and initial bubble pressure. An additional study performed with the FEM model examines thermal penetration into the surrounding ionic liquid during bubble oscillation. The results suggest the prospect of tuning ionic liquid properties for specific applications.

Ionic conduction in sodium azide under high pressure: Experimental and theoretical approaches

NASA Astrophysics Data System (ADS)

Wang, Qinglin; Ma, Yanzhang; Sang, Dandan; Wang, Xiaoli; Liu, Cailong; Hu, Haiquan; Wang, Wenjun; Zhang, Bingyuan; Fan, Quli; Han, Yonghao; Gao, Chunxiao

2018-04-01

Alkali metal azides can be used as starting materials for the synthesis of polymeric nitrogen, a potential material of high energy density. In this letter, we report the ionic transport behavior in sodium azide under high pressure by in situ impedance spectroscopy and density functional theory calculations. The ionic transportation consists of ion transfer and Warburg diffusion processes. The ionic migration channels and barrier energy were given for the high-pressure phases. The enhanced ionic conductivity of the γ phase with pressure is because of the formation of space charge regions in the grain boundaries. This ionic conduction and grain boundary effect in NaN3 under pressures could shed light on the better understanding of the conduction mechanism of alkali azides and open up an area of research for polymeric nitrogen in these compounds and other high-energy-density polynitrides.

Effects of novel triple-stage antimalarial ionic liquids on lipid membrane models.

PubMed

Ferraz, Ricardo; Pinheiro, Marina; Gomes, Ana; Teixeira, Cátia; Prudêncio, Cristina; Reis, Salette; Gomes, Paula

2017-09-01

Primaquine-based ionic liquids, obtained by acid-base reaction between parent primaquine and cinnamic acids, were recently found as triple-stage antimalarial hits. These ionic compounds displayed significant activity against both liver- and blood-stage Plasmodium parasites, as well as against stage V P. falciparum parasites. Remarkably, blood-stage activity of the ionic liquids against both chloroquine-sensitive (3D7) and resistant (Dd2) P. falciparum strains was clearly superior to those of the respective covalent (amide) analogues and of parent primaquine. Having hypothesized that such behaviour might be ascribed to an enhanced ability of the ionic compounds to permeate into Plasmodium-infected erythrocytes, we have carried out a differential scanning calorimetry-based study of the interactions between the ionic liquids and membrane models. Results provide evidence, at the molecular level, that the primaquine-derived ionic liquids may contribute to an increased permeation of the parent drug into malaria-infected erythrocytes, which has relevant implications towards novel antimalarial approaches based on ionic liquids. Copyright © 2017 Elsevier Ltd. All rights reserved.

Transport and remobilization of multi-walled carbon nanotubes in porous media during dynamic saturation change

NASA Astrophysics Data System (ADS)

Sharma, P.

2012-04-01

Nanotechnology is one of the most important technologies in this century and it is evoking a new industrial revolution. Carbon nanotubes (CNTs) are important engineered nanoparticles with unique and beneficial properties. As a result, CNT has been used in a wide range of commercial products including electronics, optical devices and drug delivery leading to their disposal in the natural environment. Literature studies have investigated the mobility of CNTs in saturated porous media under differing physical and chemical conditions. However CNT transport in temporarily changing porous media water content has not been investigated thus far (a common scenario with rainfall/infiltration events in the vadose zone). This study investigated the mobilization of multi-walled CNTs (MCNTs) in repeated wetting and drying cycles with varying flow rates and ionic strength of the inflow solution. Imbibition-drainage-imbibition cycle experiments suggest that MCNTs mobilization increased with increase in flow rates. MCNTs mobilization occurred only with first imbibition events at low ionic strengths however less mobilization happened for higher ionic strength inflow solution in the first imbibition cycle and additional MCNTs were found in the outflow solution in second imbibition cycle, using low ionic strength solution. This observation was likely due to the attachment force between MCNTs and sand surface. Most of the MCNT mobilization occurred during liquid-gas interface movement with less chance of MCNTs to jump the energy barrier at higher ionic strength solution. As a result, less detachment of MCNTs occurred from the sand surface during drainage.

Enhancement of force generated by individual myosin heads in skinned rabbit psoas muscle fibers at low ionic strength.

PubMed

Sugi, Haruo; Abe, Takahiro; Kobayashi, Takakazu; Chaen, Shigeru; Ohnuki, Yoshiki; Saeki, Yasutake; Sugiura, Seiryo

2013-01-01

Although evidence has been presented that, at low ionic strength, myosin heads in relaxed skeletal muscle fibers form linkages with actin filaments, the effect of low ionic strength on contraction characteristics of Ca(2+)-activated muscle fibers has not yet been studied in detail. To give information about the mechanism of muscle contraction, we have examined the effect of low ionic strength on the mechanical properties and the contraction characteristics of skinned rabbit psoas muscle fibers in both relaxed and maximally Ca(2+)-activated states. By progressively decreasing KCl concentration from 125 mM to 0 mM (corresponding to a decrease in ionic strength μ from 170 mM to 50 mM), relaxed fibers showed changes in mechanical response to sinusoidal length changes and ramp stretches, which are consistent with the idea of actin-myosin linkage formation at low ionic strength. In maximally Ca(2+)-activated fibers, on the other hand, the maximum isometric force increased about twofold by reducing KCl concentration from 125 to 0 mM. Unexpectedly, determination of the force-velocity curves indicated that, the maximum unloaded shortening velocity Vmax, remained unchanged at low ionic strength. This finding indicates that the actin-myosin linkages, which has been detected in relaxed fibers at low ionic strength, are broken quickly on Ca(2+) activation, so that the linkages in relaxed fibers no longer provide any internal resistance against fiber shortening. The force-velocity curves, obtained at various levels of steady Ca(2+)-activated isometric force, were found to be identical if they are normalized with respect to the maximum isometric force. The MgATPase activity of muscle fibers during isometric force generation was found not to change appreciably at low ionic strength despite the two-fold increase in Ca(2+)-activated isometric force. These results can be explained in terms of enhancement of force generated by individual myosin heads, but not by any changes in kinetic properties of cyclic actin-myosin interaction.

Surface deformation and shear flow in ligand mediated cell adhesion.

PubMed

Sircar, Sarthok; Roberts, Anthony J

2016-10-01

We present a unified, multiscale model to study the attachment/detachment dynamics of two deforming, charged, near spherical cells, coated with binding ligands and subject to a slow, homogeneous shear flow in a viscous, ionic fluid medium. The binding ligands on the surface of the cells experience both attractive and repulsive forces in an ionic medium and exhibit finite resistance to rotation via bond tilting. The microscale drag forces and couples describing the fluid flow inside the small separation gap between the cells, are calculated using a combination of methods in lubrication theory and previously published numerical results. For a selected range of material and fluid parameters, a hysteretic transition of the sticking probability curves (i.e., the function [Formula: see text]) between the adhesion phase (when [Formula: see text]) and the fragmentation phase (when [Formula: see text]) is attributed to a nonlinear relation between the total nanoscale binding forces and the separation gap between the cells. We show that adhesion is favoured in highly ionic fluids, increased deformability of the cells, elastic binders and a higher fluid shear rate (until a critical threshold value of shear rate is reached). Within a selected range of critical shear rates, the continuation of the limit points (i.e., the turning points where the slope of [Formula: see text] changes sign) predict a bistable region, indicating an abrupt switching between the adhesion and the fragmentation regimes. Although, bistability in the adhesion-fragmentation phase diagram of two deformable, charged cells immersed in an ionic aqueous environment has been identified by some in vitro experiments, but until now, has not been quantified theoretically.

[Diagnostic Significance of BAT in Anaphylaxis to Non-ionic Contrast Media].

PubMed

Zhang, Hao-yue; Xu, Su-jun; Tang, Xiao-xian; Niu, Ji-jun; Guo, Xiang-jie; Gao, Cai-rong

2015-06-01

To investigate the diagnostic significance of basophil activation test (BAT) in anaphylaxis to non-ionic contrast media through testing the content of CD63, mast cell-carboxypeptidase A3 (MC-CPA3), and terminal complement complex SC5b-9 of the individuals by testing their levels in the normal immune group and the anaphylaxis groups to β-lactam drugs and non -ionic contrast media. The CD63 expression of basophilic granulocyte in blood was detected by flow cytometry. The levels of MC-CPA3 in blood serum and SC5b-9 in blood plasma were detected by ELISA. The CD63 expression of basophilic granulocyte in blood, the levels of MC-CPA3 and SC5b-9 of anaphylaxis to non-ionic contrast media and β-lactam drugs were significantly higher than that in normal immune group (P < 0.05). There is activation of basophilic granulocytes, mast cells and complement system in anaphylaxis to non-ionic contrast media. BAT can be used to diagnose the anaphylaxis to non-ionic contrast media.

Colloid Mobilization in a Fractured Soil: Effect of Pore-Water Exchange between Preferential Flow Paths and Soil Matrix.

PubMed

Mohanty, Sanjay K; Saiers, James E; Ryan, Joseph N

2016-03-01

Exchange of water and solutes between contaminated soil matrix and bulk solution in preferential flow paths has been shown to contribute to the long-term release of dissolved contaminants in the subsurface, but whether and how this exchange can affect the release of colloids in a soil are unclear. To examine this, we applied rainfall solutions of different ionic strength on an intact soil core and compared the resulting changes in effluent colloid concentration through multiple sampling ports. The exchange of water between soil matrix and the preferential flow paths leading to each port was characterized on the basis of the bromide (conservative tracer) breakthrough time at the port. At individual ports, two rainfalls of a certain ionic strength mobilized different amounts of colloids when the soil was pre-exposed to a solution of lower or higher ionic strength. This result indicates that colloid mobilization depended on rainfall solution history, which is referred as colloid mobilization hysteresis. The extent of hysteresis was increased with increases in exchange of pore water and solutes between preferential flow paths and matrix. The results indicate that the soil matrix exchanged the old water from the previous infiltration with new infiltrating water during successive infiltration and changed the pore water chemistry in the preferential flow paths, which in turn affected the release of soil colloids. Therefore, rainfall solution history and soil heterogeneity must be considered to assess colloid mobilization in the subsurface. These findings have implications for the release of colloids, colloid-associated contaminants, and pathogens from soils.

Soft but Powerful Artificial Muscles Based on 3D Graphene-CNT-Ni Heteronanostructures.

PubMed

Kim, Jaehwan; Bae, Seok-Hu; Kotal, Moumita; Stalbaum, Tyler; Kim, Kwang J; Oh, Il-Kwon

2017-08-01

Bioinspired soft ionic actuators, which exhibit large strain and high durability under low input voltages, are regarded as prospective candidates for future soft electronics. However, due to the intrinsic drawback of weak blocking force, the feasible applications of soft ionic actuators are limited until now. An electroactive artificial muscle electro-chemomechanically reinforced with 3D graphene-carbon nanotube-nickel heteronanostructures (G-CNT-Ni) to improve blocking force and bending deformation of the ionic actuators is demonstrated. The G-CNT-Ni heteronanostructure, which provides an electrically conductive 3D network and sufficient contact area with mobile ions in the polymer electrolyte, is embedded as a nanofiller in both ionic polymer and conductive electrodes of the ionic actuators. An ionic exchangeable composite membrane consisting of Nafion, G-CNT-Ni and ionic liquid (IL) shows improved tensile modulus and strength of up to 166% and 98%, respectively, and increased ionic conductivity of 0.254 S m -1 . The ionic actuator exhibits enhanced actuation performances including three times larger bending deformation, 2.37 times higher blocking force, and 4 h durability. The electroactive artificial muscle electro-chemomechanically reinforced with 3D G-CNT-Ni heteronanostructures offers improvements over current soft ionic actuator technologies and can advance the practical engineering applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Influence of Magnetic Field on Electrokinetic Potential of Colloidal Particles

NASA Astrophysics Data System (ADS)

Koshoridze, S. I.; Levin, Yu. K.

2018-06-01

The influence of a magnetic field on the electrokinetic potential of colloidal particles in a water flow oversaturated with deposited salts is reported. For the first time, the ionic hydration and dielectric permittivity of water in the double electrical layer are taken into consideration. It is demonstrated that the magnetic field influence is increased with the decreasing dielectric permittivity of water but is decreased due to ionic hydration.

Electroosmotic flow and ionic conductance in a pH-regulated rectangular nanochannel

NASA Astrophysics Data System (ADS)

Sadeghi, Morteza; Saidi, Mohammad Hassan; Sadeghi, Arman

2017-06-01

Infinite series solutions are obtained for electrical potential, electroosmotic velocity, ionic conductance, and surface physicochemical properties of long pH-regulated rectangular nanochannels of low surface potential utilizing the double finite Fourier transform method. Closed form expressions are also obtained for channels of large height to width ratio for which the depthwise variations vanish. Neglecting the Stern layer impact, the effects of EDL (Electric Double Layer) overlap, multiple ionic species, and association/dissociation reactions on the surface are all taken into account. Moreover, finite-element-based numerical simulations are conducted to account for the end effects as well as to validate the analytical solutions. We show that, with the exception of the migratory ionic conductivity, all the physicochemical parameters are strong functions of the channel aspect ratio. Accordingly, a slit geometry is not a good representative of a rectangular channel when the width is comparable to the height. It is also observed that the distribution of the electrical potential is not uniform over the surface of a charge-regulated channel. In addition, unlike ordinary channels for which an increase in the background salt concentration is always accompanied by higher flow rates, quite the opposite may be true for a pH-regulated duct at higher salt concentrations.

Molecular dynamics simulation of low dielectric constant polymer electrolytes

NASA Astrophysics Data System (ADS)

Wheatle, Bill; Lynd, Nathaniel; Ganesan, Venkat

Recent experimental studies measured the ionic conductivities of a series of poly(glycidyl ether)s with varying neat dielectric constants (ɛ), viscosities (η), and glass transition temperatures (Tg), as hosts for lithium bistrifluoromethanesulfonimide (LiTFSI) salt. In such a context, it was demonstrated that the ionic conductivity of these polymer electrolytes was a function of ɛ rather than Tg or η, suggesting that there may exist regimes in which ionic conductivity is not limited by slow segmental dynamics but rather by low ionic dissociation. Motivated by such results, we used atomistic molecular dynamics to study the structure and transport characteristics of the same set of host polymers. We found that the coordination number of TFSI- about Li+ in the first solvation shell and the total fraction of free ions increased as a function of ɛ, implying the polymer hosts enhanced ion dissociation. In addition, we found that increasing the dielectric constant of the host polymer enhanced self-correlated ion transport, as evidenced by an increase in the diffusion coefficients of each ion species. Overall, we confirmed that limited ion dissociation in low- ɛ polymer electrolyte hosts hampers ionic conductivity. We would like to thank the National Science Foundation Graduate Research Fellowship Program for funding this research endeavor.

Total arsenic and selenium analysis in Marcellus shale, high-salinity water, and hydrofracture flowback wastewater.

PubMed

Balaba, Ronald S; Smart, Ronald B

2012-11-01

Trace levels of arsenic and selenium can be toxic to living organisms yet their quantitation in high ionic strength or high salinity aqueous media is difficult due to the matrix interferences which can either suppress or enhance the analyte signal. A modified thiol cotton fiber (TCF) method employing lower flow rates and centrifugation has been used to remove the analyte from complex aqueous media and minimize the matrix interferences. This method has been tested using a USGS (SGR-1b) certified reference shale. It has been used to analyze Marcellus shale samples following microwave digestion as well as spiked samples of high salinity water (HSW) and flow back wastewater (WRF6) obtained from an actual gas well drilling operation. Quantitation of arsenic and selenium is carried out by graphite furnace atomic spectroscopy (GFAAS). Extraction of arsenic and selenium from Marcellus shale exposed to HSW and WRF6 for varying lengths of time is also reported. Copyright © 2012 Elsevier Ltd. All rights reserved.

Gadolinium-enhanced MR images of the growing piglet skeleton: ionic versus nonionic contrast agent.

PubMed

Menezes, Nina M; Olear, Elizabeth A; Li, Xiaoming; Connolly, Susan A; Zurakowski, David; Foley, Mary; Shapiro, Frederic; Jaramillo, Diego

2006-05-01

To determine whether there are differences in the distribution of ionic and nonionic gadolinium-based contrast agents by evaluating contrast enhancement of the physis, epiphyseal cartilage, secondary ossification center, and metaphysis in the knees of normal piglets. Following approval from the Subcommittee on Research Animal Care, knees of 12 3-week-old piglets were imaged at 3-T magnetic resonance (MR) imaging after intravenous injection of gadoteridol (nonionic contrast agent; n = 6) or gadopentetate dimeglumine (ionic contrast agent; n = 6). Early enhancement evaluation with gradient-echo MR imaging was quantified and compared (Student t test) by means of enhancement ratios. Distribution of contrast material was assessed and compared (Student t test) by means of T1 measurements obtained before and at three 15-minute intervals after contrast agent administration. The relative visibility of the physis, epiphyseal cartilage, secondary ossification center, and metaphysis was qualitatively assessed by two observers and compared (Wilcoxon signed rank test). Differences in matrix content and cellularity that might explain the imaging findings were studied at histologic evaluation. Enhancement ratios were significantly higher for gadoteridol than for gadopentetate dimeglumine in the physis, epiphyseal cartilage, and secondary ossification center (P < .05). After contrast agent administration, T1 values decreased sharply for both agents-but more so for gadoteridol. Additionally, there was less variability in T1 values across structures with this contrast agent. Gadoteridol resulted in greater visibility of the physis, while gadopentetate dimeglumine resulted in greater contrast between the physis and metaphysis (P < .05). The results suggest different roles for the two gadolinium-based contrast agents: The nonionic contrast medium is better suited for evaluating perfusion and anatomic definition in the immature skeleton, while the ionic contrast medium is better for evaluating cartilage fixed-charge density. (c) RSNA, 2006.

Thermophysical Properties of Nanoparticle-Enhanced Ionic Liquids (NEILs) Heat-Transfer Fluids

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

Fox, Elise B.; Visser, Ann E.; Bridges, Nicholas J.

2013-06-20

An experimental investigation was completed on nanoparticle enhanced ionic liquid heat transfer fluids as an alternative to conventional organic based heat transfer fluids (HTFs). These nanoparticle-based HTFs have the potential to deliver higher thermal conductivity than the base fluid without a significant increase in viscosity at elevated temperatures. The effect of nanoparticle morphology and chemistry on thermophysical properties was examined. Whisker shaped nanomaterials were found to have the largest thermal conductivity temperature dependence and were also less likely to agglomerate in the base fluid than spherical shaped nanomaterials.

Dissection of the Voltage Losses of an Acidic Quinone Redox Flow Battery

DOE PAGES

Chen, Qing; Gerhardt, Michael R.; Aziz, Michael J.

2017-03-28

We measure the polarization characteristics of a quinone-bromide redox flow battery with interdigitated flow fields, using electrochemical impedance spectroscopy and voltammetry of a full cell and of a half cell against a reference electrode. We find linear polarization behavior at 50% state of charge all the way to the short-circuit current density of 2.5 A/cm 2. We uniquely identify the polarization area-specific resistance (ASR) of each electrode, the membrane ASR to ionic current, and the electronic contact ASR. We use voltage probes to deduce the electronic current density through each sheet of carbon paper in the quinone-bearing electrode. By alsomore » interpreting the results using the Newman 1-D porous electrode model, we deduce the volumetric exchange current density of the porous electrode. We uniquely evaluate the power dissipation and identify a correspondence to the contributions to the electrode ASR from the faradaic, electronic, and ionic transport processes. We find that, within the electrode, more power is dissipated in the faradaic process than in the electronic and ionic conduction processes combined, despite the observed linear polarization behavior. We examine the sensitivity of the ASR to the values of the model parameters. The greatest performance improvement is anticipated from increasing the volumetric exchange current density.« less

Combining autohydrolysis and ionic liquid microwave treatment to enhance enzymatic hydrolysis of Eucalyptus globulus wood.

PubMed

Rigual, Victoria; Santos, Tamara M; Domínguez, Juan Carlos; Alonso, M Virginia; Oliet, Mercedes; Rodriguez, Francisco

2018-03-01

The combination of autohydrolysis and ionic liquid microwave treatments of eucalyptus wood have been studied to facilitate sugar production in a subsequent enzymatic hydrolysis step. Three autohydrolysis conditions (150 °C, 175 °C and 200 °C) in combination with two ionic liquid temperatures (80 °C and 120 °C) were compared in terms of chemical composition, enzymatic digestibility and sugar production. Morphology was measured (using SEM) and the biomass surface was visualized with confocal fluorescence microscopy. The synergistic cooperation of both treatments was demonstrated, enhancing cellulose accessibility. At intermediate autohydrolysis conditions (175 °C) and low ionic liquid temperature (80 °C), a glucan digestibility of 84.4% was obtained. Using SEM micrographs, fractal dimension (as a measure of biomass complexity) and lacunarity (as a measure of homogeneity) were calculated before and after pretreatment. High fractals dimensions and low lacunarities correspond to morphologically complex and homogeneous samples, that are better digested by enzyme cocktails. Copyright © 2017 Elsevier Ltd. All rights reserved.

Strain tuning and strong enhancement of ionic conductivity in SrZrO 3-RE 2O 3 (RE = Sm, Eu, Gd, Dy, and Er) nanocomposite films

DOE PAGES

Lee, Shinbuhm; Zhang, Wenrui; Khatkhatay, Fauzia; ...

2015-06-05

Fast ion transport channels at interfaces in thin films have attracted great attention due to a range of potential applications for energy materials and devices, for, solid oxide fuel cells, sensors, and memories. Here, it is shown that in vertical nanocomposite heteroepitaxial films of SrZrO 3–RE 2O 3 (RE = Sm, Eu, Gd, Dy, and Er) the ionic conductivity of the composite can be tuned and strongly enhanced using embedded, stiff, and vertical nanopillars of RE 2O 3. With increasing lattice constant of RE 2O 3 from Er 2O 3 to Sm 2O 3, it is found that the tensilemore » strain in the SrZrO 3 increases proportionately, and the ionic conductivity of the composite increases accordingly, by an order of magnitude. Lastly, the results here conclusively show, for the first time, that strain in films can be effectively used to tune the ionic conductivity of the materials.« less

Disorder-induced transition from grain boundary to bulk dominated ionic diffusion in pyrochlores

DOE PAGES

Perriot, Romain; Dholabhai, Pratik P.; Uberuaga, Blas P.

2017-05-04

In this paper, we use molecular dynamics simulations to investigate the role of grain boundaries (GBs) on ionic diffusion in pyrochlores, as a function of the GB type, chemistry of the compound, and level of cation disorder. We observe that the presence of GBs promotes oxygen transport in ordered and low-disordered systems, as the GBs are found to have a higher concentration of mobile carriers with higher mobilities than in the bulk. Thus, in ordered samples, the ionic diffusion is 2D, localized along the grain boundary. When cation disorder is introduced, bulk carriers begin to contribute to the overall diffusion,more » while the GB contribution is only slightly enhanced. In highly disordered samples, the diffusive behavior at the GBs is bulk-like, and the two contributions (bulk vs. GB) can no longer be distinguished. There is thus a transition from 2D/GB dominated oxygen diffusivity to 3D/bulk dominated diffusivity versus disorder in pyrochlores. Finally, these results provide new insights into the possibility of using internal interfaces to enhance ionic conductivity in nanostructured complex oxides.« less

Fluidic nanotubes and devices

DOEpatents

Yang, Peidong [Berkeley, CA; He, Rongrui [El Cerrito, CA; Goldberger, Joshua [Berkeley, CA; Fan, Rong [El Cerrito, CA; Wu, Yiying [Albany, CA; Li, Deyu [Albany, CA; Majumdar, Arun [Orinda, CA

2008-04-08

Fluidic nanotube devices are described in which a hydrophilic, non-carbon nanotube, has its ends fluidly coupled to reservoirs. Source and drain contacts are connected to opposing ends of the nanotube, or within each reservoir near the opening of the nanotube. The passage of molecular species can be sensed by measuring current flow (source-drain, ionic, or combination). The tube interior can be functionalized by joining binding molecules so that different molecular species can be sensed by detecting current changes. The nanotube may be a semiconductor, wherein a tubular transistor is formed. A gate electrode can be attached between source and drain to control current flow and ionic flow. By way of example an electrophoretic array embodiment is described, integrating MEMs switches. A variety of applications are described, such as: nanopores, nanocapillary devices, nanoelectrophoretic, DNA sequence detectors, immunosensors, thermoelectric devices, photonic devices, nanoscale fluidic bioseparators, imaging devices, and so forth.

Fluidic nanotubes and devices

DOEpatents

Yang, Peidong; He, Rongrui; Goldberger, Joshua; Fan, Rong; Wu, Yiying; Li, Deyu; Majumdar, Arun

2010-01-10

Fluidic nanotube devices are described in which a hydrophilic, non-carbon nanotube, has its ends fluidly coupled to reservoirs. Source and drain contacts are connected to opposing ends of the nanotube, or within each reservoir near the opening of the nanotube. The passage of molecular species can be sensed by measuring current flow (source-drain, ionic, or combination). The tube interior can be functionalized by joining binding molecules so that different molecular species can be sensed by detecting current changes. The nanotube may be a semiconductor, wherein a tubular transistor is formed. A gate electrode can be attached between source and drain to control current flow and ionic flow. By way of example an electrophoretic array embodiment is described, integrating MEMs switches. A variety of applications are described, such as: nanopores, nanocapillary devices, nanoelectrophoretic, DNA sequence detectors, immunosensors, thermoelectric devices, photonic devices, nanoscale fluidic bioseparators, imaging devices, and so forth.

Lithium-Based High Energy Density Flow Batteries

NASA Technical Reports Server (NTRS)

Bugga, Ratnakumar V. (Inventor); West, William C. (Inventor); Kindler, Andrew (Inventor); Smart, Marshall C. (Inventor)

2014-01-01

Systems and methods in accordance with embodiments of the invention implement a lithium-based high energy density flow battery. In one embodiment, a lithium-based high energy density flow battery includes a first anodic conductive solution that includes a lithium polyaromatic hydrocarbon complex dissolved in a solvent, a second cathodic conductive solution that includes a cathodic complex dissolved in a solvent, a solid lithium ion conductor disposed so as to separate the first solution from the second solution, such that the first conductive solution, the second conductive solution, and the solid lithium ionic conductor define a circuit, where when the circuit is closed, lithium from the lithium polyaromatic hydrocarbon complex in the first conductive solution dissociates from the lithium polyaromatic hydrocarbon complex, migrates through the solid lithium ionic conductor, and associates with the cathodic complex of the second conductive solution, and a current is generated.

Measurement of the Structure and Molecular Dynamics of Ionic Solutions for Redox Flow Battery

NASA Astrophysics Data System (ADS)

Li, Zhixia; Robertson, Lily; Moore, Jeffery; Zhang, Yang

Redox flow battery (RFB) is a promising electrical energy storage technology with great potential to finally realize alternative energy sources for the next-generation vehicles and at grid scales. The design of RFB is unique as the power scales separately from the energy capacity. The latter depends on the size of storage tanks and the concentration of the active materials. Redox-active organic molecules are excellent candidates with high synthetic tunability for both redox properties as well as, importantly, solubility. However, upon increasing concentrations, the flow cell has less cycling stability and more capacity fade. Further, after charging the battery, the viscosity increases while the ionic conductivity decreases, and thus the cell becomes overall ineffective. To understand the mechanism of the increased viscosity, we performed differential scanning calorimetry, wide and small angle X-rays scattering, and quasi-elastic neutron scattering measurements. Herein, we will present the measurement results and relative analysis.

Impact of Carrier Fluid Composition on Recovery of Nanoparticles and Proteins in Flow Field Flow Fractionation

PubMed Central

Schachermeyer, Samantha; Ashby, Jonathan; Kwon, MinJung; Zhong, Wenwan

2012-01-01

Flow field flow fractionation (F4) is an invaluable separation tool for large analytes, including nanoparticles and biomolecule complexes. However, sample loss due to analyte-channel membrane interaction limits extensive usage of F4 at present, which could be strongly affected by the carrier fluid composition. This work studied the impacts of carrier fluid (CF) composition on nanoparticle (NP) recovery in F4, with focus on high ionic strength conditions. Successful analysis of NPs in a biomolecules-friendly environment could expand the applicability of F4 to the developing field of nanobiotechnology. Recovery of the unfunctionalized polystyrene NPs of 199-, 102-, and 45-nm in CFs with various pH (6.2, 7.4 and 8.2), increasing ionic strength (0–0.1 M), and different types of co- and counter-ions, were investigated. Additionally, elution of the 85-nm carboxylate NPs and two proteins, human serum albumin (HSA) and immunoglobulin (IgG), at high ionic strengths (0–0.15 M) was investigated. Our results suggested that; 1) Electrostatic repulsion between the negatively charged NPs and the regenerated cellulose membrane was the main force to avoid particle adsorption on the membrane; 2) Larger particles experienced higher attractive force and thus were influenced more by variation in CF composition; and 3) Buffers containing weak anions or NPs with weak anion as the surface functional groups provided higher tolerance to the increase in ionic strength, owing to more anions being trapped inside the NP porous structure. Protein adsorption onto the membrane was also briefly investigated in salted CFs, using human serum albumin and immunoglobulin. We believe our findings could help to identify the basic carrier fluid composition for higher sample recovery in F4 analysis of nanoparticles in a protein-friendly environment, which will be useful for applying F4 in bioassays and in nanotoxicology studies. PMID:23058938

Enhanced photoluminescence from single nitrogen-vacancy defects in nanodiamonds coated with phenol-ionic complexes.

PubMed

Bray, Kerem; Previdi, Rodolfo; Gibson, Brant C; Shimoni, Olga; Aharonovich, Igor

2015-03-21

Fluorescent nanodiamonds are attracting major attention in the field of bio-sensing and bio-labeling. In this work we demonstrate a robust approach to achieve an encapsulation of individual nanodiamonds with phenol-ionic complexes that enhance the photoluminescence from single nitrogen vacancy (NV) centers. We show that single NV centres in the coated nanodiamonds also exhibit shorter lifetimes, opening another channel for high resolution sensing. We propose that the nanodiamond encapsulation reduces the non-radiative decay pathways of the NV color centers. Our results provide a versatile and assessable way to enhance photoluminescence from nanodiamond defects that can be used in a variety of sensing and imaging applications.

Enhanced pearl-chain formation by electrokinetic interaction with the bottom surface of vessel.

PubMed

Nishimura, Satoshi; Matsumura, Hideo; Kosuge, Katsunori; Yamaguchi, Tomohiko

2007-08-14

Counterions in an electric double layer (EDL) around a colloidal particle accumulate on one side of the EDL and are deficient on the other side under an electric field, resulting in an imbalance of ionic concentration in the EDL, that is to say, the ionic polarization of EDL. It is well known that the ionic polarization of EDL induces electric dipole moments whereby the alignments of colloidal particles (e.g., pearl chains) are formed under alternating electric fields. In this study, we focus on the effect of the frequency of applied electric fields (100 Hz-1 kHz) on the alignment of silica particles settling at the bottom of a silica glass vessel. In digital imaging analyses for pearl chains of silica particles, it is confirmed that surface distances between two neighboring particles decrease but the number of particles in a pearl chain increases as the frequency of the applied electric field is lowered from 1 kHz to 100 Hz. More interestingly, electrical conductance measurements suggest that the induced ionic polarization of EDL around silica particles at the bottom of the silica vessel is enhanced as the frequency is lowered from 1 kHz to 100 Hz, whereas the ionic polarization around isolated silica particles in uniform dispersions is alleviated by the relaxation of ionic concentration in the EDL as a result of the diffusion of counterions. This curious phenomenon can be explained by considering that the ionic polarization of EDL of silica particles at the bottom of a vessel is affected by the electro-osmosis of the silica surface at the bottom of the vessel.

Dysprosium electrodeposition from a hexaalkylguanidinium-based ionic liquid.

PubMed

Berger, Claudia A; Arkhipova, Maria; Maas, Gerhard; Jacob, Timo

2016-08-07

The rare-earth element dysprosium (Dy) is an important additive that increases the magnetocrystalline anisotropy of neodymium magnets and additionally prevents from demagnetizing at high temperatures. Therefore, it is one of the most important elements for high-tech industries and is mainly used in permanent magnetic applications, for example in electric vehicles, industrial motors and direct-drive wind turbines. In an effort to develop a more efficient electrochemical technique for depositing Dy on Nd-magnets in contrast to commonly used costly physical vapor deposition, we investigated the electrochemical behavior of dysprosium(iii) trifluoromethanesulfonate in a custom-made guanidinium-based room-temperature ionic liquid (RTIL). We first examined the electrodeposition of Dy on an Au(111) model electrode. The investigation was carried out by means of cyclic voltammetry (CV) and X-ray photoelectron spectroscopy (XPS). The initial stages of metal deposition were followed by in situ scanning tunneling microscopy (STM). CV measurements revealed a large cathodic reduction peak, which corresponds to the growth of monoatomic high islands, based on STM images taken during the initial stages of deposition. XPS identified these deposited islands as dysprosium. A similar reduction peak was also observed on an Nd-Fe-B substrate, and positively identified as deposited Dy using XPS. Finally, we varied the concentration of the Dy precursor, electrolyte flow and temperature during Dy deposition and demonstrated that each of these parameters could be used to increase the thickness of the Dy deposit, suggesting that these parameters could be tuned simultaneously in a temperature-controlled flow cell to enhance the thickness of the Dy layer.

β-cyclodextrin-ionic liquid polymer based dynamically coating for simultaneous determination of tetracyclines by capillary electrophoresis.

PubMed

Zhou, Chunyan; Deng, Jingjing; Shi, Guoyue; Zhou, Tianshu

2017-04-01

Tetracyclines are a group of broad spectrum antibiotics widely used in animal husbandry to prevent and treat diseases. However, the improper use of tetracyclines may result in the presence of their residues in animal tissues or waste. Recently, great attention has been drawn towards the green solvents ionic liquids. Ionic liquids have been employed as a coating material to modify the electroosmotic flow in capillary electrophoresis. In this study, a functionalized ionic liquid, mono-6-deoxy-6-(3-methylimidazolium)-β-cyclodextrin tosylate, was synthesized and used for the simultaneous separation and quantification of tetracyclines by capillary electrophoresis. Good separation efficiency could be achieved due to the multiple functions of β-cyclodextrin derived ionic liquid, including the electrostatic interaction, the hydrogen bonding, and the cavity structure in β-cyclodextrin ionic liquid which can entrap the tetracyclines to form inclusion complex. After optimization, baseline separation achieved in 25 min with the running buffer consisted of 10 mmol/L, pH 7.2 phosphate buffer and 20 mmol/L β-cyclodextrin ionic liquid. The satisfied result demonstrated that the β-cyclodextrin ionic liquid is an ideal background electrolyte modifier in the separation of tetracyclines with high stability and good reproducibility. And it is an effective strategy to design and synthesize specific ILs as additive applied in separation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Impurity effects on ionic-liquid-based supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Kun; Lian, Cheng; Henderson, Douglas; Wu, Jianzhong

2017-02-01

Small amounts of an impurity may affect the key properties of an ionic liquid and such effects can be dramatically amplified when the electrolyte is under confinement. Here the classical density functional theory is employed to investigate the impurity effects on the microscopic structure and the performance of ionic-liquid-based electrical double-layer capacitors, also known as supercapacitors. Using a primitive model for ionic species, we study the effects of an impurity on the double layer structure and the integral capacitance of a room temperature ionic liquid in model electrode pores and find that an impurity strongly binding to the surface of a porous electrode can significantly alter the electric double layer structure and dampen the oscillatory dependence of the capacitance with the pore size of the electrode. Meanwhile, a strong affinity of the impurity with the ionic species affects the dependence of the integral capacitance on the pore size. Up to 30% increase in the integral capacitance can be achieved even at a very low impurity bulk concentration. By comparing with an ionic liquid mixture containing modified ionic species, we find that the cooperative effect of the bounded impurities is mainly responsible for the significant enhancement of the supercapacitor performance.

Microchip electrophoresis of oligosaccharides using large-volume sample stacking with an electroosmotic flow pump in a single channel.

PubMed

Kawai, Takayuki; Sueyoshi, Kenji; Kitagawa, Fumihiko; Otsuka, Koji

2010-08-01

The applicability of an online preconcentration technique, large-volume sample stacking with an electroosmotic flow pump (LVSEP), to microchip zone electrophoresis (MCZE) for the analysis of oligosaccharides was investigated. Since the sample stacking and separation proceeded continuously without polarity switching in LVSEP, a single "straight" channel microchip could be employed. In the MCZE analysis of oligosaccharides, sample adsorption onto the channel surface should be suppressed, so the straight microchannel was modified with poly(vinyl alcohol) (PVA). So far, the mechanism of LVSEP in the polymer-coated capillary or microchannel has not been reported, and thus, the LVSEP process in the PVA-coated channel was investigated by fluorescence imaging. Although it is well-known that the PVA coating can suppress the electroosmotic flow (EOF), an enhanced EOF with a mobility of 4.4 x 10(-4) cm(2)/(V x s) was observed in a low ionic strength sample solution. It was revealed that such temporarily enhanced EOF in the sample zone worked as the driving force to remove the sample matrix in LVSEP. To evaluate the analytical performance of LVSEP-MCZE, oligosaccharides were analyzed in the PVA-coated straight channel. As a result, both the glucose ladder and oligosaccharides obtained from bovine ribonuclease B were well enriched and separated with up to 2200-2900-fold sensitivity enhancement compared to those in a conventional MCZE analysis. The run-to-run repeatabilities of the migration time and peak height were good with relative standard deviations of 1.1% and 7.2%, respectively, which were better than those of normal MCZE. By applying the LVSEP technique to MCZE, a complicated voltage program for fluidic control could be simplified from four channels for two steps to two channels for one step.

The effects of high concentrations of ionic liquid on GB1 protein structure and dynamics probed by high-resolution magic-angle-spinning NMR spectroscopy.

PubMed

Warner, Lisa; Gjersing, Erica; Follett, Shelby E; Elliott, K Wade; Dzyuba, Sergei V; Varga, Krisztina

2016-12-01

Ionic liquids have great potential in biological applications and biocatalysis, as some ionic liquids can stabilize proteins and enhance enzyme activity, while others have the opposite effect. However, on the molecular level, probing ionic liquid interactions with proteins, especially in solutions containing high concentration of ionic liquids, has been challenging. In the present work the 13 C, 15 N-enriched GB1 model protein was used to demonstrate applicability of high-resolution magic-angle-spinning (HR-MAS) NMR spectroscopy to investigate ionic liquid - protein interactions. Effect of an ionic liquid (1-butyl-3-methylimidazolium bromide, [C 4 -mim]Br) on GB1was studied over a wide range of the ionic liquid concentrations (0.6 to 3.5 M, which corresponds to 10%-60% v/v). Interactions between GB1 and [C 4 -mim]Br were observed from changes in the chemical shifts of the protein backbone as well as the changes in 15 N ps-ns dynamics and rotational correlation times. Site-specific interactions between the protein and [C 4 -mim]Br were assigned using 3D methods under HR-MAS conditions. Thus, HR-MAS NMR is a viable tool that could aid in elucidation of the molecular mechanism of ionic liquid - protein interactions.

Distributed flow estimation and closed-loop control of an underwater vehicle with a multi-modal artificial lateral line.

PubMed

DeVries, Levi; Lagor, Francis D; Lei, Hong; Tan, Xiaobo; Paley, Derek A

2015-03-25

Bio-inspired sensing modalities enhance the ability of autonomous vehicles to characterize and respond to their environment. This paper concerns the lateral line of cartilaginous and bony fish, which is sensitive to fluid motion and allows fish to sense oncoming flow and the presence of walls or obstacles. The lateral line consists of two types of sensing modalities: canal neuromasts measure approximate pressure gradients, whereas superficial neuromasts measure local flow velocities. By employing an artificial lateral line, the performance of underwater sensing and navigation strategies is improved in dark, cluttered, or murky environments where traditional sensing modalities may be hindered. This paper presents estimation and control strategies enabling an airfoil-shaped unmanned underwater vehicle to assimilate measurements from a bio-inspired, multi-modal artificial lateral line and estimate flow properties for feedback control. We utilize potential flow theory to model the fluid flow past a foil in a uniform flow and in the presence of an upstream obstacle. We derive theoretically justified nonlinear estimation strategies to estimate the free stream flowspeed, angle of attack, and the relative position of an upstream obstacle. The feedback control strategy uses the estimated flow properties to execute bio-inspired behaviors including rheotaxis (the tendency of fish to orient upstream) and station-holding (the tendency of fish to position behind an upstream obstacle). A robotic prototype outfitted with a multi-modal artificial lateral line composed of ionic polymer metal composite and embedded pressure sensors experimentally demonstrates the distributed flow sensing and closed-loop control strategies.

Ionic liquid-assisted photochemical synthesis of ZnO/Ag2O heterostructures with enhanced visible light photocatalytic activity

NASA Astrophysics Data System (ADS)

Zhao, Shuo; Zhang, Yiwei; Zhou, Yuming; Zhang, Chao; Fang, Jiasheng; Sheng, Xiaoli

2017-07-01

ZnO/Ag2O heterostructures have been successfully fabricated using ionic liquids (ILs) as templates by a simple photochemical route. The influence of the type of ionic liquid and synthetic method on the morphology of ZnO, as well as the photocatalytic activity for the degradation of Rhodamine B (RhB), tetracycline (TC) and ciprofloxacin (CIP) under ultraviolet and visible light irradiation was studied. The samples were characterized by XRD, SEM, TEM, PL and UV-vis DRS. The results established that the type of ionic liquid and synthetic method played an important role in the growth of ZnO nanoparticles. And as-fabricated ZnO/Ag2O materials exhibited self-assembled flower-like architecture whose size was about 3 μm. Moreover, as-prepared ZnO/Ag2O exhibited the enhanced photocatalytic activity than ZnO sample, which may be due to the special structure, heterojunction, enhanced adsorption capability of dye, the improved separation rate of photogenerated electron-hole pairs. According to the results of radical trapping experiments, it can be found that •OH and h+ were the main active species for the photocatalytic degradation of RhB. It is valuable to develop this facile route preparing the highly dispersive flower-like ZnO/Ag2O materials, which can be beneficial for environmental protection.

Structural manipulation approaches towards enhanced sodium ionic conductivity in Na-rich antiperovskites

DOE PAGES

Wang, Yonggang; Wang, Qingfei; Liu, Zhenpu; ...

2015-06-10

High-performance solid electrolytes are critical for realizing all-solid-state batteries with enhance safety and cycling efficiency. However, currently available candidates (sulfides and the NASICON-typ ceramics) still suffer from drawbacks such as inflammability, high-cost and unfavorable machinability Here we present the structural manipulation approaches to improve the sodium ionic conductivity in series of affordable Na-rich antiperovskites. Experimentally, the whole solid solutions of Na 3OX (X ¼ Cl Br, I) are synthesized via a facile and timesaving route from the cheapest raw materials (Na, NaOH an NaX). The materials are nonflammable, suitable for thermoplastic processing due to low melting temperature (<300° C) withoutmore » decomposing. Notably, owing to the flexibility of perovskite-type structure it's feasible to control the local structure features by means of size-mismatch substitution an unequivalent-doping for a favorable sodium ionic diffusion pathway. Enhancement of sodium ioni conductivity by 2 magnitudes is demonstrated by these chemical tuning methods. The optimized sodiu ionic conductivity in Na 2.9Sr 0.05OBr 0.6I 0.4 bulk samples reaches 1.9 10 - 3 S/cm at 200° C and even highe at elevated temperature. Here, we believe further chemical tuning efforts on Na-rich antiperovskites wil promote their performance greatly for practical all-solid state battery applications.« less

Effect of nanochitosan and succinonitrile on the AC ionic conductivity of plasticized nanocomposite solid polymer electrolytes (PNCSPE)

NASA Astrophysics Data System (ADS)

Karuppasamy, K.; Vani, C. Vijil; Nichelson, A.; Balakumar, S.; Shajan, X. Sahaya

2013-06-01

In the present study, the filler chitosan was converted into nanochitosan by ionotropic gelation method. Plasticized nanocomposite solid polymer electrolytes (PNCSPE) composed of poly ethylene oxide as host polymer, LiBOB (lithium bis(oxalatoborate)) as salt, SN as plasticizer and nanochitosan as filler were prepared by membrane hot-press technique. Succinonitrile and nanochitosan incorporation in PEO-LiBOB matrix enhanced the room temperature ionic conductivity. The highest ionic conductivities were found to be in the order of 10-3.2 S/cm.

Dielectric Modulation of Ion Transport near Interfaces

NASA Astrophysics Data System (ADS)

Antila, Hanne S.; Luijten, Erik

2018-03-01

Ion mobility and ionic conductance in nanodevices are known to deviate from bulk behavior, a phenomenon often attributed to surface effects. We demonstrate that dielectric mismatch between the electrolyte and the surface can qualitatively alter ionic transport in a counterintuitive manner. Instead of following the polarization-induced modulation of the concentration profile, mobility is enhanced or reduced by changes in the ionic atmosphere near the interface and affected by a polarization force parallel to the surface. In addition to revealing this mechanism, we explore the effect of salt concentration and electrostatic coupling.

Preparation and characterization of nonaqueous proton-conducting membranes with protic ionic liquids.

PubMed

Lu, Fei; Gao, Xinpei; Yan, Xiaojun; Gao, Hejun; Shi, Lijuan; Jia, Han; Zheng, Liqiang

2013-08-14

Hybrid Nafion membranes were successfully fabricated by incorporating with protic imidazolium ionic liquids 1-(2-aminoethyl)-3-methylimidazolium chloride ([MimAE]Cl), 1-(2-hydroxylethyl)-3-methylimidazolium chloride ([MimHE]Cl), and 1-carboxylmethyl-3-methylimidazolium chloride ([MimCM]Cl) for high-temperature fuel cells. The composite membranes were characterized by impedance spectroscopy, small-angle X-ray scattering (SAXS), scanning electronic microscopy (SEM), and thermogravimetric analysis (TGA). The incorporated protic ionic liquids enhance the doping of phosphoric acid (PA) and result in a relatively high ionic conductivity. The Nafion/10 wt % [MimAE]Cl/PA composite membrane exhibits an ionic conductivity of 6.0 mS/cm at 130 °C without humidification. [MimAE]Cl can swell the Nafion matrix more homogeneously than [MimHE]Cl or [MimCM]Cl, which results in a better ionic conductivity. It is notable that the composite Nafion/IL/PA membranes have a better thermal stability than the pristine Nafion membranes.

Ionic electroactive polymer actuators as active microfluidic mixers

DOE PAGES

Meis, Catherine; Montazami, Reza; Hashemi, Nastaran

2015-11-06

On-chip sample processing is integral to the continued development of lab-on-a-chip devices for various applications. An active microfluidic mixer prototype is proposed using ionic electroactive polymer actuators (IEAPAs) as artificial cilia. A proof-of-concept experiment was performed in which the actuators were shown to produce localized flow pattern disruptions in the laminar flow regime. Suggestions for further engineering and optimization of a scaled-down, complete device are provided. Furthermore, the device in its current state of development necessitates further engineering, the use of IEAPAs addresses issues currently associated with the use of electromechanical actuators as active microfluidic mixers and may prove tomore » be a useful alternative to other similar materials.« less

On the chemical stabilities of ionic liquids.

PubMed

Sowmiah, Subbiah; Srinivasadesikan, Venkatesan; Tseng, Ming-Chung; Chu, Yen-Ho

2009-09-25

Ionic liquids are novel solvents of interest as greener alternatives to conventional organic solvents aimed at facilitating sustainable chemistry. As a consequence of their unusual physical properties, reusability, and eco-friendly nature, ionic liquids have attracted the attention of organic chemists. Numerous reports have revealed that many catalysts and reagents were supported in the ionic liquid phase, resulting in enhanced reactivity and selectivity in various important reaction transformations. However, synthetic chemists cannot ignore the stability data and intermolecular interactions, or even reactions that are directly applicable to organic reactions in ionic liquids. It is becoming evident from the increasing number of reports on use of ionic liquids as solvents, catalysts, and reagents in organic synthesis that they are not totally inert under many reaction conditions. While in some cases, their unexpected reactivity has proven fortuitously advantageous in others is has been a problem, it is imperative that when selecting an ionic liquid for a particular synthetic application, attention be paid to its compatibility with the reaction conditions. Even though, more than 200 room temperature ionic liquids are known, only a few reports have commented their effects on reaction mechanisms or rate/stability. Therefore, rather than attempting to give a comprehensive overview of ionic liquid chemistry, this review focuses on the non-innocent nature of ionic liquids, with a decided emphasis to clearly illuminate the ability of ionic liquids to affect the mechanistic aspects of some organic reactions thereby affecting and promoting the yield and selectivity.

Development of a Physiologically Based Computational Kidney Model to Describe the Renal Excretion of Hydrophilic Agents in Rats

PubMed Central

Niederalt, Christoph; Wendl, Thomas; Kuepfer, Lars; Claassen, Karina; Loosen, Roland; Willmann, Stefan; Lippert, Joerg; Schultze-Mosgau, Marcus; Winkler, Julia; Burghaus, Rolf; Bräutigam, Matthias; Pietsch, Hubertus; Lengsfeld, Philipp

2013-01-01

A physiologically based kidney model was developed to analyze the renal excretion and kidney exposure of hydrophilic agents, in particular contrast media, in rats. In order to study the influence of osmolality and viscosity changes, the model mechanistically represents urine concentration by water reabsorption in different segments of kidney tubules and viscosity dependent tubular fluid flow. The model was established using experimental data on the physiological steady state without administration of any contrast media or drugs. These data included the sodium and urea concentration gradient along the cortico-medullary axis, water reabsorption, urine flow, and sodium as well as urea urine concentrations for a normal hydration state. The model was evaluated by predicting the effects of mannitol and contrast media administration and comparing to experimental data on cortico-medullary concentration gradients, urine flow, urine viscosity, hydrostatic tubular pressures and single nephron glomerular filtration rate. Finally the model was used to analyze and compare typical examples of ionic and non-ionic monomeric as well as non-ionic dimeric contrast media with respect to their osmolality and viscosity. With the computational kidney model, urine flow depended mainly on osmolality, while osmolality and viscosity were important determinants for tubular hydrostatic pressure and kidney exposure. The low diuretic effect of dimeric contrast media in combination with their high intrinsic viscosity resulted in a high viscosity within the tubular fluid. In comparison to monomeric contrast media, this led to a higher increase in tubular pressure, to a reduction in glomerular filtration rate and tubular flow and to an increase in kidney exposure. The presented kidney model can be implemented into whole body physiologically based pharmacokinetic models and extended in order to simulate the renal excretion of lipophilic drugs which may also undergo active secretion and reabsorption. PMID:23355822

Formation of positively charged gold nanoparticle monolayers on silica sensors.

PubMed

Oćwieja, Magdalena; Maciejewska-Prończuk, Julia; Adamczyk, Zbigniew; Roman, Maciej

2017-09-01

Formation of positively charged gold nanoparticle monolayers on the Si/SiO 2 was studied under in situ conditions using quartz microbalance (QCM). The gold nanoparticles were synthesized in a chemical reduction method using sodium borohydride as reducing agent. Cysteamine hydrochloride was applied to generate a positive surface charge of nanoparticles. The micrographs obtained from transmission electron microscopy (TEM) revealed that the average size of nanoparticles was equal to 12±3nm. The stability of nanoparticle suspensions under controlled pH and ionic strength was determined by dynamic light scattering (DLS). The electrophoretic mobility measurements showed that the zeta potential of nanoparticles was positive, decreasing with ionic strength and pH from 56mV at pH 4.2 and I=10 -4 M to 22mV at pH 8.3 and I=3×10 -3 M. The surface enhanced Raman spectroscopy (SERS) confirmed chemisorption of cysteamine on nanoparticles and the contribution of amine moieties in the generation of nanoparticle charge. The influence of suspension concentration, ionic strength and flow rate on the kinetics of nanoparticle deposition on the sensors was quantitatively determined. It was confirmed that the deposition for the low coverage regime is governed by the bulk mass transfer that results in a linear increase of the coverage with time. The significant increase in the maximum coverage of gold monolayers with ionic strength was interpreted as due to the decreasing range of the electrostatic interactions among deposited particles. Moreover, the hydratation of formed monolayers, their structure and the stability were determined by the comparison of the QCM results with those obtained by AFM and SEM. The experimental data were adequately interpreted in terms of the extended random sequential adsorption (eRSA) model that considers the bulk and surface transfer steps in a rigorous way. The obtained results are useful for a facile fabrication of gold nanoparticle-based biosensors capable to bind target molecules via available amine moieties. Copyright © 2017 Elsevier Inc. All rights reserved.

Development of flame retardant cotton fabric based on ionic liquids via sol-gel technique.

NASA Astrophysics Data System (ADS)

Bentis, A.; Boukhriss, A.; Boyer, D.; Gmouh, S.

2017-10-01

In this study, flame retardant cotton fabrics were developed by the sol-gel method, in order to enhance their flame retardant proprieties. For this aim, seven sols were prepared using tetraethylorthosilicate (TEOS) and different ionic liquids (ILs) consist on pyridinium and Methylimidazolium cations with different anions such as: PF6-, CH3COO-, and Br-. Those sols were applied separately to the cotton fabrics by a pad-dry-cure process. The flame retardant properties of functionalized cotton fabrics before and after washing were determined by the vertical flame tests according to ISO6940:2004(F) standard. The effects of anions have been thoroughly investigated, aiming at the optimization of the targeted properties. Thermogravimetric and mechanical according to NF EN ISO 13934-1:2013standard, analyses have been also investigated. The results showed that flame retardancy, thermal stability and mechanical properties of treated fabrics were enhanced by using ionic liquids.

Ionic imbalance induced self-propulsion of liquid metals

PubMed Central

Zavabeti, Ali; Daeneke, Torben; Chrimes, Adam F.; O'Mullane, Anthony P.; Zhen Ou, Jian; Mitchell, Arnan; Khoshmanesh, Khashayar; Kalantar-zadeh, Kourosh

2016-01-01

Components with self-propelling abilities are important building blocks of small autonomous systems and the characteristics of liquid metals are capable of fulfilling self-propulsion criteria. To date, there has been no exploration regarding the effect of electrolyte ionic content surrounding a liquid metal for symmetry breaking that generates motion. Here we show the controlled actuation of liquid metal droplets using only the ionic properties of the aqueous electrolyte. We demonstrate that pH or ionic concentration gradients across a liquid metal droplet induce both deformation and surface Marangoni flow. We show that the Lippmann dominated deformation results in maximum velocity for the self-propulsion of liquid metal droplets and illustrate several key applications, which take advantage of such electrolyte-induced motion. With this finding, it is possible to conceive the propulsion of small entities that are constructed and controlled entirely with fluids, progressing towards more advanced soft systems. PMID:27488954

Ionic imbalance induced self-propulsion of liquid metals.

PubMed

Zavabeti, Ali; Daeneke, Torben; Chrimes, Adam F; O'Mullane, Anthony P; Zhen Ou, Jian; Mitchell, Arnan; Khoshmanesh, Khashayar; Kalantar-Zadeh, Kourosh

2016-08-04

Components with self-propelling abilities are important building blocks of small autonomous systems and the characteristics of liquid metals are capable of fulfilling self-propulsion criteria. To date, there has been no exploration regarding the effect of electrolyte ionic content surrounding a liquid metal for symmetry breaking that generates motion. Here we show the controlled actuation of liquid metal droplets using only the ionic properties of the aqueous electrolyte. We demonstrate that pH or ionic concentration gradients across a liquid metal droplet induce both deformation and surface Marangoni flow. We show that the Lippmann dominated deformation results in maximum velocity for the self-propulsion of liquid metal droplets and illustrate several key applications, which take advantage of such electrolyte-induced motion. With this finding, it is possible to conceive the propulsion of small entities that are constructed and controlled entirely with fluids, progressing towards more advanced soft systems.

Ionic imbalance induced self-propulsion of liquid metals

NASA Astrophysics Data System (ADS)

Zavabeti, Ali; Daeneke, Torben; Chrimes, Adam F.; O'Mullane, Anthony P.; Zhen Ou, Jian; Mitchell, Arnan; Khoshmanesh, Khashayar; Kalantar-Zadeh, Kourosh

2016-08-01

Components with self-propelling abilities are important building blocks of small autonomous systems and the characteristics of liquid metals are capable of fulfilling self-propulsion criteria. To date, there has been no exploration regarding the effect of electrolyte ionic content surrounding a liquid metal for symmetry breaking that generates motion. Here we show the controlled actuation of liquid metal droplets using only the ionic properties of the aqueous electrolyte. We demonstrate that pH or ionic concentration gradients across a liquid metal droplet induce both deformation and surface Marangoni flow. We show that the Lippmann dominated deformation results in maximum velocity for the self-propulsion of liquid metal droplets and illustrate several key applications, which take advantage of such electrolyte-induced motion. With this finding, it is possible to conceive the propulsion of small entities that are constructed and controlled entirely with fluids, progressing towards more advanced soft systems.

Enhancement of Force Generated by Individual Myosin Heads in Skinned Rabbit Psoas Muscle Fibers at Low Ionic Strength

PubMed Central

Sugi, Haruo; Abe, Takahiro; Kobayashi, Takakazu; Chaen, Shigeru; Ohnuki, Yoshiki; Saeki, Yasutake; Sugiura, Seiryo

2013-01-01

Although evidence has been presented that, at low ionic strength, myosin heads in relaxed skeletal muscle fibers form linkages with actin filaments, the effect of low ionic strength on contraction characteristics of Ca2+-activated muscle fibers has not yet been studied in detail. To give information about the mechanism of muscle contraction, we have examined the effect of low ionic strength on the mechanical properties and the contraction characteristics of skinned rabbit psoas muscle fibers in both relaxed and maximally Ca2+-activated states. By progressively decreasing KCl concentration from 125 mM to 0 mM (corresponding to a decrease in ionic strength μ from 170 mM to 50 mM), relaxed fibers showed changes in mechanical response to sinusoidal length changes and ramp stretches, which are consistent with the idea of actin-myosin linkage formation at low ionic strength. In maximally Ca2+-activated fibers, on the other hand, the maximum isometric force increased about twofold by reducing KCl concentration from 125 to 0 mM. Unexpectedly, determination of the force-velocity curves indicated that, the maximum unloaded shortening velocity Vmax, remained unchanged at low ionic strength. This finding indicates that the actin-myosin linkages, which has been detected in relaxed fibers at low ionic strength, are broken quickly on Ca2+ activation, so that the linkages in relaxed fibers no longer provide any internal resistance against fiber shortening. The force-velocity curves, obtained at various levels of steady Ca2+-activated isometric force, were found to be identical if they are normalized with respect to the maximum isometric force. The MgATPase activity of muscle fibers during isometric force generation was found not to change appreciably at low ionic strength despite the two-fold increase in Ca2+-activated isometric force. These results can be explained in terms of enhancement of force generated by individual myosin heads, but not by any changes in kinetic properties of cyclic actin-myosin interaction. PMID:23691080

Performance of Carbon/Polytetrafluoroethylene (PTFE) Air Cathodes from pH 0 to 14 for Li-Air Batteries

DTIC Science & Technology

2007-12-01

aqueous and aqueous electrolytes are kept separate by a non-electronically conducting ceramic membrane impervious to water, but with a high ionic...thought of as being solvated by the ceramic membrane as it passes from non-aqueous to aqueous electrolyte. The half-cell reaction at the lithium...overall charge in the reaction, positive lithium ions flow through an ionically conducting ceramic membrane from the non-aqueous anode compartment to

Carbon/PTFE Electrode for Lithium/Air-Water Batteries

DTIC Science & Technology

2007-03-01

non-electronically conducting ceramic membrane impervious to water but with a high ionic conductivity for lithium-ions. LiTixAly(PO4)3 is one such...example of a ceramic composition that has been used in this manner. The lithium ion can be thought of as being solvated by the ceramic membrane as it...through 5) provides current. To balance the overall charge in the reaction, positive lithium ions flow 1 through an ionically conducting ceramic

Influence of Electrical and Ionic Conductivities of Organic Electronic Ion Pump on Acetylcholine Exchange Performance

PubMed Central

Abdullayeva, Nazrin; Sankir, Mehmet

2017-01-01

By using an easy and effective method of depositing conjugated polymers (PEDOT:PSS) on flexible substrates, a new design for organic bioelectronic devices has been developed. The purpose was to build up a system that mimics the motion of neurotransmitters in the synaptic cleft by obtaining an electrical to chemical signal transport. Fourier transform infrared (FTIR) spectroscopy and Raman measurements have demonstrated that electrochemical overoxidation region which separates the pristine PEDOT:PSS electrodes and allows ionic conduction has been achieved successfully. The influence of both electrical and ionic conductivities on organic electronic ion pump (OEIP) performances has been studied. The ultimate goal was to achieve the highest equilibrium current density at the lowest applied voltage via enhancing the electrical conductivity of PEDOT:PSS and ionic conductivity of electrochemically overoxidized region. The highest equilibrium current density, which corresponds to 4.81 × 1017 number of ions of acetylcholine was about 41 μA cm−2 observed for the OEIP with the electrical conductivities of 54 S cm−1. This was a threshold electrical conductivity beyond which the OEIP performances were not changed much. Once Nafion™ has been applied for enhancing the ionic conductivity, the equilibrium current density increased about ten times and reached up to 408 μA cm−2. Therefore, it has been demonstrated that the OEIP performance mainly scales with the ionic conductivity. A straightforward method of producing organic bioelectronics is proposed here may provide a clue for their effortless mass production in the near future. PMID:28772946

Integrated study of first principles calculations and experimental measurements for Li-ionic conductivity in Al-doped solid-state LiGe2(PO4)3 electrolyte

NASA Astrophysics Data System (ADS)

Kang, Joonhee; Chung, Habin; Doh, Chilhoon; Kang, Byoungwoo; Han, Byungchan

2015-10-01

Understanding of the fundamental mechanisms causing significant enhancement of Li-ionic conductivity by Al3+ doping to a solid LiGe2(PO4)3 (LGP) electrolyte is pursued using first principles density functional theory (DFT) calculations combined with experimental measurements. Our results indicate that partial substitution Al3+ for Ge4+ in LiGe2(PO4)3 (LGP) with aliovalent (Li1+xAlxGe2-x(PO4)3, LAGP) improves the Li-ionic conductivity about four-orders of the magnitude. To unveil the atomic origin we calculate plausible diffusion paths of Li in LGP and LAGP materials using DFT calculations and a nudged elastic band method, and discover that LAGP had additional transport paths for Li with activation barriers as low as only 34% of the LGP. Notably, these new atomic channels manifest subtle electrostatic environments facilitating cooperative motions of at least two Li atoms. Ab-initio molecular dynamics predict Li-ionic conductivity for the LAGP system, which is amazingly agreed experimental measurement on in-house made samples. Consequently, we suggest that the excess amounts of Li caused by the aliovalent Al3+ doping to LGP lead to not only enhancing Li concentration but also opening new conducting paths with substantially decreases activation energies and thus high ionic conductivity of LAGP solid-state electrolyte.

Enhanced photoluminescence from single nitrogen-vacancy defects in nanodiamonds coated with phenol-ionic complexes

NASA Astrophysics Data System (ADS)

Bray, Kerem; Previdi, Rodolfo; Gibson, Brant C.; Shimoni, Olga; Aharonovich, Igor

2015-03-01

Fluorescent nanodiamonds are attracting major attention in the field of bio-sensing and bio-labeling. In this work we demonstrate a robust approach to achieve an encapsulation of individual nanodiamonds with phenol-ionic complexes that enhance the photoluminescence from single nitrogen vacancy (NV) centers. We show that single NV centres in the coated nanodiamonds also exhibit shorter lifetimes, opening another channel for high resolution sensing. We propose that the nanodiamond encapsulation reduces the non-radiative decay pathways of the NV color centers. Our results provide a versatile and assessable way to enhance photoluminescence from nanodiamond defects that can be used in a variety of sensing and imaging applications.Fluorescent nanodiamonds are attracting major attention in the field of bio-sensing and bio-labeling. In this work we demonstrate a robust approach to achieve an encapsulation of individual nanodiamonds with phenol-ionic complexes that enhance the photoluminescence from single nitrogen vacancy (NV) centers. We show that single NV centres in the coated nanodiamonds also exhibit shorter lifetimes, opening another channel for high resolution sensing. We propose that the nanodiamond encapsulation reduces the non-radiative decay pathways of the NV color centers. Our results provide a versatile and assessable way to enhance photoluminescence from nanodiamond defects that can be used in a variety of sensing and imaging applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr07510b

Modeling, fabrication and plasma actuator coupling of flexible pressure sensors for flow separation detection and control in aeronautical applications

NASA Astrophysics Data System (ADS)

Francioso, L.; De Pascali, C.; Pescini, E.; De Giorgi, M. G.; Siciliano, P.

2016-06-01

Preventing the flow separation could enhance the performance of propulsion systems and future civil aircraft. To this end, a fast detection of boundary layer separation is mandatory for a sustainable and successful application of active flow control devices, such as plasma actuators. The present work reports on the design, fabrication and functional tests of low-cost capacitive pressure sensors coupled with dielectric barrier discharge (DBD) plasma actuators to detect and then control flow separation. Finite element method (FEM) simulations were used to obtain information on the deflection and the stress distribution in different-shaped floating membranes. The sensor sensitivity as a function of the pressure load was also calculated by experimental tests. The results of the calibration of different capacitive pressure sensors are reported in this work, together with functional tests in a wind tunnel equipped with a curved wall plate on which a DBD plasma actuator was mounted to control the flow separation. The flow behavior was experimentally investigated by particle image velocimetry (PIV) measurements. Statistical and spectral analysis, applied to the output signals of the pressure sensor placed downstream of the profile leading edge, demonstrated that the sensor is able to discriminate different ionic wind velocity and turbulence conditions. The sensor sensitivity in the 0-100 Pa range was experimentally measured and it ranged between 0.0030 and 0.0046 pF Pa-1 for the best devices.

Direct hydrothermal growth of GDC nanorods for low temperature solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Hong, Soonwook; Lee, Dohaeng; Yang, Hwichul; Kim, Young-Beom

2018-06-01

We report a novel synthesis technique of gadolinia-doped ceria (GDC) nano-rod (NRs) via direct hydrothermal process to enhance performance of low temperature solid oxide fuel cell by increasing active reaction area and ionic conductivity at interface between cathode and electrolyte. The cerium nitrate hexahydrate, gadolinium nitrate hexahydrate and urea were used to synthesis GDC NRs for growth on diverse substrate. The directly grown GDC NRs on substrate had a width from 819 to 490 nm and height about 2200 nm with a varied urea concentration. Under the optimized urea concentration of 40 mMol, we confirmed that GDC NRs able to fully cover the substrate by enlarging active reaction area. To maximize ionic conductivity of GDC NRs, we synthesis varied GDC NRs with different ratio of gadolinium and cerium precursor. Electrochemical analysis revealed a significant enhanced performance of fuel cells applying synthesized GDC NRs with a ratio of 2:8 gadolinium and cerium precursor by reducing polarization resistance, which was chiefly attributed to the enlarged active reaction area and enhanced ionic conductivity of GDC NRs. This method of direct hydrothermal growth of GDC NRs enhancing fuel cell performance was considered to apply other types of catalyzing application using nano-structure such as gas sensing and electrolysis fields.

Determination and characterization by numerical simulations of flow mixing due to electrokinetic instabilities in cross-shaped microchannels

NASA Astrophysics Data System (ADS)

Guerrero, Esteban; Chen, Daming; Hageman, Logan; Guzman, Amador

2017-11-01

This article describes a computational study of flow mixing in microchannels due to electrokinetic instabilities that are compared to experimental results obtained in a cross- microchannel with an ionic solution of potassium chloride with two different ionic concentrations, with the purpose of determining the parameter combinations to produce the onset of flow mixing and its characteristics. For the numerical simulation process carried out using a finite element method-based commercial code, we applied a typical zeta potential used in other articles as a boundary condition for the microchannel walls. For the experiments, we used a commercial silicon glass (Caliper NS95) microchannel. For determining a flow mixing regime, we use the concept of ``mixing index'' established by (Fu et al., 2005) for an electrical conductivity ratio range of 18 to 52 with an electric field range of 1100 to 1900 V/cm. From our numerical simulation results we have found a threshold for the electrical Rayleigh number for starting a flow mixing regime, and a minimum microchannel characteristic length for achieving a 90% of flow mixing that will allow us to significantly reduce the mixing time. Vicerrectoria de Investigacion y Departamento de Ingeniera Mecánica y Metalúrgica Pontificia Universidad Catolica de Chile.

The effects of high concentrations of ionic liquid on GB1 protein structure and dynamics probed by high-resolution magic-angle-spinning NMR spectroscopy

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

Warner, Lisa; Gjersing, Erica; Follett, Shelby E.

Ionic liquids have great potential in biological applications and biocatalysis, as some ionic liquids can stabilize proteins and enhance enzyme activity, while others have the opposite effect. However, on the molecular level, probing ionic liquid interactions with proteins, especially in solutions containing high concentrations of ionic liquids, has been challenging. In the present work the 13C, 15N-enriched GB1 model protein was used to demonstrate applicability of high-resolution magic-angle-spinning (HR-MAS) NMR spectroscopy to investigate ionic liquid-protein interactions. Effect of an ionic liquid (1-butyl-3-methylimidazolium bromide, [C 4-mim]Br) on GB1was studied over a wide range of the ionic liquid concentrations (0.6-3.5 M, whichmore » corresponds to 10-60% v/v). Interactions between GB1 and [C 4-mim]Br were observed from changes in the chemical shifts of the protein backbone as well as the changes in 15N ps-ns dynamics and rotational correlation times. Site-specific interactions between the protein and [C 4-mim]Br were assigned using 3D methods under HR-MAS conditions. Furthermore, HR-MAS NMR is a viable tool that could aid in elucidation of molecular mechanisms of ionic liquid-protein interactions.« less

The effects of high concentrations of ionic liquid on GB1 protein structure and dynamics probed by high-resolution magic-angle-spinning NMR spectroscopy

DOE PAGES

Warner, Lisa; Gjersing, Erica; Follett, Shelby E.; ...

2016-08-11

Ionic liquids have great potential in biological applications and biocatalysis, as some ionic liquids can stabilize proteins and enhance enzyme activity, while others have the opposite effect. However, on the molecular level, probing ionic liquid interactions with proteins, especially in solutions containing high concentrations of ionic liquids, has been challenging. In the present work the 13C, 15N-enriched GB1 model protein was used to demonstrate applicability of high-resolution magic-angle-spinning (HR-MAS) NMR spectroscopy to investigate ionic liquid-protein interactions. Effect of an ionic liquid (1-butyl-3-methylimidazolium bromide, [C 4-mim]Br) on GB1was studied over a wide range of the ionic liquid concentrations (0.6-3.5 M, whichmore » corresponds to 10-60% v/v). Interactions between GB1 and [C 4-mim]Br were observed from changes in the chemical shifts of the protein backbone as well as the changes in 15N ps-ns dynamics and rotational correlation times. Site-specific interactions between the protein and [C 4-mim]Br were assigned using 3D methods under HR-MAS conditions. Furthermore, HR-MAS NMR is a viable tool that could aid in elucidation of molecular mechanisms of ionic liquid-protein interactions.« less

Sequential Vapor Infiltration Treatment Enhances the Ionic Current Rectification Performance of Composite Membranes Based on Mesoporous Silica Confined in Anodic Alumina.

PubMed

Liang, Yanyan; Liu, Zhengping

2016-12-20

Ionic current rectification of nanofluidic diode membranes has been studied widely in recent years because it is analogous to the functionality of biological ion channels in principle. We report a new method to fabricate ionic current rectification membranes based on mesoporous silica confined in anodic aluminum oxide (AAO) membranes. Two types of mesostructured silica nanocomposites, hexagonal structure and nanoparticle stacked structure, were used to asymmetrically fill nanochannels of AAO membranes by a vapor-phase synthesis (VPS) method with aspiration approach and were further modified via sequence vapor infiltration (SVI) treatment. The ionic current measurements indicated that SVI treatment can modulate the asymmetric ionic transport in prepared membranes, which exhibited clear ionic current rectification phenomenon under optimal conditions. The ionic current rectifying behavior is derived from the asymmetry of surface conformations, silica species components, and hydrophobic wettability, which are created by the asymmetrical filling type, silica depositions on the heterogeneous membranes, and the condensation of silanol groups. This article provides a considerable strategy to fabricate composite membranes with obvious ionic current rectification performance via the cooperation of the VPS method and SVI treatment and opens up the potential of mesoporous silica confined in AAO membranes to mimic fluid transport in biological processes.

Impurity effects on ionic-liquid-based supercapacitors

DOE PAGES

Liu, Kun; Lian, Cheng; Henderson, Douglas; ...

2016-12-27

Small amounts of an impurity may affect the key properties of an ionic liquid and such effects can be dramatically amplified when the electrolyte is under confinement. Here the classical density functional theory is employed to investigate the impurity effects on the microscopic structure and the performance of ionic-liquid-based electrical double-layer capacitors, also known as supercapacitors. Using a primitive model for ionic species, we study the effects of an impurity on the double layer structure and the integral capacitance of a room temperature ionic liquid in model electrode pores and find that an impurity strongly binding to the surface ofmore » a porous electrode can significantly alter the electric double layer structure and dampen the oscillatory dependence of the capacitance with the pore size of the electrode. Meanwhile, a strong affinity of the impurity with the ionic species affects the dependence of the integral capacitance on the pore size. Up to 30% increase in the integral capacitance can be achieved even at a very low impurity bulk concentration. As a result, by comparing with an ionic liquid mixture containing modified ionic species, we find that the cooperative effect of the bounded impurities is mainly responsible for the significant enhancement of the supercapacitor performance.« less

Fluorescence recognition of chiral amino alcohols by using a novel ionic liquid sensor.

PubMed

Cai, Pengfei; Wu, Datong; Zhao, Xiaoyong; Pan, Yuanjiang

2017-08-07

A novel task-specific ionic liquid derived from l-phenylalaninol was prepared as an enantioselective fluorescent sensor for the first time. Fluorescent chiral ionic liquid 1 (FCIL1) is found to exhibit highly enantioselective fluorescence enhancements toward both aromatic and non-aromatic chiral amino alcohols. When (S)-FCIL1 was treated with the enantiomers of phenylalaninol, a great fluorescence enhancement at 349 nm could be observed and the value of the enantiomeric fluorescence difference (ef) is 5.92. This demonstrated that the chiral sensor (S)-FCIL1 exhibited an excellent enantioselective response behaviour to d-phenylalaninol. Besides that, both the fluorescence intensity at 349 nm (I 349 ) and the ratio of I 349 to I 282 depend linearly on the concentration of amino alcohols. Both the concentration and the enantiomeric composition could be determined by using the chiral ionic liquid. Differently, the sensor treated with the enantiomers of 2-amino-1-butanol showed an opposite result: the fluorescence intensity of the S-enantiomer is higher than that of the R-enantiomer. Furthermore, the size of the substituents on the chiral carbon might be important for the enantioselective fluorescent response.

Innovative polymer nanocomposite electrolytes: nanoscale manipulation of ion channels by functionalized graphenes.

PubMed

Choi, Bong Gill; Hong, Jinkee; Park, Young Chul; Jung, Doo Hwan; Hong, Won Hi; Hammond, Paula T; Park, Hoseok

2011-06-28

The chemistry and structure of ion channels within the polymer electrolytes are of prime importance for studying the transport properties of electrolytes as well as for developing high-performance electrochemical devices. Despite intensive efforts on the synthesis of polymer electrolytes, few studies have demonstrated enhanced target ion conduction while suppressing unfavorable ion or mass transport because the undesirable transport occurs through an identical pathway. Herein, we report an innovative, chemical strategy for the synthesis of polymer electrolytes whose ion-conducting channels are physically and chemically modulated by the ionic (not electronic) conductive, functionalized graphenes and for a fundamental understanding of ion and mass transport occurring in nanoscale ionic clusters. The functionalized graphenes controlled the state of water by means of nanoscale manipulation of the physical geometry and chemical functionality of ionic channels. Furthermore, the confinement of bound water within the reorganized nanochannels of composite membranes was confirmed by the enhanced proton conductivity at high temperature and the low activation energy for ionic conduction through a Grotthus-type mechanism. The selectively facilitated transport behavior of composite membranes such as high proton conductivity and low methanol crossover was attributed to the confined bound water, resulting in high-performance fuel cells.

Continuous synthesis of peralkylated imidazoles and their transformation into ionic liquids with improved (electro)chemical stabilities.

PubMed

Maton, Cedric; De Vos, Nils; Roman, Bart I; Vanecht, Evert; Brooks, Neil R; Binnemans, Koen; Schaltin, Stijn; Fransaer, Jan; Stevens, Christian V

2012-09-17

A versatile and efficient method to synthesize tetrasubstituted imidazoles via a one-pot modified Debus-Radziszewski reaction and their subsequent transformation into the corresponding imidazolium ionic liquids is reported. The tetrasubstituted imidazoles were also synthesized by means of a continuous flow process. This straightforward synthetic procedure allows for a fast and selective synthesis of tetrasubstituted imidazoles on a large scale. The completely substituted imidazolium dicyanamide and bis(trifluoromethylsulfonyl)imide salts were obtained via a metathesis reaction of the imidazolium iodide salts. The melting points and viscosities are of the same order of magnitude as for their non-substituted analogues. In addition to the superior chemical stability of these novel ionic liquids, which allows them to be applied in strong alkaline media, the improved thermal and electrochemical stabilities of these compounds compared with conventional imidazolium ionic liquids is also demonstrated by thermogravimetrical analysis (TGA) and cyclic voltammetry (CV). Although increased substitution of the ionic liquids does not further increase thermal stability, a definite increase in cathodic stability is observable. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Removal of natural organic matter by titanium tetrachloride: The effect of total hardness and ionic strength.

PubMed

Zhao, Y X; Shon, H K; Phuntsho, S; Gao, B Y

2014-02-15

This study is the first attempt to investigate the effect of total hardness and ionic strength on coagulation performance and the floc characteristics of titanium tetrachloride (TiCl4). Membrane fouling under different total hardness and ionic strength conditions was also evaluated during a coagulation-ultrafiltration (C-UF) hybrid process. Coagulation experiments were performed with two simulated waters, using humic acid (HA, high molecular weight) and fulvic acid (FA, relatively low molecular weight), respectively, as model natural organic matter (NOM). Results show that both particle and organic matter removal can be enhanced by increasing total hardness and ionic strength. Floc characteristics were significantly influenced by total hardness and ionic strength and were improved in terms of floc size, growth rate, strength, recoverability and compactness. The results of the UF tests show that the pre-coagulation with TiCl4 significantly improves the membrane permeate fluxes. Under different total hardness and ionic strength conditions, the membrane permeate flux varied according to both NOM and floc characteristics. The increase in total hardness and ionic strength improved the membrane permeate flux in the case of HA simulated water treatment. Copyright © 2014 Elsevier Ltd. All rights reserved.

Clinical observation of the adverse drug reactions caused by non-ionic iodinated contrast media: results from 109,255 cases who underwent enhanced CT examination in Chongqing, China.

PubMed

Li, X; Chen, J; Zhang, L; Liu, H; Wang, S; Chen, X; Fang, J; Wang, S; Zhang, W

2015-03-01

To analyse the pattern and factors that influence the incidence of adverse drug reactions (ADRs) induced by non-ionic iodinated contrast media and to evaluate their safety profiles. Data from 109,255 cases who underwent enhanced CT examination from 1 January 2008 to 31 August 2013 were analysed. ADRs were classified according to the criteria issued by the American College of Radiology and the Chinese Society of Radiology. A total of 375 (0.34%) patients had ADRs, including 281 mild (0.26%); 80 moderate (0.07%); and 14 severe (0.01%) ADRs; no death was found. 302 (80.53%) of the ADRs occurred within 15 min after examination. Patients aged 40-49 years (204 cases, 0.43%; p < 0.01) or who underwent coronary CT angiography (93 cases, 0.61%; p < 0.01) were at a higher risk of ADRs. Female patients (180 cases, 0.40%; p < 0.01) or outpatients had significantly higher incidence rates of ADRs. The symptoms and signs of most of the ADRs were resolved spontaneously within 24 h after appropriate treatment without sequelae. The occurrence of ADRs is caused by the combined effects of multiple factors. The ADRs induced by non-ionic iodinated contrast media are mainly mild ones, while moderate or severe ADRs are relatively rare, suggesting that enhanced CT examination with non-ionic iodinated contrast media is highly safe, and severe adverse events will seldom occur under appropriate care. The study included 109,255 patients enrolled in various types of enhanced CT examinations, which could reflect ADR conditions and regulations in Chinese population accurately and reliably.

Clinical observation of the adverse drug reactions caused by non-ionic iodinated contrast media: results from 109,255 cases who underwent enhanced CT examination in Chongqing, China

PubMed Central

Li, X; Chen, J; Zhang, L; Liu, H; Wang, S; Chen, X; Fang, J; Wang, S

2015-01-01

Objective: To analyse the pattern and factors that influence the incidence of adverse drug reactions (ADRs) induced by non-ionic iodinated contrast media and to evaluate their safety profiles. Methods: Data from 109,255 cases who underwent enhanced CT examination from 1 January 2008 to 31 August 2013 were analysed. ADRs were classified according to the criteria issued by the American College of Radiology and the Chinese Society of Radiology. Results: A total of 375 (0.34%) patients had ADRs, including 281 mild (0.26%); 80 moderate (0.07%); and 14 severe (0.01%) ADRs; no death was found. 302 (80.53%) of the ADRs occurred within 15 min after examination. Patients aged 40–49 years (204 cases, 0.43%; p < 0.01) or who underwent coronary CT angiography (93 cases, 0.61%; p < 0.01) were at a higher risk of ADRs. Female patients (180 cases, 0.40%; p < 0.01) or outpatients had significantly higher incidence rates of ADRs. The symptoms and signs of most of the ADRs were resolved spontaneously within 24 h after appropriate treatment without sequelae. Conclusion: The occurrence of ADRs is caused by the combined effects of multiple factors. The ADRs induced by non-ionic iodinated contrast media are mainly mild ones, while moderate or severe ADRs are relatively rare, suggesting that enhanced CT examination with non-ionic iodinated contrast media is highly safe, and severe adverse events will seldom occur under appropriate care. Advances in knowledge: The study included 109,255 patients enrolled in various types of enhanced CT examinations, which could reflect ADR conditions and regulations in Chinese population accurately and reliably. PMID:25582519

Ionic liquid foam floatation coupled with ionic liquid dispersive liquid-liquid microextraction for the separation and determination of estrogens in water samples by high-performance liquid chromatography with fluorescence detection.

PubMed

Zhang, Rui; Wang, Chuanliu; Yue, Qiaohong; Zhou, Tiecheng; Li, Na; Zhang, Hanqi; Hao, Xiaoke

2014-11-01

An ionic liquid foam floatation coupled with ionic liquid dispersive liquid-liquid microextraction method was proposed for the extraction and concentration of 17-α-estradiol, 17-β-estradiol-benzoate, and quinestrol in environmental water samples by high-performance liquid chromatography with fluorescence detection. 1-Hexyl-3-methylimidazolium tetrafluoroborate was applied as foaming agent in the foam flotation process and dispersive solvent in microextraction. The introduction of the ion-pairing and salting-out agent NH4 PF6 was beneficial to the improvement of recoveries for the hydrophobic ionic liquid phase and analytes. Parameters of the proposed method including concentration of 1-hexyl-3-methylimidazolium tetrafluoroborate, flow rate of carrier gas, floatation time, types and concentration of ionic liquids, salt concentration in samples, extraction time, and centrifugation time were evaluated. The recoveries were between 98 and 105% with relative standard deviations lower than 7% for lake water and well water samples. The isolation of the target compounds from the water was found to be efficient, and the enrichment factors ranged from 4445 to 4632. This developing method is free of volatile organic solvents compared with regular extraction. Based on the unique properties of ionic liquids, the application of foam floatation, and dispersive liquid-liquid microextraction was widened. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ionic Attachment as a Feasible Approach to Heterogenizing Anionic Solution Catalysts. The Carbonylation of Methanol,

DTIC Science & Technology

1980-08-01

carbonylation of methanol to acetic acid reaction is well suited for a demonstration of the feasibility and value of ionically binding a catalyst to a...approximate doubling of the reaction rate. This result suggests that a liquid flow system design in which there is a large catalyst to methanol ratio could...Heterogenizing Anionic Solution Catalysts . The Carbonylation of Methanol by Russell S. Drago, Eric D. Nyberg, Anton El A’mma and Alan Zombeck ABSTRACT -’Few

Reactions of Ions with Ionic Liquid Vapors by Selected-Ion Flow Tube Mass Spectrometry

DTIC Science & Technology

2011-03-04

Internet at http://pubs.acs.org. References (1) Emel’yanenko, V. N.; Verevkin, S. P.; Heintz, A.; Corfield, J.-A.; Deyko, A.; Lovelock , K. R. J...Spectrometry, and ab Initio Calculations J. Phys. Chem. B 2008, 112, 11734-11742. (2) Lovelock , K. R. J.; Deyko, A.; Licence, P.; Jones, R. G. Vaporisation of...Licence, P.; Lovelock , K. R. J.; Satterly, C. J.; Villar-Garcia, I. J. Vapourisation of ionic liquids PCCP 2007, 9, 982-990. (14) Chiu, Y.-H

Can ionophobic nanopores enhance the energy storage capacity of electric-double-layer capacitors containing nonaqueous electrolytes?

DOE PAGES

Lian, Cheng; Univ. of California, Riverside, CA; Liu, Honglai; ...

2016-08-22

The ionophobicity effect of nanoporous electrodes on the capacitance and the energy storage capacity of nonaqueous-electrolyte supercapacitors is studied by means of the classical density functional theory (DFT). It has been hypothesized that ionophobic nanopores may create obstacles in charging, but they store energy much more efficiently than ionophilic pores. In this paper, we find that, for both ionic liquids and organic electrolytes, an ionophobic pore exhibits a charging behavior different from that of an ionophilic pore, and that the capacitance–voltage curve changes from a bell shape to a two-hump camel shape when the pore ionophobicity increases. For electric-double-layer capacitorsmore » containing organic electrolytes, an increase in the ionophobicity of the nanopores leads to a higher capacity for energy storage. Without taking into account the effects of background screening, the DFT predicts that an ionophobic pore containing an ionic liquid does not enhance the supercapacitor performance within the practical voltage ranges. However, by using an effective dielectric constant to account for ion polarizability, the DFT predicts that, like an organic electrolyte, an ionophobic pore with an ionic liquid is also able to increase the energy stored when the electrode voltage is beyond a certain value. We find that the critical voltage for an enhanced capacitance in an ionic liquid is larger than that in an organic electrolyte. Finally, our theoretical predictions provide further understanding of how chemical modification of porous electrodes affects the performance of supercapacitors.« less

The gelation influence on diffusion and conductivity enhancement effect in renewable ionic gels based on a LMWG.

PubMed

Bielejewski, M; Rachocki, A; Kaszyńska, J; Tritt-Goc, J

2018-02-21

This paper reports the interdisciplinary study on molecular dynamics, ionic interactions and electrical conductivity in a quaternary ammonium salt (TMABr) ionogel based on a low molecular weight gelator (LMWG) in a wide range of electrolyte molar concentrations. The thermal scanning conductometry (TSC) was used to investigate the electric properties of the ionogels. The prepared TMABr/H 2 O/LMWG ionogel exhibits better ion transport properties than the dissociated TMA + cation in solution. The enhanced ionic conductivity effect (EICE) was observed in the concentration range of the TMABr salt up to 1 M. To investigate the transport properties of the TMA + cation and solvent molecules in the gel and sol phase, the NMR diffusiometry method was used. The field-cycling relaxometry method (FFC NMR) was applied to study the local motions of the electrolyte at the surface of the gelator matrix. On the basis of the obtained data, the higher ionic conductivity observed in the gel phase has been related to the microstructure of the gel matrix. The possible explanation for the origin of this effect has been given. The investigated system is a thermally reversible physical gel, all registered data were reproducible upon transforming the sample from gel to sol and back to the gel state, confirming the enhancement effect as a permanent property of the investigated ionogels. Therefore, the EICE has been proposed to be used as an internal sensor to monitor the condition of the ionogel phase, thus making them smart materials.

MS-2 and poliovirus transport in porous media: Hydrophobic effects and chemical perturbations

NASA Astrophysics Data System (ADS)

Bales, Roger C.; Li, Shimin; Maguire, Kimberly M.; Yahya, Moyasar T.; Gerba, Charles P.

1993-04-01

In a series of pH 7 continuous-flow column experiments, removal of the bacteriophage MS-2 by attachment to silica beads had a strong, systematic dependence on the amount of hydrophobic surface present on the beads. With no hydrophobic surface, removal of phage at pH 5 was much greater than at pH 7. Release of attached phage at both pH values did occur, but was slow; breakthrough curves exhibited tailing. Poliovirus attached to silica beads at pH 5.5 much more than at pH 7.0, and attachment was also slowly reversible. Time scales for phage and poliovinis attachment were of the order of hours. The sticking efficiency factor (α), reflecting microscaie physicochemical influences on virus attachment, was in the range of 0.0007-0.02. Phage release was small but measurable under steady state conditions. Release was enhanced by lowering ionic strength and by introducing beef extract, a high-ionic-strength protein solution. Results show that viruses experience reversible attachment/detachment (sometimes termed sorption), that large chemical perturbations are needed to induce rapid virus detachment, and that viruses should be quite mobile in sandy porous media. Even small amounts of hydrophobic organic material in the porous media (≥0.001%) can retard virus transport.

Physicochemical factors affecting ethanol adsorption by activated carbon.

PubMed

Bradley, K J; Hamdy, M K; Toledo, R T

1987-03-01

Powder and granular activated charcoal were evaluated for ethanol adsorptivity from aqueous mixtures using an adsorption isotherm. Ethanol adsorption capacity was more pronounced at 25 degrees C as compared to 5, 15, and 40 degrees C. When pH of the ethanol-buffer mixture (0.09 ionic strength) was changed from acidic (2.3) to neutral and then to alkaline (11.2), ethanol adsorption was decreased. Increasing ionic strength of the ethanol-buffer mixtures from 0.05 to 0.09 enhanced ethanol adsorption but a further increase to 0.14 showed no significant effect. Ethanol adsorption was more efficient from an aqueous ethanol mixture as compared to semidefined and nondefined fermentation worts, respectively. Heating granular charcoal to 400 degrees C for 1 h and 600 degrees C for 3 h in N(2) increased ethanol adsorptivity and heating to 1000 degrees C (1 h) in CO(2) decreased it when ethanol was removed from dilute solutions by simple pass adsorption in a carbon packed column. Granular charcoal was superior to powdered charcoal and an inverse relationship was noted between the weight of the granular carbon bed in the column and ethanol adsorbed/g carbon. Decreasing the column feed flow rate from 7.5 to 2.0 L aqueous ethanol/min increased the adsorption rate.

Molecular Friction-Induced Electroosmotic Phenomena in Thin Neutral Nanotubes.

PubMed

Vuković, Lela; Vokac, Elizabeth; Král, Petr

2014-06-19

We reveal by classical molecular dynamics simulations electroosmotic flows in thin neutral carbon (CNT) and boron nitride (BNT) nanotubes filled with ionic solutions of hydrated monovalent atomic ions. We observe that in (12,12) BNTs filled with single ions in an electric field, the net water velocity increases in the order of Na(+) < K(+) < Cl(-), showing that different ions have different power to drag water in thin nanotubes. However, the effect gradually disappears in wider nanotubes. In (12,12) BNTs containing neutral ionic solutions in electric fields, we observe net water velocities going in the direction of Na(+) for (Na(+), Cl(-)) and in the direction of Cl(-) for (K(+), Cl(-)). We hypothesize that the electroosmotic flows are caused by different strengths of friction between ions with different hydration shells and the nanotube walls.

Motion of Molecular Probes and Viscosity Scaling in Polyelectrolyte Solutions at Physiological Ionic Strength

PubMed Central

Sozanski, Krzysztof; Wisniewska, Agnieszka; Kalwarczyk, Tomasz; Sznajder, Anna; Holyst, Robert

2016-01-01

We investigate transport properties of model polyelectrolyte systems at physiological ionic strength (0.154 M). Covering a broad range of flow length scales—from diffusion of molecular probes to macroscopic viscous flow—we establish a single, continuous function describing the scale dependent viscosity of high-salt polyelectrolyte solutions. The data are consistent with the model developed previously for electrically neutral polymers in a good solvent. The presented approach merges the power-law scaling concepts of de Gennes with the idea of exponential length scale dependence of effective viscosity in complex liquids. The result is a simple and applicable description of transport properties of high-salt polyelectrolyte solutions at all length scales, valid for motion of single molecules as well as macroscopic flow of the complex liquid. PMID:27536866

Simultaneous improvement in ionic conductivity and flexibility of solid polymer electrolytes for thin film lithium ion batteries

NASA Astrophysics Data System (ADS)

Ji, Jianying

Solid polymer electrolytes (SPEs) provide advantages over liquid electrolytes in terms of safety, reliability, less temperature sensitive, and simplicity of design. With the use of a SPE in lithium batteries, high specific energy and specific power, safe operation, flexibility in packaging, and low cost of fabrication can be expected. However, after 30 years, SPEs have rarely found commercial success due to the low ionic conductivity and/or insufficient mechanical properties, both of which are related to the movement of the polymer chains. Many physical/chemical methods have been exploited to simultaneously create enhancement in ionic conductivity and mechanical properties, and some suggested ways have shown promise. However, the complex strategies have always introduced other challenge issues and incurred extra costs for manufacturing. In such a context, the development of dry solid state electrolytes is the central challenge to be faced worldwide. This thesis deals with the approaches to improving ionic conductivity and mechanical properties simultaneously. The method is to apply two kinds of controllable organic fillers: copolymer and protein. Our work revealed that the commercial available copolymer, poly (ethylene oxide)- block-polyethylene (PEO-b-PE), possesses a capability for enhancing the multiple performances of poly(ethylene oxide)(PEO)-based polymer electrolyte. And the effects of composition and molecular weight of the copolymers on performance of the resulting SPEs were examined. It was found that increasing the PE block percentage in the copolymer resulted in a significant increase in both ionic conductivity and mechanical properties, while increasing the molecular weight of the copolymer resulted in better mechanical properties, and an identical ionic conductivity. A rubber-like, soy protein-based SPE (s-SPE)was obtained by employing soy protein isolate (SPI), a soy product usually used as rigid fillers for enhancing mechanical properties of polymers, blended with poly(ethylene oxide)(PEO). The results indicated that the s-SPE with 55 wt% of SPI possesses a fully amorphous uniform structure having low Tg, in contrast with crystalline PEO-based SPE having discernable Tg and Tm. The conductivity and elasticity are both significantly improved with SPI involvement. Remarkably, this film has been elongated up to 100% without loss of ionic conductivity and 700% without mechanical damage.

Excimer Formation Dynamics of Dipyrenyldecane in Structurally Different Ionic Liquids.

PubMed

Yadav, Anita; Pandey, Siddharth

2017-12-07

Ionic liquids, being composed of ions alone, may offer alternative pathways for molecular aggregation. These pathways could be controlled by the chemical structure of the cation and the anion of the ionic liquids. Intramolecular excimer formation dynamics of a bifluorophoric probe, 1,3-bis(1-pyrenyl)decane [1Py(10)1Py], where the fluorophoric pyrene moieties are separated by a long decyl chain, is investigated in seven different ionic liquids in 10-90 °C temperature range. The long alkyl separator allows for ample interaction with the solubilizing milieu prior to the formation of the excimer. The ionic liquids are composed of two sets, one having four ionic liquids of 1-butyl-3-methylimidazolium cation ([bmim + ]) with different anions and the other having four ionic liquids of bis(trifluoromethylsulfonyl)imide anion ([Tf 2 N - ]) with different cations. The excimer-to-monomer emission intensity ratio (I E /I M ) is found to increase with increasing temperature in sigmoidal fashion. Chemical structure of the ionic liquid controls the excimer formation efficiency, as I E /I M values within ionic liquids with the same viscosities are found to be significantly different. The excited-state intensity decay kinetics of 1Py(10)1Py in ionic liquids do not adhere to a simplistic Birk's scheme, where only one excimer conformer forms after excitation. The apparent rate constants of excimer formation (k a ) in highly viscous ionic liquids are an order of magnitude lower than those reported in organic solvents. In general, the higher the viscosity of the ionic liquid, the more sensitive is the k a to the temperature with higher activation energy, E a . The trend in E a is found to be similar to that for activation energy of the viscous flow (E a,η ). Stokes-Einstein relationship is not followed in [bmim + ] ionic liquids; however, with the exception of [choline][Tf 2 N], it is found to be followed in [Tf 2 N - ] ionic liquids suggesting the cyclization dynamics of 1Py(10)1Py to be diffusion-controlled and to depend on the viscosity of the ionic liquid irrespective of the identity of the cation. The dependence of ionic liquid structure on cyclization dynamics to form intramolecular excimer is amply highlighted.

High-ionic-strength electroosmotic flows in uncharged hydrophobic nanochannels.

PubMed

Kim, Daejoong; Darve, Eric

2009-02-01

We report molecular dynamics simulation results of high-ionic-strength electroosmotic flows inside uncharged nanochannels. The possibility of this unusual electrokinetic phenomenon has been discussed by Dukhin et al. [A. Dukhin, S. Dukhin, P. Goetz, Langmuir 21 (2005) 9990]. Our computed velocity profiles clearly indicate the presence of a net flow with a maximum velocity around 2 m/s. We found the apparent zeta potential to be -29.7+/-6.8 mV, using the Helmholtz-Smoluchowski relation and the measured mean velocity. This value is comparable to experimentally measured values in Dukhin et al. and references therein. We also investigate the orientations of water molecules in response to an electric field by computing polarization density. Water molecules in the bulk region are oriented along the direction of the external electric field, while their near-wall orientation shows oscillations. The computation of three-dimensional density distributions of sodium and chloride ions around each individual water molecule show that chloride ions tend to concentrate near a water molecule, whereas sodium ions are diffusely distributed.

Compact Electron Gun Based on Secondary Emission Through Ionic Bombardment

PubMed Central

Diop, Babacar; Bonnet, Jean; Schmid, Thomas; Mohamed, Ajmal

2011-01-01

We present a new compact electron gun based on the secondary emission through ionic bombardment principle. The driving parameters to develop such a gun are to obtain a quite small electron gun for an in-flight instrument performing Electron Beam Fluorescence measurements (EBF) on board of a reentry vehicle in the upper atmosphere. These measurements are useful to characterize the gas flow around the vehicle in terms of gas chemical composition, temperatures and velocity of the flow which usually presents thermo-chemical non-equilibrium. Such an instrument can also be employed to characterize the upper atmosphere if placed on another carrier like a balloon. In ground facilities, it appears as a more practical tool to characterize flows in wind tunnel studies or as an alternative to complex electron guns in industrial processes requiring an electron beam. We describe in this paper the gun which has been developed as well as its different features which have been characterized in the laboratory. PMID:22163896

Benzyl-Functionalized Room Temperature Ionic Liquids for CO2/N2 Separation

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

Mahurin, Shannon Mark; Dai, Thomas N; Yeary, Joshua S

2011-01-01

In this work, three classes of room temperature ionic liquids (RTILs), including imidazolium, pyridinium, and pyrrolidinium ionic liquids with a benzyl group appended to the cation, were synthesized and tested for their performance in separating CO{sub 2} and N{sub 2}. All RTILs contained the bis(trifluoromethylsulfonyl)imide anion, permitting us to distinguish the impact of the benzyl moiety attached to the cation on gas separation performance. In general, the attachment of the benzyl group increased the viscosity of the ionic liquid compared with the unfunctionalized analogs and decreased the CO{sub 2} permeability. However, all of the benzyl-modified ionic liquids exhibited enhanced CO{submore » 2}/N{sub 2} selectivities compared with alkyl-based ionic liquids, with values ranging from 22.0 to 33.1. In addition, CO{sub 2} solubilities in the form of Henry's constants were also measured and compared with unfunctionalized analogs. Results of the membrane performance tests and CO{sub 2} solubility measurements demonstrate that the benzyl-functionalized RTILs have significant potential for use in the separation of carbon dioxide from combustion products.« less

Isolation and Characterisation of 1-Alkyl-3-Methylimidazolium Chloride Ionic Liquid-Tolerant and Biodegrading Marine Bacteria

PubMed Central

Megaw, Julianne; Busetti, Alessandro; Gilmore, Brendan F.

2013-01-01

The aim of this study was to isolate and identify marine-derived bacteria which exhibited high tolerance to, and an ability to biodegrade, 1-alkyl-3-methylimidazolium chloride ionic liquids. The salinity and hydrocarbon load of some marine environments may induce selective pressures which enhance the ability of microbes to grow in the presence of these liquid salts. The isolates obtained in this study generally showed a greater ability to grow in the presence of the selected ionic liquids compared to microorganisms described previously, with two marine-derived bacteria, Rhodococcus erythropolis and Brevibacterium sanguinis growing in concentrations exceeding 1 M 1-ethyl-3-methylimidazolium chloride. The ability of these bacteria to degrade the selected ionic liquids was assessed using High Performance Liquid Chromatography (HPLC), and three were shown to degrade the selected ionic liquids by up to 59% over a 63-day test period. These bacterial isolates represent excellent candidates for further potential applications in the bioremediation of ionic liquid-containing waste or following accidental environmental exposure. PMID:23560109

Ion-mediated enhancement of xylem hydraulic conductivity in four Acer species: relationships with ecological and anatomical features.

PubMed

Nardini, Andrea; Dimasi, Federica; Klepsch, Matthias; Jansen, Steven

2012-12-01

The 'ionic effect', i.e., changes in xylem hydraulic conductivity (k(xyl)) due to variation of the ionic sap composition in vessels, was studied in four Acer species growing in contrasting environments differing in water availability. Hydraulic measurements of the ionic effect were performed together with measurements on the sap electrical conductivity, leaf water potential and vessel anatomy. The low ionic effect recorded in Acer pseudoplatanus L. and Acer campestre L. (15.8 and 14.7%, respectively), which represented two species from shady and humid habitats, was associated with a low vessel grouping index, high sap electrical conductivity and least negative leaf water potential. Opposite traits were found for Acer monspessulanum L. and Acer platanoides L., which showed an ionic effect of 23.6 and 23.1%, respectively, and represent species adapted to higher irradiance and/or lower water availability. These findings from closely related species provide additional support that the ionic effect could function as a compensation mechanism for embolism-induced loss of k(xyl), either as a result of high evaporative demand or increased risk of hydraulic failure.

Direct observation and determination of the mechanisms governing mobility of asbestos in porous media

NASA Astrophysics Data System (ADS)

Seiphoori, A.; Ortiz, C. P.; Jerolmack, D. J.

2017-12-01

Transport of asbestos through soil by groundwater is typically considered to be negligible. There are indications, however, that under some conditions of pore-water/soil chemistry asbestos may become mobile, implying that buried contaminants could migrate from a disposal site and surface elsewhere. Shape, size and surface charge may influence the physical and chemical interactions of colloids with the soil matrix, and asbestos consists of elongated particles with different size and unique surface charge properties. Although chemical factors such as pH and ionic strength of pore water may affect the transport properties, the presence of dissolved organic carbon (DOC) has been identified to remarkably enhance the mobility of colloids including asbestos. To date, there is no explanation for how the presence of DOC may facilitate the mobilization of asbestos in soil - mainly because the soil medium has been treated as a black box without the possibility of observing particles within the matrix. Here, we investigated the mobility of chrysotile asbestos particles ( 10 um long) in porous media by developing a flow cell with an optically-transparent porous medium composed of granules of a refractive-index matched material. This enabled us to observe and track the particles within the water-saturated porous medium using in situ microscopy. The aqueous suspension of asbestos fibers was passed through this artificial soil, while the physical and chemical interaction of asbestos particles with the medium and their pore-scale distribution were analyzed. We studied the effects of changing solution chemistry (e.g., ionic strength, pH, and DOC content) on transport, attachment and aggregation of chrysotile particles. Experiments revealed a novel mechanism where the DOC-associated nanoparticles attach to chrysotile fibers by an electrostatic attraction, which facilitates their mobilization through the porous medium while modulating aggregation among fibers. Although pH and ionic strength also influenced aggregation and the attachment rate of particles to the substrate, the effect of DOC was more pronounced. This work may lead to enhanced predictions for the fate and transport of asbestos (as well as other contaminants) in the environment, and has implications for the mobility of asbestos particles in the human body.

Infrared Chemiluminescence Studies of Ion-Molecule Reactions in a Flowing Afterglow.

DTIC Science & Technology

1982-01-01

reaction rate constants and branching ratios have been addressed in drift tubes and flow drift systems, and the translational energy distribution of atomic...composed of about 40 thin cylindrical sections of flow tube , separated by mylar spacers and connected by precision resistors. In the region of LIF... tube radius (Albritton, 1967). For proper operation of a drift tube , ionic species of only one polarity can be present. Efficient separation of

Towards an understanding of induced-charge electrokinetics at large applied voltages in concentrated solutions.

PubMed

Bazant, Martin Z; Kilic, Mustafa Sabri; Storey, Brian D; Ajdari, Armand

2009-11-30

The venerable theory of electrokinetic phenomena rests on the hypothesis of a dilute solution of point-like ions in quasi-equilibrium with a weakly charged surface, whose potential relative to the bulk is of order the thermal voltage (kT/e approximately 25 mV at room temperature). In nonlinear electrokinetic phenomena, such as AC or induced-charge electro-osmosis (ACEO, ICEO) and induced-charge electrophoresis (ICEP), several V approximately 100 kT/e are applied to polarizable surfaces in microscopic geometries, and the resulting electric fields and induced surface charges are large enough to violate the assumptions of the classical theory. In this article, we review the experimental and theoretical literatures, highlight discrepancies between theory and experiment, introduce possible modifications of the theory, and analyze their consequences. We argue that, in response to a large applied voltage, the "compact layer" and "shear plane" effectively advance into the liquid, due to the crowding of counterions. Using simple continuum models, we predict two general trends at large voltages: (i) ionic crowding against a blocking surface expands the diffuse double layer and thus decreases its differential capacitance, and (ii) a charge-induced viscosity increase near the surface reduces the electro-osmotic mobility; each trend is enhanced by dielectric saturation. The first effect is able to predict high-frequency flow reversal in ACEO pumps, while the second may explain the decay of ICEO flow with increasing salt concentration. Through several colloidal examples, such as ICEP of an uncharged metal sphere in an asymmetric electrolyte, we show that nonlinear electrokinetic phenomena are generally ion-specific. Similar theoretical issues arise in nanofluidics (due to confinement) and ionic liquids (due to the lack of solvent), so the paper concludes with a general framework of modified electrokinetic equations for finite-sized ions.

Influence of natural organic matter on transport and retention of polymer coated silver nanoparticles in porous media.

PubMed

Yang, Xinyao; Lin, Shihong; Wiesner, Mark R

2014-01-15

Interactions between organic matter (OM) and engineered polymer coatings as they affect the retention of polyvinylpyrrolidone (PVP) polymer-coated silver nanoparticles (AgNPs) were studied. Two distinct types of OM-cysteine representing low molecular weight multivalent functional groups, and Suwannee River Humic Acid (HA) representing high molecular weight polymers, were investigated with respect to their effects on particle stability in aggregation and deposition. Aggregation of the PVP coated AgNPs (PVP-AgNPs) was enhanced by cysteine addition at high ionic strengths, which was attributed to cysteine binding to the AgNPs and replacing the otherwise steric stabilizing agent PVP. In contrast the addition of HA did not increase aggregation rates and decreased PVP-AgNP deposition to the silica porous medium, consistent with enhanced electrosteric stabilization by the HA. Although cysteine also reduced deposition in the porous medium, the mechanisms of reduced deposition appear to be enhanced electric double layer (EDL) interaction at low ionic strengths. At higher ionic strengths, aggregation was favored leading to lower deposition due to smaller diffusion coefficients and single collector efficiencies despite the reduced EDL interactions. Copyright © 2013 Elsevier B.V. All rights reserved.

Dysprosium electrodeposition from a hexaalkylguanidinium-based ionic liquid

NASA Astrophysics Data System (ADS)

Berger, Claudia A.; Arkhipova, Maria; Maas, Gerhard; Jacob, Timo

2016-07-01

The rare-earth element dysprosium (Dy) is an important additive that increases the magnetocrystalline anisotropy of neodymium magnets and additionally prevents from demagnetizing at high temperatures. Therefore, it is one of the most important elements for high-tech industries and is mainly used in permanent magnetic applications, for example in electric vehicles, industrial motors and direct-drive wind turbines. In an effort to develop a more efficient electrochemical technique for depositing Dy on Nd-magnets in contrast to commonly used costly physical vapor deposition, we investigated the electrochemical behavior of dysprosium(iii) trifluoromethanesulfonate in a custom-made guanidinium-based room-temperature ionic liquid (RTIL). We first examined the electrodeposition of Dy on an Au(111) model electrode. The investigation was carried out by means of cyclic voltammetry (CV) and X-ray photoelectron spectroscopy (XPS). The initial stages of metal deposition were followed by in situ scanning tunneling microscopy (STM). CV measurements revealed a large cathodic reduction peak, which corresponds to the growth of monoatomic high islands, based on STM images taken during the initial stages of deposition. XPS identified these deposited islands as dysprosium. A similar reduction peak was also observed on an Nd-Fe-B substrate, and positively identified as deposited Dy using XPS. Finally, we varied the concentration of the Dy precursor, electrolyte flow and temperature during Dy deposition and demonstrated that each of these parameters could be used to increase the thickness of the Dy deposit, suggesting that these parameters could be tuned simultaneously in a temperature-controlled flow cell to enhance the thickness of the Dy layer.The rare-earth element dysprosium (Dy) is an important additive that increases the magnetocrystalline anisotropy of neodymium magnets and additionally prevents from demagnetizing at high temperatures. Therefore, it is one of the most important elements for high-tech industries and is mainly used in permanent magnetic applications, for example in electric vehicles, industrial motors and direct-drive wind turbines. In an effort to develop a more efficient electrochemical technique for depositing Dy on Nd-magnets in contrast to commonly used costly physical vapor deposition, we investigated the electrochemical behavior of dysprosium(iii) trifluoromethanesulfonate in a custom-made guanidinium-based room-temperature ionic liquid (RTIL). We first examined the electrodeposition of Dy on an Au(111) model electrode. The investigation was carried out by means of cyclic voltammetry (CV) and X-ray photoelectron spectroscopy (XPS). The initial stages of metal deposition were followed by in situ scanning tunneling microscopy (STM). CV measurements revealed a large cathodic reduction peak, which corresponds to the growth of monoatomic high islands, based on STM images taken during the initial stages of deposition. XPS identified these deposited islands as dysprosium. A similar reduction peak was also observed on an Nd-Fe-B substrate, and positively identified as deposited Dy using XPS. Finally, we varied the concentration of the Dy precursor, electrolyte flow and temperature during Dy deposition and demonstrated that each of these parameters could be used to increase the thickness of the Dy deposit, suggesting that these parameters could be tuned simultaneously in a temperature-controlled flow cell to enhance the thickness of the Dy layer. Electronic supplementary information (ESI) available. See DOI: 10.1039/C6NR01351A

Self-Healing Behavior of Ethylene-Based Ionomers

NASA Technical Reports Server (NTRS)

Kalista, Stephen J., Jr.; Ward, Thomas C.; Oyetunji, Zainab

2004-01-01

The self-healing behavior of poly(ethylene-co-methacrylic acid) (EMAA)-based ionomers holds tremendous potential for use in a wide variety of unique applications. However, to effectively utilize this self-healing behavior and to design novel materials which possess this ability, the mechanism by which they heal must first be understood ionomers are a class of polymers that can be described as copolymers containing less than 15 mol% ionic content whereby the bulk properties are governed by ionic interactions within the polymer. These ionic groups aggregate into discrete regions known as multiplets which overlap forming clusters that act as physical cross-links profoundly influencing the bulk physical properties. These clusters possess an order-disorder transition (T(sub i)) where the clustered regions may rearrange themselves given time and stimuli. Recognizing the strong influence of these ionic regions on other well understood ionomer properties, their role in self-heating behavior will be assessed. The self-healing behavior is observed following projectile puncture. It has been suggested that during impact energy is passed to the ionomer material, heating it to the melt state. After penetration, it is proposed that the ionic regions maintain their attractions and flow together patching the hole. Thus, the importance of this ionic character and is unique interaction must be established. This will be accomplished through examination of materials with varying ionic content and through the analysis of the T(sub i). The specific ionomer systems examined include a number of ethylene-based materials. Materials of varying ionic content, including the non-ionic base copolymers, will be examined by peel tests, projectile impact and DSC analysis. The information will also be compared with some basic data on LDPE material.

Low-sample flow secondary electrospray ionization: improving vapor ionization efficiency.

PubMed

Vidal-de-Miguel, G; Macía, M; Pinacho, P; Blanco, J

2012-10-16

In secondary electrospray ionization (SESI) systems, gaseous analytes exposed to an elecrospray plume become ionized after charge is transferred from the charging electrosprayed particles to the sample species. Current SESI systems have shown a certain potential. However, their ionization efficiency is limited by space charge repulsion and by the high sample flows required to prevent vapor dilution. As a result, they have a poor conversion ratio of vapor into ions. We have developed and tested a new SESI configuration, termed low-flow SESI, that permits the reduction of the required sample flows. Although the ion to vapor concentration ratio is limited, the ionic flow to sample vapor flow ratio theoretically is not. The new ionizer is coupled to a planar differential mobility analyzer (DMA) and requires only 0.2 lpm of vapor sample flow to produce 3.5 lpm of ionic flow. The achieved ionization efficiency is 1/700 (one ion for every 700 molecules) for TNT and, thus, compared with previous SESI ionizers coupled with atmospheric pressure ionization-mass spectrometry (API-MS) (Mesonero, E.; Sillero, J. A.; Hernández, M.; Fernandez de la Mora, J. Philadelphia PA, 2009) has been improved by a large factor of at least 50-100 (our measurements indicate 70). The new ionizer coupled with the planar DMA and a triple quadrupole mass spectrometer (ABSciex API5000) requires only 20 fg (50 million molecules) to produce a discernible signal after mobility and MS(2) analysis.

Dynamic, nonlinear feedback regulation of slow pacemaking by A-type potassium current in ventral tegmental area neurons.

PubMed

Khaliq, Zayd M; Bean, Bruce P

2008-10-22

We analyzed ionic currents that regulate pacemaking in dopaminergic neurons of the mouse ventral tegmental area by comparing voltage trajectories during spontaneous firing with ramp-evoked currents in voltage clamp. Most recordings were made in brain slice, with key experiments repeated using acutely dissociated neurons, which gave identical results. During spontaneous firing, net ionic current flowing between spikes was calculated from the time derivative of voltage multiplied by cell capacitance, signal-averaged over many firing cycles to enhance resolution. Net inward interspike current had a distinctive nonmonotonic shape, reaching a minimum (generally <1 pA) between -60 and -55 mV. Under voltage clamp, ramps over subthreshold voltages elicited a time- and voltage-dependent outward current that peaked near -55 mV. This current was undetectable with 5 mV/s ramps and increased steeply with depolarization rate over the range (10-50 mV/s) typical of natural pacemaking. Ramp-evoked subthreshold current was resistant to alpha-dendrotoxin, paxilline, apamin, and tetraethylammonium but sensitive to 4-aminopyridine and 0.5 mM Ba2+, consistent with A-type potassium current (I(A)). Same-cell comparison of currents elicited by various ramp speeds with natural spontaneous depolarization showed how the steep dependence of I(A) on depolarization rate results in small net inward currents during pacemaking. These results reveal a mechanism in which subthreshold I(A) is near zero at steady state, but is engaged at depolarization rates >10 mV/s to act as a powerful, supralinear feedback element. This feedback mechanism explains how net ionic current can be constrained to <1-2 pA but reliably inward, thus enabling slow, regular firing.

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

Chen, Qing; Gerhardt, Michael R.; Aziz, Michael J.

We measure the polarization characteristics of a quinone-bromide redox flow battery with interdigitated flow fields, using electrochemical impedance spectroscopy and voltammetry of a full cell and of a half cell against a reference electrode. We find linear polarization behavior at 50% state of charge all the way to the short-circuit current density of 2.5 A/cm 2. We uniquely identify the polarization area-specific resistance (ASR) of each electrode, the membrane ASR to ionic current, and the electronic contact ASR. We use voltage probes to deduce the electronic current density through each sheet of carbon paper in the quinone-bearing electrode. By alsomore » interpreting the results using the Newman 1-D porous electrode model, we deduce the volumetric exchange current density of the porous electrode. We uniquely evaluate the power dissipation and identify a correspondence to the contributions to the electrode ASR from the faradaic, electronic, and ionic transport processes. We find that, within the electrode, more power is dissipated in the faradaic process than in the electronic and ionic conduction processes combined, despite the observed linear polarization behavior. We examine the sensitivity of the ASR to the values of the model parameters. The greatest performance improvement is anticipated from increasing the volumetric exchange current density.« less

Ionic transport through sub-10 nm diameter hydrophobic high-aspect ratio nanopores: experiment, theory and simulation

PubMed Central

Balme, Sébastien; Picaud, Fabien; Manghi, Manoel; Palmeri, John; Bechelany, Mikhael; Cabello-Aguilar, Simon; Abou-Chaaya, Adib; Miele, Philippe; Balanzat, Emmanuel; Janot, Jean Marc

2015-01-01

Fundamental understanding of ionic transport at the nanoscale is essential for developing biosensors based on nanopore technology and new generation high-performance nanofiltration membranes for separation and purification applications. We study here ionic transport through single putatively neutral hydrophobic nanopores with high aspect ratio (of length L = 6 μm with diameters ranging from 1 to 10 nm) and with a well controlled cylindrical geometry. We develop a detailed hybrid mesoscopic theoretical approach for the electrolyte conductivity inside nanopores, which considers explicitly ion advection by electro-osmotic flow and possible flow slip at the pore surface. By fitting the experimental conductance data we show that for nanopore diameters greater than 4 nm a constant weak surface charge density of about 10−2 C m−2 needs to be incorporated in the model to account for conductance plateaus of a few pico-siemens at low salt concentrations. For tighter nanopores, our analysis leads to a higher surface charge density, which can be attributed to a modification of ion solvation structure close to the pore surface, as observed in the molecular dynamics simulations we performed. PMID:26036687

Fractionation of poly(methacrylic acid) and poly(vinyl pyridine) in aqueous and organic mobile phases by multidetector thermal field-flow fractionation.

PubMed

Greyling, Guilaume; Pasch, Harald

2017-08-25

Multidetector thermal field-flow fractionation (ThFFF) is shown to be a versatile characterisation platform that can be used to characterise hydrophilic polymers in a variety of organic and aqueous solutions with various ionic strengths. It is demonstrated that ThFFF fractionates isotactic and syndiotactic poly(methacrylic acid) (PMAA) as well as poly(2-vinyl pyridine) (P2VP) and poly(4-vinyl pyridine) (P4VP) according to microstructure in organic solvents and that the ionic strength of the mobile phase has no influence on the retention behaviour of the polymers. With regard to aqueous solutions, it is shown that, despite the weak retention, isotactic and syndiotactic PMAA show different retention behaviours which can qualitatively be attributed to microstructure. Additionally, it is shown that the ionic strength of the mobile phase has a significant influence on the thermal diffusion of polyelectrolytes in aqueous solutions and that the addition of an electrolyte is essential to achieve a microstructure-based separation of P2VP and P4VP in aqueous solutions. Copyright © 2017 Elsevier B.V. All rights reserved.

Communication: Unusual structure and transport in ionic liquid-hexane mixtures

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

Liang, Min; Khatun, Sufia; Castner, Edward W., E-mail: ecastner@rci.rutgers.edu

2015-03-28

Ionic liquids having a sufficiently amphiphilic cation can dissolve large volume fractions of alkanes, leading to mixtures with intriguing properties on molecular length scales. The trihexyl(tetradecyl)phosphonium cation paired with the bis(trifluoromethylsulfonyl)amide anion provides an ionic liquid that can dissolve large mole fractions of hexane. We present experimental results on mixtures of n-C{sub 6}D{sub 14} with this ionic liquid. High-energy X-ray scattering studies reveal a persistence of the characteristic features of ionic liquid structure even for 80% dilution with n-C{sub 6}D{sub 14}. Nuclear magnetic resonance self-diffusion results reveal decidedly non-hydrodynamic behavior where the self-diffusion of the neutral, non-polar n-C{sub 6}D{sub 14}more » is on average a factor of 21 times faster than for the cation. Exploitation of the unique structural and transport properties of these mixtures may lead to new opportunities for designer solvents for enhanced chemical reactivity and interface science.« less

Process intensification of biodiesel production by using microwave and ionic liquids as catalyst

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

Handayani, Prima Astuti; Chemical Engineering Program, Faculty of Engineering, Semarang State University; Abdullah

The energy crisis pushes the development and intensification of biodiesel production process. Biodiesel is produced by transesterification of vegetable oils or animal fats and conventionally produced by using acid/base catalyst. However, the conventional method requires longer processing time and obtains lower yield of biodiesel. The microwave has been intensively used to accelerate production process and ionic liquids has been introduced as source of catalyst. This paper discusses the overview of the development of biodiesel production through innovation using microwave irradiation and ionic liquids catalyst to increase the yield of biodiesel. The potential microwave to reduce the processing time will bemore » discussed and compared with other energy power, while the ionic liquids as a new generation of catalysts in the chemical industry will be also discussed for its use. The ionic liquids has potential to enhance the economic and environmental aspects because it has a low corrosion effect, can be recycled, and low waste form.« less

Structure and mechanisms underlying ion transport in ternary polymer electrolytes containing ionic liquids

NASA Astrophysics Data System (ADS)

Mogurampelly, Santosh; Ganesan, Venkat

2017-02-01

We use all atom molecular dynamics simulations to investigate the influence of 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6) ionic liquid on the structure and transport properties of poly(ethylene oxide) (PEO) polymer electrolytes doped with LiPF6 salt. We observe enhanced diffusivities of the Li+, PF6-, and BMIM+ ions with increasing loading of the ionic liquid. Interplay between the different ion-ion and ion-polymer interactions is seen to lead to a destabilization of the Li-PF6 coordination and increase in the strength of association between the Li+ cations and the polymer backbone. As a consequence, the polymer segmental relaxation times are shown to be only moderately affected by the addition of ionic liquids. The ionic-liquid induced changes in the mobilities of Li+ ions are seen to be correlated to polymer segmental relaxation times. However, the mobilities of BMIM+ ions are seen to be more strongly correlated to the BMIM-PF6 ion-pair relaxation times.

Process intensification of biodiesel production by using microwave and ionic liquids as catalyst

NASA Astrophysics Data System (ADS)

Handayani, Prima Astuti; Abdullah, dan Hadiyanto

2015-12-01

The energy crisis pushes the development and intensification of biodiesel production process. Biodiesel is produced by transesterification of vegetable oils or animal fats and conventionally produced by using acid/base catalyst. However, the conventional method requires longer processing time and obtains lower yield of biodiesel. The microwave has been intensively used to accelerate production process and ionic liquids has been introduced as source of catalyst. This paper discusses the overview of the development of biodiesel production through innovation using microwave irradiation and ionic liquids catalyst to increase the yield of biodiesel. The potential microwave to reduce the processing time will be discussed and compared with other energy power, while the ionic liquids as a new generation of catalysts in the chemical industry will be also discussed for its use. The ionic liquids has potential to enhance the economic and environmental aspects because it has a low corrosion effect, can be recycled, and low waste form.

Effect of Aprotic Solvents on the Dynamics of a Room Temperature Ionic Liquid

NASA Astrophysics Data System (ADS)

Osti, Naresh; van Aken, Katherine; Thompson, Matthew; Tiet, Felix; Jiang, De-En; Cummings, Peter; Gogotsi, Yury; Mamontov, Eugene

Room temperature ionic liquids (RTILs) have attracted much attention as electrolytes in energy storage devices because of their peculiar physical and chemical characteristics. However, their remarkably high viscosity, which results in low conductivity and diffusivity, may adversely affect the charging and discharging rates. Despite changing molecular configurations, use of aprotic solvent allows to enhance the transport properties of ionic liquids by disrupting the cation-anion interactions. We explore the impact of dipole moment of aprotic solvents on the cation-anion interaction and transport in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [BMIM +][Tf2N-], RTIL using molecular dynamics (MD) simulations and quasi-elastic neutrons scattering (QENS) measurements. We observed an increase in cation diffusivity with the increasing dipole moment of the solvent. This effect is due to a decrease in the solvation free energy induced by the increasing solvent polarity. A clear nano-phase separation into ionic liquid-rich and ionic liquid-poor phases as observed by QENS will be also discussed.

Communication: Unusual structure and transport in ionic liquid-hexane mixtures

DOE PAGES

Liang, Min; Khatun, Sufia; Castner, Edward W.

2015-03-28

Ionic liquids having a sufficiently amphiphilic cation can dissolve large volume fractions of alkanes, leading to mixtures with intriguing properties on molecular length scales. The trihexyl(tetradecyl)phosphonium cation paired with the bis(trifluoromethylsulfonyl)amide anion provides an ionic liquid that can dissolve large mole fractions of hexane. We present experimental results on mixtures of n-C 6D 14 with this ionic liquid. High- energy X-ray scattering studies reveal a persistence of the characteristic features of ionic liquid structure even for 80% dilution with n-C 6D 14. NMR self-diffusion results reveal decidedly non-hydrodynamic behavior where the self-diffusion of the neutral, non-polar n-C 6D 14 ismore » on average a factor of 21 times faster than for the cation. Exploitation of the unique structural and transport properties of these mixtures may lead to new opportunities for designer solvents for enhanced chemical reactivity and interface science.« less

Molecular dynamics study of thermodynamic stability and dynamics of [Li(glyme)]+ complex in lithium-glyme solvate ionic liquids

NASA Astrophysics Data System (ADS)

Shinoda, Wataru; Hatanaka, Yuta; Hirakawa, Masashi; Okazaki, Susumu; Tsuzuki, Seiji; Ueno, Kazuhide; Watanabe, Masayoshi

2018-05-01

Equimolar mixtures of glymes and organic lithium salts are known to produce solvate ionic liquids, in which the stability of the [Li(glyme)]+ complex plays an important role in determining the ionic dynamics. Since these mixtures have attractive physicochemical properties for application as electrolytes, it is important to understand the dependence of the stability of the [Li(glyme)]+ complex on the ion dynamics. A series of microsecond molecular dynamics simulations has been conducted to investigate the dynamic properties of these solvate ionic liquids. Successful solvate ionic liquids with high stability of the [Li(glyme)]+ complex have been shown to have enhanced ion dynamics. Li-glyme pair exchange rarely occurs: its characteristic time is longer than that of ion diffusion by one or two orders of magnitude. Li-glyme pair exchange most likely occurs through cluster formation involving multiple [Li(glyme)]+ pairs. In this process, multiple exchanges likely take place in a concerted manner without the production of energetically unfavorable free glyme or free Li+ ions.

Development of cellulase-nanoconjugates with enhanced ionic liquid and thermal stability for in situ lignocellulose saccharification.

PubMed

Grewal, Jasneet; Ahmad, Razi; Khare, S K

2017-10-01

The present work aimed to improve catalytic efficiency of Trichoderma reesei cellulase for enhanced saccharification. The cellulase was immobilized on two nanomatrices i.e. magnetic and silica nanoparticles with immobilization efficiency of 85% and 76% respectively. The nanobioconjugates exhibited increase in V max , temperature optimum, pH and thermal stability as compared with free enzyme. These could be efficiently reused for five repeated cycles and were stable in 1-ethyl-3-methylimidazoliumacetate [EMIM][Ac], an ionic liquid. Ionic liquids (IL) are used as green solvents to dissolve lignocellulosic biomass and facilitate better saccharification. The cellulase immobilized on magnetic nanoparticles was used for in situ saccharification of [EMIM][Ac] pretreated sugarcane bagasse and wheat straw for two cycles. The structural deconstruction and decrease in biomass crystallinity was confirmed by SEM, XRD and FTIR. The high hydrolysis yields (∼89%) obtained in this one-pot process coupled with IL stability and recycled use of immobilized cellulase, potentiates its usefulness in biorefineries. Copyright © 2017 Elsevier Ltd. All rights reserved.

Hydrogen bonding in ionic liquids.

PubMed

Hunt, Patricia A; Ashworth, Claire R; Matthews, Richard P

2015-03-07

Ionic liquids (IL) and hydrogen bonding (H-bonding) are two diverse fields for which there is a developing recognition of significant overlap. Doubly ionic H-bonds occur when a H-bond forms between a cation and anion, and are a key feature of ILs. Doubly ionic H-bonds represent a wide area of H-bonding which has yet to be fully recognised, characterised or explored. H-bonds in ILs (both protic and aprotic) are bifurcated and chelating, and unlike many molecular liquids a significant variety of distinct H-bonds are formed between different types and numbers of donor and acceptor sites within a given IL. Traditional more neutral H-bonds can also be formed in functionalised ILs, adding a further level of complexity. Ab initio computed parameters; association energies, partial charges, density descriptors as encompassed by the QTAIM methodology (ρBCP), qualitative molecular orbital theory and NBO analysis provide established and robust mechanisms for understanding and interpreting traditional neutral and ionic H-bonds. In this review the applicability and extension of these parameters to describe and quantify the doubly ionic H-bond has been explored. Estimating the H-bonding energy is difficult because at a fundamental level the H-bond and ionic interaction are coupled. The NBO and QTAIM methodologies, unlike the total energy, are local descriptors and therefore can be used to directly compare neutral, ionic and doubly ionic H-bonds. The charged nature of the ions influences the ionic characteristics of the H-bond and vice versa, in addition the close association of the ions leads to enhanced orbital overlap and covalent contributions. The charge on the ions raises the energy of the Ylp and lowers the energy of the X-H σ* NBOs resulting in greater charge transfer, strengthening the H-bond. Using this range of parameters and comparing doubly ionic H-bonds to more traditional neutral and ionic H-bonds it is clear that doubly ionic H-bonds cover the full range of weak through to very strong H-bonds.

A highly permeable and enhanced surface area carbon-cloth electrode for vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Zhou, X. L.; Zhao, T. S.; Zeng, Y. K.; An, L.; Wei, L.

2016-10-01

In this work, a high-performance porous electrode, made of KOH-activated carbon-cloth, is developed for vanadium redox flow batteries (VRFBs). The macro-scale porous structure in the carbon cloth formed by weaving the carbon fibers in an ordered manner offers a low tortuosity (∼1.1) and a broad pore distribution from 5 μm to 100 μm, rendering the electrode a high hydraulic permeability and high effective ionic conductivity, which are beneficial for the electrolyte flow and ion transport through the porous electrode. The use of KOH activation method to create nano-scale pores on the carbon-fiber surfaces leads to a significant increase in the surface area for redox reactions from 2.39 m2 g-1 to 15.4 m2 g-1. The battery assembled with the present electrode delivers an energy efficiency of 80.1% and an electrolyte utilization of 74.6% at a current density of 400 mA cm-2, as opposed to an electrolyte utilization of 61.1% achieved by using a conventional carbon-paper electrode. Such a high performance is mainly attributed to the combination of the excellent mass/ion transport properties and the high surface area rendered by the present electrode. It is suggested that the KOH-activated carbon-cloth electrode is a promising candidate in redox flow batteries.

Bifunctional Crosslinking Agents Enhance Anion Exchange Membrane Efficacy for Vanadium Redox Flow Batteries.

PubMed

Wang, Wenpin; Xu, Min; Wang, Shubo; Xie, Xiaofeng; Lv, Yafei; Ramani, Vijay K

2014-06-02

A series of cross-linked fluorinated poly (aryl ether oxadiazole) membranes (FPAEOM) derivatized with imidazolium groups were prepared. Poly (N-vinylimidazole) (PVI) was used as the bifunctional cross-linking agent to: a) lower vanadium permeability, b) enhance dimensional stability, and c) concomitantly provide added ion exchange capacity in the resultant anion exchange membranes. At a molar ratio of PVI to FPAEOM of 1.5, the resultant membrane (FPAEOM-1.5 PVI) had an ion exchange capacity of 2.2 meq g-1, a vanadium permeability of 6.8×10-7 cm2 min-1, a water uptake of 68 wt.%, and an ionic conductivity of 22.0 mS cm-1, all at 25°C. Single cells prepared with the FPAEOM-1.5 PVI membrane exhibited a higher coulombic efficiency (> 92%) and energy efficiency (> 86%) after 40 test cycles in vanadium redox flow battery. The imidazolium cation showed high chemical stability in highly acidic and oxidizing vanadium solution as opposed to poor stability in alkaline solutions. Based on our DFT studies, this was attributed to the lower HOMO energy (-7.265 eV) of the HSO4- ion (compared to the OH- ion; -5.496 eV) and the larger HOMO-LUMO energy gap (6.394 eV) of dimethylimidazolium bisulfate ([DMIM] [HSO4]) as compared to [DMIM] [OH] (5.387 eV).

Improvement of Biodesulfurization Rate of Alginate Immobilized Rhodococcus erythropolis R1

PubMed Central

Derikvand, Peyman; Etemadifar, Zahra

2014-01-01

Background: Sulfur oxides released from the burning of oil causes severe environmental pollution. The sulfur can be removed via the 4S pathway in biodesulfurization (BDS). Immobilization approaches have been developed to prevent cell contamination of oil during the BDS process. Objectives: The encapsulation of Rhodococcus erythropolis R1 in calcium alginate beads was studied in order to enhance conversion of dibenzothiophene (DBT) to 2-hydroxy biphenyl (2-HBP) as the final product. Also the effect of different factors on the BDS process was investigated. Materials and Methods: Calcium alginate capsules were prepared using peristaltic pumps with different needle sizes to control the beads sizes. Scanning electron microscopy and flow cytometry methods were used to study the distribution and viability of encapsulated cells, respectively. Two non-ionic surfactants and also nano Ƴ-Al2O3were used with the ratio of 0.5% (v/v) and 1:5 (v/v) respectively to investigate their BDS efficiency. In addition, the effect of different bead sizes and different concentrations of sodium alginate in BDS activity was studied. Results: The 2% (w/v) sodium alginate beads with 1.5mm size were found to be the optimum for beads stability and efficient 2-HBP production. The viability of encapsulated cells decreased by 12% after 20 h of desulfurization, compared to free cells. Adding the non-ionic surfactants markedly enhanced the rate of BDS, because of increasing mass transfer of DBT to the gel matrix. In addition, Span 80 was more effective than Tween 80. The nanoƳ-Al2O3 particles could increase BDS rate by up to two-folds greater than that of the control beads. Conclusions: The nano Ƴ-Al2O3 can improve the immobilized biocatalyst for excellent efficiency of DBT desulfurization. Also the BDS activity can be enhanced by setting the other explained factors at optimum levels. PMID:25147685

Improvement of Biodesulfurization Rate of Alginate Immobilized Rhodococcus erythropolis R1.

PubMed

Derikvand, Peyman; Etemadifar, Zahra

2014-03-01

Sulfur oxides released from the burning of oil causes severe environmental pollution. The sulfur can be removed via the 4S pathway in biodesulfurization (BDS). Immobilization approaches have been developed to prevent cell contamination of oil during the BDS process. The encapsulation of Rhodococcus erythropolis R1 in calcium alginate beads was studied in order to enhance conversion of dibenzothiophene (DBT) to 2-hydroxy biphenyl (2-HBP) as the final product. Also the effect of different factors on the BDS process was investigated. Calcium alginate capsules were prepared using peristaltic pumps with different needle sizes to control the beads sizes. Scanning electron microscopy and flow cytometry methods were used to study the distribution and viability of encapsulated cells, respectively. Two non-ionic surfactants and also nano Ƴ-Al2O3were used with the ratio of 0.5% (v/v) and 1:5 (v/v) respectively to investigate their BDS efficiency. In addition, the effect of different bead sizes and different concentrations of sodium alginate in BDS activity was studied. The 2% (w/v) sodium alginate beads with 1.5mm size were found to be the optimum for beads stability and efficient 2-HBP production. The viability of encapsulated cells decreased by 12% after 20 h of desulfurization, compared to free cells. Adding the non-ionic surfactants markedly enhanced the rate of BDS, because of increasing mass transfer of DBT to the gel matrix. In addition, Span 80 was more effective than Tween 80. The nanoƳ-Al2O3 particles could increase BDS rate by up to two-folds greater than that of the control beads. The nano Ƴ-Al2O3 can improve the immobilized biocatalyst for excellent efficiency of DBT desulfurization. Also the BDS activity can be enhanced by setting the other explained factors at optimum levels.

Multilevel Molecular Modeling Approach for a Rational Design of Ionic Current Sensors for Nanofluidics.

PubMed

Kirch, Alexsandro; de Almeida, James M; Miranda, Caetano R

2018-05-10

The complexity displayed by nanofluidic-based systems involves electronic and dynamic aspects occurring across different size and time scales. To properly model such kind of system, we introduced a top-down multilevel approach, combining molecular dynamics simulations (MD) with first-principles electronic transport calculations. The potential of this technique was demonstrated by investigating how the water and ionic flow through a (6,6) carbon nanotube (CNT) influences its electronic transport properties. We showed that the confinement on the CNT favors the partially hydrated Na, Cl, and Li ions to exchange charge with the nanotube. This leads to a change in the electronic transmittance, allowing for the distinguishing of cations from anions. Such an ionic trace may handle an indirect measurement of the ionic current that is recorded as a sensing output. With this case study, we are able to show the potential of this top-down multilevel approach, to be applied on the design of novel nanofluidic devices.

On the mobility of carriers at semi-coherent oxide heterointerfaces

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

Dholabhai, Pratik P.; Martinez, Enrique Saez; Brown, Nicholas Taylor

In the quest to develop new materials with enhanced ionic conductivity for battery and fuel cell applications, nano-structured oxides have attracted attention. Experimental reports indicate that oxide heterointerfaces can lead to enhanced ionic conductivity, but these same reports cannot elucidate the origin of this enhancement, often vaguely referring to pipe diffusion at misfit dislocations as a potential explanation. However, this highlights the need to understand the role of misfit dislocation structure at semi-coherent oxide heterointerfaces in modifying carrier mobilities. Here, we use atomistic and kinetic Monte Carlo (KMC) simulations to develop a model of oxygen vacancy migration at SrTiO 3/MgOmore » interfaces, chosen because the misfit dislocation structure can be modified by changing the termination chemistry. We use atomistic simulations to determine the energetics of oxygen vacancies at both SrO and TiO 2 terminated interfaces, which are then used as the basis of the KMC simulations. While this model is approximate (as revealed by select nudged elastic band calculations), it highlights the role of the misfit dislocation structure in modifying the oxygen vacancy dynamics. We find that oxygen vacancy mobility is significantly reduced at either interface, with slight differences at each interface due to the differing misfit dislocation structure. Here, we conclude that if such semi-coherent oxide heterointerfaces induce enhanced ionic conductivity, it is not a consequence of higher carrier mobility.« less

Performance enhancement of molten carbonate-based direct carbon fuel cell (MC-DCFC) via adding mixed ionic-electronic conductors into Ni anode catalyst layer

NASA Astrophysics Data System (ADS)

Lee, Eun-Kyung; Park, Shin-Ae; Jung, Hyun-Woo; Kim, Yong-Tae

2018-05-01

A high overpotential in the anode of Direct Carbon Fuel Cells (DCFC) is ascribed to the sluggish kinetics of solid fuel oxidation. In this study, we demonstrate a unique approach to enhance the performance of molten-carbonate electrolyte based DCFC (MC-DCFC) by decreasing a serious polarization loss at the anode side; a simple addition of lanthanum strontium cobalt ferrite (LSCF) having a function of mixed ionic-electronic conductors (MIEC) into the Ni anode catalyst layer. Ni:LSCF = 1:1 showed markedly enhanced peak power density of 111 mW/cm2, approximately two-fold higher value than that for the anode using solely Ni and one of the best record in the literature value using carbon black fuel without any contribution of generated syngas oxidation. As can be noted from the electrochemical impedance spectroscopy data, the ohmic and the charge transfer resistance of the anode was markedly decreased owing to the high ionic-electronic conductivity of the MIECs. Furthermore, the enhanced performance can be also attributed to the maximized TPBs (triple phase boundaries) that participate in the carbon oxidation reaction. Based on the results, we suggest that the addition of MIEC materials into the Ni anode catalyst layer is a promising approach to improve the performance of MC-DCFC.

On the mobility of carriers at semi-coherent oxide heterointerfaces

DOE PAGES

Dholabhai, Pratik P.; Martinez, Enrique Saez; Brown, Nicholas Taylor; ...

2017-08-17

In the quest to develop new materials with enhanced ionic conductivity for battery and fuel cell applications, nano-structured oxides have attracted attention. Experimental reports indicate that oxide heterointerfaces can lead to enhanced ionic conductivity, but these same reports cannot elucidate the origin of this enhancement, often vaguely referring to pipe diffusion at misfit dislocations as a potential explanation. However, this highlights the need to understand the role of misfit dislocation structure at semi-coherent oxide heterointerfaces in modifying carrier mobilities. Here, we use atomistic and kinetic Monte Carlo (KMC) simulations to develop a model of oxygen vacancy migration at SrTiO 3/MgOmore » interfaces, chosen because the misfit dislocation structure can be modified by changing the termination chemistry. We use atomistic simulations to determine the energetics of oxygen vacancies at both SrO and TiO 2 terminated interfaces, which are then used as the basis of the KMC simulations. While this model is approximate (as revealed by select nudged elastic band calculations), it highlights the role of the misfit dislocation structure in modifying the oxygen vacancy dynamics. We find that oxygen vacancy mobility is significantly reduced at either interface, with slight differences at each interface due to the differing misfit dislocation structure. Here, we conclude that if such semi-coherent oxide heterointerfaces induce enhanced ionic conductivity, it is not a consequence of higher carrier mobility.« less

Thermal boundary conductance of hydrophilic and hydrophobic ionic liquids

NASA Astrophysics Data System (ADS)

Oyake, Takafumi; Sakata, Masanori; Yada, Susumu; Shiomi, Junichiro

2015-03-01

A solid/liquid interface plays a critical role for understanding mechanisms of biological and physical science. Moreover, carrier density of the surface is dramatically enhanced by electric double layer with ionic liquid, salt in the liquid state. Here, we have measured the thermal boundary conductance (TBC) across an interface of gold thin film and ionic liquid by using time-domain thermoreflectance technique. Following the prior researches, we have identified the TBC of two interfaces. One is gold and hydrophilic ionic liquid, N,N-Diethyl-N-methyl-N-(2-methoxyethyl) ammonium tetrafluoroborate (DEME-BF4), which is a hydrophilic ionic liquid, and the other is N,N-Diethyl-N-methyl-N-(2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide (DEME-TFSI), which is a hydrophobic ionic liquid. We found that the TBC between gold and DEME-TFIS (19 MWm-2K-1) is surprisingly lower than the interface between gold and DEME-BF4 (45 MWm-2K-1). With these data, the importance of the wetting angle and ion concentration for the thermal transport at the solid/ionic liquid interface is discussed. Part of this work is financially supported by Japan Society for the Promotion of Science (JSPS) and Japan Science and Technology Agency. The author is financially supported by JSPS Fellowship.

Electroactive nanostructured polymer actuators fabricated using sulfonated styrenic pentablock copolymer/montmorillonite/ionic liquid nanocomposite membranes

NASA Astrophysics Data System (ADS)

Lee, Jang-Woo; Hong, Soon Man; Koo, Chong Min

2014-08-01

High-bendable, air-operable ionic polymer-metal composite (IPMC) actuators composed of electroactive nanostructured middle-block sulfonated styrenic pentablock copolymer (SSPB)/sulfonated montmorillonite (s-MMT) nanocomposite electrolyte membranes with bulky imidazolium ionic liquids (ILs) incorporated were fabricated and their bending actuation performances were evaluated. The SSPB-based IPMC actuators showed larger air-operable bending displacements, higher displacement rates, and higher energy efficiency of actuations without conventional IPMC bottlenecks, including back relaxation and actuation instability during actuation in air, than the Nafion counterpart. Incorporation of s-MMT into the SSPB matrix further enhanced the actuation performance of the IPMC actuators in terms of displacement, displacement rate, and energy efficiency. The remarkably high performance of the SSPB/s-MMT/IL IPMCs was considered to be due to the microphase-separated large ionic domains of the SSPB (the average diameter of the ionic domain: ca. 20 nm) and the role of s-MMT as an ionic bridge between the ionic domains, and the ion pumping effect of the bulky imidazolium cations of the ILs as well. The microphase-separated nanostructure of the composite membranes caused a high dimensional stability upon swelling in the presence of ILs, which effectively preserved the original electrode resistance against swelling, leading to a high actuation performance of IPMC.

Radiation-grafted fluoropolymers soaked with imidazolium-based ionic liquids for high-performance ionic polymer-metal composite actuators.

PubMed

Lee, Jang Yeol; Wang, Hyuck Sik; Yoon, Bye Ri; Han, Man Jae; Jho, Jae Young

2010-11-01

On purpose to develop a polymer actuator with high stability in air-operation as well as large bending displacement, a series of ionic polymer-metal composites (IPMC) was constructed with poly(styrene sulfonate)-grafted fluoropolymers as ionomeric matrix and immidazolium-based ionic liquids (IL) as inner solvent. The prepared IPMC actuators exhibited greatly enhanced bending displacement compared to Nafion-based actuators. The actuators were stable in air-operation, maintaining initial displacement for up to 10(4) cycles or 24 h. Investigating the material parameters and morphology of the IPMCs, high ion exchange capacity of the ionomers resulted in high ion conductivity and robust electrode of IPMC, which synergistically contributed to the high bending performance. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Towards an all-copper redox flow battery based on a copper-containing ionic liquid.

PubMed

Schaltin, Stijn; Li, Yun; Brooks, Neil R; Sniekers, Jeroen; Vankelecom, Ivo F J; Binnemans, Koen; Fransaer, Jan

2016-01-07

The first redox flow battery (RFB), based on the all-copper liquid metal salt [Cu(MeCN)4][Tf2N], is presented. Liquid metal salts (LMS) are a new type of ionic liquid that functions both as solvent and electrolyte. Non-aqueous electrolytes have advantages over water-based solutions, such as a larger electrochemical window and large thermal stability. The proof-of-concept is given that LMSs can be used as the electrolyte in RFBs. The main advantage of [Cu(MeCN)4][Tf2N] is the high copper concentration, and thus high charge and energy densities of 300 kC l(-1) and 75 W h l(-1) respectively, since the copper(i) ions form an integral part of the electrolyte. A Coulombic efficiency up to 85% could be reached.

The ionic DTI model (iDTI) of dynamic diffusion tensor imaging (dDTI)

PubMed Central

Makris, Nikos; Gasic, Gregory P.; Garrido, Leoncio

2014-01-01

Measurements of water molecule diffusion along fiber tracts in CNS by diffusion tensor imaging (DTI) provides a static map of neural connections between brain centers, but does not capture the electrical activity along axons for these fiber tracts. Here, a modification of the DTI method is presented to enable the mapping of active fibers. It is termed dynamic diffusion tensor imaging (dDTI) and is based on a hypothesized “anisotropy reduction due to axonal excitation” (“AREX”). The potential changes in water mobility accompanying the movement of ions during the propagation of action potentials along axonal tracts are taken into account. Specifically, the proposed model, termed “ionic DTI model”, was formulated as follows.•First, based on theoretical calculations, we calculated the molecular water flow accompanying the ionic flow perpendicular to the principal axis of fiber tracts produced by electrical conduction along excited myelinated and non-myelinated axons.•Based on the changes in molecular water flow we estimated the signal changes as well as the changes in fractional anisotropy of axonal tracts while performing a functional task.•The variation of fractional anisotropy in axonal tracts could allow mapping the active fiber tracts during a functional task. Although technological advances are necessary to enable the robust and routine measurement of this electrical activity-dependent movement of water molecules perpendicular to axons, the proposed model of dDTI defines the vectorial parameters that will need to be measured to bring this much needed technique to fruition. PMID:25431757

Extremely dense microstructure and enhanced ionic conductivity in hot-isostatic pressing treated cubic garnet-type solid electrolyte of Ga2O3-doped Li7La3Zr2O12

NASA Astrophysics Data System (ADS)

Qin, Shiying; Zhu, Xiaohong; Jiang, Yue; Ling, Ming’En; Hu, Zhiwei; Zhu, Jiliang

A large number of pores and a low relative density that are frequently observed in solid electrolytes reduce severely their ionic conductivity and thus limit their applicability. Here, we report on the use of hot isostatic pressing (HIP) for ameliorating the garnet-type lithium-ion conducting solid electrolyte of Ga2O3-doped Li7La3Zr2O12 (Ga-LLZO) with nominal composition of Li6.55Ga0.15La3Zr2O12. The Ga-LLZO pellets were conventionally sintered at 1075∘C for 12h, and then were followed by HIP treatment at 120MPa and 1160∘C under an Ar atmosphere. It is found that the HIP-treated Ga-LLZO shows an extremely dense microstructure and a significantly enhanced ionic conductivity. Coherent with the increase in relative density from 90.5% (untreated) to 97.5% (HIP-treated), the ionic conductivity of the HIP-treated Ga-LLZO reaches as high as 1.13×10‑3S/cm at room temperature (25∘C), being two times higher than that of 4.58×10‑4S/cm for the untreated one.

Polarization Effects on the Cellulose Dissolution in Ionic Liquids: Molecular Dynamics Simulations with Polarization Model and Integrated Tempering Enhanced Sampling Method.

PubMed

Kan, Zigui; Zhu, Qiang; Yang, Lijiang; Huang, Zhixiong; Jin, Biaobing; Ma, Jing

2017-05-04

Conformation of cellulose with various degree of polymerization of n = 1-12 in ionic liquid 1,3-dimethylimidazolium chloride ([C 1 mim]Cl) and the intermolecular interaction between them was studied by means of molecular dynamics (MD) simulations with fixed-charge and charge variable polarizable force fields, respectively. The integrated tempering enhanced sampling method was also employed in the simulations in order to improve the sampling efficiency. Cellulose undergoes significant conformational changes from a gaseous right-hand helical twist along the long axis to a flexible conformation in ionic liquid. The intermolecular interactions between cellulose and ionic liquid were studied by both infrared spectrum measurements and theoretical simulations. Designated by their puckering parameters, the pyranose rings of cellulose oligomers are mainly arranged in a chair conformation. With the increase in the degree of polymerization of cellulose, the boat and skew-boat conformations of cellulose appear in the MD simulations, especially in the simulations with polarization model. The number and population of hydrogen bonds between the cellulose and the chloride anions show that chloride anion is prone to form HBs whenever it approaches the hydroxyl groups of cellulose and, thus, each hydroxyl group is fully hydrogen bonded to the chloride anion. MD simulations with polarization model presented more abundant conformations than that with nonpolarization model. The application of the enhanced sampling method further enlarged the conformational spaces that could be visited by facilitating the system escaping from the local minima. It was found that the electrostatics interactions between the cellulose and ionic liquid contribute more to the total interaction energies than the van der Waals interactions. Although the interaction energy between the cellulose and anion is about 2.9 times that between the cellulose and cation, the role of cation is non-negligible. In contrast, the interaction energy between the cellulose and water is too weak to dissolve cellulose in water.

Label-free biosensing with functionalized nanopipette probes.

PubMed

Umehara, Senkei; Karhanek, Miloslav; Davis, Ronald W; Pourmand, Nader

2009-03-24

Nanopipette technology can uniquely identify biomolecules such as proteins based on differences in size, shape, and electrical charge. These differences are determined by the detection of changes in ionic current as the proteins interact with the nanopipette tip coated with probe molecules. Here we show that electrostatic, biotin-streptavidin, and antibody-antigen interactions on the nanopipette tip surface affect ionic current flowing through a 50-nm pore. Highly charged polymers interacting with the glass surface modulated the rectification property of the nanopipette electrode. Affinity-based binding between the probes tethered to the surface and their target proteins caused a change in the ionic current due to a partial blockade or an altered surface charge. These findings suggest that nanopipettes functionalized with appropriate molecular recognition elements can be used as nanosensors in biomedical and biological research.

Experimental and Theoretical Study on Supramolecular Ionic Liquid (IL)-Asphaltene Complex Interactions and Their Effects on the Flow Properties of Heavy Crude Oils.

PubMed

Hernández-Bravo, R; Miranda, A D; Martínez-Magadán, J-M; Domínguez, J M

2018-04-19

A combined study for understanding the molecular interactions of asphaltenes with molecular species such as ionic liquids (ILs) comprised experimental measurements and computational numerical simulation calculations, using density-functional theory (DFT) with dispersion corrections, molecular dynamics (MD) calculations, and experimental rheological characterization of the heavy crude oils (HCOs), before and after doping with ILs, respectively. The main results show that ILs influence the asphaltenic dimer association by forming supramolecular complexes that modify the properties of crude oils such as viscosity and interfacial tension. The IL-cation and asphaltene-π ligand molecular interactions seem to dominate the interactions between ionic liquids and asphaltenes, where ILs' high aromaticity index induces a strong interaction with the aromatic hard core of asphaltenes.

Influences of porous reservoir Laplace pressure on emissions from passively fed ionic liquid electrospray sources

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

Courtney, Daniel G., E-mail: dcourtney@alum.mit.edu; Shea, Herbert

2015-09-07

Passively fed ionic liquid electrospray sources are capable of efficiently emitting a variety of ion beams with promising applications to spacecraft propulsion and as focused ion beams. Practical devices will require integrated or coupled ionic liquid reservoirs; the effects of which have not been explored in detail. Porous reservoirs are a simple, scalable solution. However, we have shown that their pore size can dramatically alter the beam composition. Emitting the ionic liquid 1-ethyl-3-methylimidazolium bis(triflouromethylsulfonyl)amide, the same device was shown to yield either an ion or droplet dominated beam when using reservoirs of small or large pore size, respectively; with themore » latter having a mass flow in excess of 15 times larger than the former at negative polarity. Another source, emitting nearly purely ionic beams of 1-ethyl-3-methylimidazolium tetrafluoroborate, was similarly shown to emit a significant droplet population when coupled to reservoirs of large (>100 μm) pores; constituting a reduction in propulsive efficiency from greater than 70% to less than 30%. Furthermore, we show that reservoir selection can alter the voltage required to obtain and sustain emission, increasing with smaller pore size.« less

Online analysis of five organic ultraviolet filters in environmental water samples using magnetism-enhanced monolith-based in-tube solid phase microextraction coupled with high-performance liquid chromatography.

PubMed

Mei, Meng; Huang, Xiaojia

2017-11-24

Due to the endocrine disrupting properties, organic UV filters have been a great risk for humans and other organisms. Therefore, development of accurate and effective analytical methods is needed for the determination of UV filters in environmental waters. In this work, a fast, sensitive and environmentally friendly method combining magnetism-enhanced monolith-based in-tube solid phase microextraction with high-performance liquid chromatography with diode array detection (DAD) (ME-MB-IT/SPME-HPLC-DAD) for the online analysis of five organic UV filters in environmental water samples was developed. To extract UV filters effectively, an ionic liquid-based monolithic capillary column doped with magnetic nanoparticles was prepared by in-situ polymerization and used as extraction medium of online ME-MB-IT/SPME-HPLC-DAD system. Several extraction conditions including the intensity of magnetic field, sampling and desorption flow rate, volume of sample and desorption solvent, pH value and ionic strength of sample matrix were optimized thoroughly. Under the optimized conditions, the extraction efficiencies for five organic UV filters were in the range of 44.0-100%. The limits of detection (S/N=3) and limits of quantification (S/N=10) were 0.04-0.26μg/L and 0.12-0.87μg/L, respectively. The precisions indicated by relative standard deviations (RSDs) were less than 10% for both intra- and inter-day variabilities. Finally, the developed method was successfully applied to the determination of UV filters in three environmental water samples and satisfactory results were obtained. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of pH in a Pd-based ethanol membraneless air breathing nanofluidic fuel cell with flow-through electrodes

NASA Astrophysics Data System (ADS)

López-Rico, C. A.; Galindo-de-la-Rosa, J.; Ledesma-García, J.; Arriaga, L. G.; Guerra-Balcázar, M.; Arjona, N.

2015-12-01

In this work, a nanofluidic fuel cell (NFC) in which streams flow through electrodes was used to investigate the role of pH in the cell performance using ethanol as fuel and two Pd nanoparticles as electrocatalysts: one commercially available (Pd/C from ETEK) and other synthesized using ionic liquids (Pd/C IL). The cell performances for both electrocatalysts in acid/acid (anodic/cathodic) streams were of 18.05 and 9.55 mW cm-2 for Pd/C ETEK and Pd/C IL. In alkaline/alkaline streams, decrease to 15.94 mW cm-2 for Pd/C ETEK and increase to 15.37 mW cm-2 for Pd/C IL. In alkaline/acidic streams both electrocatalysts showed similar cell voltages (up to 1 V); meanwhile power densities were of 87.6 and 99.4 mW cm-2 for Pd/C ETEK and Pd/C IL. The raise in cell performance can be related to a decrease in activation losses, the combined used of alkaline and acidic streams and these high values compared with flow-over fuel cells can be related to the enhancement of the cathodic mass transport by using three dimensional porous electrodes and two sources of oxygen: from air and from a saturated solution.

Effect of Structure on Transport Properties (Viscosity, Ionic Conductivity, and Self-Diffusion Coefficient) of Aprotic Heterocyclic Anion (AHA) Room-Temperature Ionic Liquids. 1. Variation of Anionic Species.

PubMed

Sun, Liyuan; Morales-Collazo, Oscar; Xia, Han; Brennecke, Joan F

2015-12-03

A series of room temperature ionic liquids (RTILs) based on 1-ethyl-3-methylimidazolium ([emim](+)) with different aprotic heterocyclic anions (AHAs) were synthesized and characterized as potential electrolyte candidates for lithium ion batteries. The density and transport properties of these ILs were measured over the temperature range between 283.15 and 343.15 K at ambient pressure. The temperature dependence of the transport properties (viscosity, ionic conductivity, self-diffusion coefficient, and molar conductivity) is fit well by the Vogel-Fulcher-Tamman (VFT) equation. The best-fit VFT parameters, as well as linear fits to the density, are reported. The ionicity of these ILs was quantified by the ratio of the molar conductivity obtained from the ionic conductivity and molar concentration to that calculated from the self-diffusion coefficients using the Nernst-Einstein equation. The results of this study, which is based on ILs composed of both a planar cation and planar anions, show that many of the [emim][AHA] ILs exhibit very good conductivity for their viscosities and provide insight into the design of ILs with enhanced dynamics that may be suitable for electrolyte applications.

CADDIS Volume 2. Sources, Stressors and Responses: Simple and Detailed Conceptual Model Diagram Downloads

EPA Pesticide Factsheets

Simple and detailed conceptual model diagram and associated narrative for ammonia, dissolved oxygen, flow alteration, herbicides, insecticides, ionic strength, metals, nutrients, ph, physical habitat, sediments, temperature, unspecified toxic chemicals.

Enhanced transport of biodegradable polymer-coated nanoiron particles in sand columns

NASA Astrophysics Data System (ADS)

Jung, B.; O'Carroll, D.; Sleep, B.

2009-05-01

The use of nanoscale zerovalent iron has shown promise as a technology for remediation of subsurface contamination by chlorinated solvents. However, the delivery of nanoiron particles to target contaminated subsurface zones is hindered by the aggregation of particles due to magnetic attraction. To overcome the limitations of aggregation and increase nanoiron mobility in porous media, nanoiron particles have been coated with various polymers. Polymer adsorption onto nanoiron particles provides electrosteric stabilization, increases the mobility, and decreases the attachment onto the soil surface. Various polymers were investigated in this study, including carboxylmethyl cellulose (CMC) and guar gum, both of which are biodegradable. In sand column experiments the transport of nanoiron particles was investigated as a function of type of electrolyte, ionic strength, flow velocity, and nanoiron particle concentration. Settling curves showed the enhanced stability of polymer-coated nanoiron particles compared to bare commercial nanoiron particles (bare RNIP-10DS). A newly developed nanoparticle transport numerical model was used to quantify the attachment efficiency, as well as investigate dominant nanoparticle transport and removal mechanisms. Finally the particle-collector interaction energy was predicted using DLVO (Derjaguin-Landau-Verwey-Overbeek) theory.

Effects of ionic radius of redox-inactive bio-related metal ions on the radical-scavenging activity of flavonoids evaluated using photometric titration.

PubMed

Waki, Tsukasa; Kobayashi, Shigeki; Matsumoto, Ken-ichiro; Ozawa, Toshihiko; Kamada, Tadashi; Nakanishi, Ikuo

2013-10-28

Mg(2+) enhanced the scavenging activity of (+)-catechin and quercetin against the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH˙), while Al(3+) decreased their activity. Such effects of Mg(2+) and Al(3+) were not observed for kaempferol. Na(+) and Ca(2+) with large ionic radii showed little effect on the DPPH˙-scavenging activity of these three flavonoids.

Desulfurization of oxidized diesel using ionic liquids

NASA Astrophysics Data System (ADS)

Wilfred, Cecilia D.; Salleh, M. Zulhaziman M.; Mutalib, M. I. Abdul

2014-10-01

The extraction of oxidized sulfur compounds from diesel were carried out using ten types of ionic liquids consisting of different cation and anion i.e. 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazoium thiocyanate, 1-butyl-3-methylimidazoium dicyanamide, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazoliumhexafluorophosphate, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, trioctylmethylammonium chloride, 1-propionitrile-3-butylimidazolium thiocyanate, 1-propionitrile-3-butylimidazolium dicyanamide and 1-butyl-6-methylquinolinium dicyanamide. The oxidation of diesel was successfully done using phosphotungstic acid as the catalyst, hydrogen peroxide (H2O2) as the oxidant and trioctylmethylammonium chloride as the phase transfer agent. The oxidation of diesel changes the sulfur compounds into sulfone which increases its polarity and enhances the ionic liquid's extraction performance. Result showed that ionic liquid [C4mquin][N(CN)2] performed the highest sulfur removal (91% at 1:5 diesel:IL ratio) compared to the others.

Incorporation of metal nanoparticles into wood substrate and methods

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

Rector, Kirk D; Lucas, Marcel

Metal nanoparticles were incorporated into wood. Ionic liquids were used to expand the wood cell wall structure for nanoparticle incorporation into the cell wall structure. Nanoparticles of elemental gold or silver were found to be effective surface enhanced Raman spectroscopy (SERS) imaging contrast or sensing agents. Nanoparticles of elemental iron were found to be efficient microwave absorbers and caused localized heating for disrupting the integrity of the lignocellulosic matrix. Controls suggest that the localized heating around the iron nanoparticles reduces losses of cellulose in the form of water, volatiles and CO.sub.2. The ionic liquid is needed during the incorporation processmore » at room temperature. The use of small amounts of ionic liquid combined with the absence of an ionic liquid purification step and a lower energy and water use are expected to reduce costs in an up-scaled pretreatment process.« less

Ionic liquids as refolding additives: N′-alkyl and N′-(ω-hydroxyalkyl) N-methylimidazolium chlorides

PubMed Central

Lange, Christian; Patil, Ganesh; Rudolph, Rainer

2005-01-01

The purpose of this work was to investigate the influence of a series of N′-alkyl and N′-(ω-hydroxy-alkyl)-N-methylimidazolium chlorides on the renaturation of two model proteins, namely hen egg white lysozyme and the single-chain antibody fragment ScFvOx. All tested ionic liquids acted as refolding enhancers, with varying efficacies and efficiencies. The results of the refolding screening could be interpreted by taking into account the effect of the studied ionic liquids on protein aggregation, together with the systematic variations of their influence on the stability of native proteins in solution. More hydrophobic imidazolium cations carrying longer alkyl chains were increasingly destabilizing, while terminal hydroxylation of the alkyl chain made the salts more compatible with protein stability. The studied ionic liquids can be classified as preferentially bound, slightly to moderately chaotropic cosolvents for proteins. PMID:16195554

Partial breaking of the Coulombic ordering of ionic liquids confined in carbon nanopores

PubMed Central

Futamura, Ryusuke; Iiyama, Taku; Takasaki, Yuma; Gogotsi, Yury; Biggs, Mark J.; Salanne, Mathieu; Ségalini, Julie; Simon, Patrice; Kaneko, Katsumi

2017-01-01

Ionic liquids are composed of equal quantities of positive and negative ions. In the bulk, electrical neutrality occurs in these liquids due to Coulombic ordering, in which ion shells of alternating charge form around a central ion. Their structure under confinement is far less well understood. This hinders the widespread application of ionic liquids in technological applications. Here we use scattering experiments to resolve the structure of the widely used ionic liquid (EMI-TFSI) when it is confined inside nanoporous carbons. We show that Coulombic ordering reduces when the pores can only accommodate a single layer of ions. Instead, equally-charged ion pairs are formed due to the induction of an electric potential of opposite sign in the carbon pore walls. This non-Coulombic ordering is further enhanced in the presence of an applied external electric potential. This finding opens the door for the design of better materials for electrochemical applications. PMID:28920938

Mixed ionic and electronic conducting ceramic membranes for hydrocarbon processing

DOEpatents

Van Calcar, Pamela; Mackay, Richard; Sammells, Anthony F.

2002-01-01

The invention relates to mixed phase materials for the preparation of catalytic membranes which exhibit ionic and electronic conduction and which exhibit improved mechanical strength compared to single phase ionic and electronic conducting materials. The mixed phase materials are useful for forming gas impermeable membranes either as dense ceramic membranes or as dense thin films coated onto porous substrates. The membranes and materials of this invention are useful in catalytic membrane reactors in a variety of applications including synthesis gas production. One or more crystalline second phases are present in the mixed phase material at a level sufficient to enhance the mechanical strength of the mixture to provide membranes for practical application in CMRs.

Enhancement of superconducting transition temperature in FeSe electric-double-layer transistor with multivalent ionic liquids

NASA Astrophysics Data System (ADS)

Miyakawa, Tomoki; Shiogai, Junichi; Shimizu, Sunao; Matsumoto, Michio; Ito, Yukihiro; Harada, Takayuki; Fujiwara, Kohei; Nojima, Tsutomu; Itoh, Yoshimitsu; Aida, Takuzo; Iwasa, Yoshihiro; Tsukazaki, Atsushi

2018-03-01

We report on an enhancement of the superconducting transition temperature (Tc) of the FeSe-based electric-double-layer transistor (FeSe-EDLT) by applying the multivalent oligomeric ionic liquids (ILs). The IL composed of dimeric cation (divalent IL) enables a large amount of charge accumulation on the surface of the FeSe ultrathin film, resulting in inducing electron-rich conduction even in a rather thick 10 nm FeSe channel. The onset Tc in FeSe-EDLT with the divalent IL is enhanced to be approaching about 50 K at the thin limit, which is about 7 K higher than that in EDLT with conventional monovalent ILs. The enhancement of Tc is a pronounced effect of the application of the divalent IL, in addition to the large capacitance, supposing preferable interface formation of ILs driven by geometric and/or Coulombic effect. The present finding strongly indicates that multivalent ILs are powerful tools for controlling and improving physical properties of materials.

Optimized anion exchange membranes for vanadium redox flow batteries.

PubMed

Chen, Dongyang; Hickner, Michael A; Agar, Ertan; Kumbur, E Caglan

2013-08-14

In order to understand the properties of low vanadium permeability anion exchange membranes for vanadium redox flow batteries (VRFBs), quaternary ammonium functionalized Radel (QA-Radel) membranes with three ion exchange capacities (IECs) from 1.7 to 2.4 mequiv g(-1) were synthesized and 55-60 μm thick membrane samples were evaluated for their transport properties and in-cell battery performance. The ionic conductivity and vanadium permeability of the membranes were investigated and correlated to the battery performance through measurements of Coulombic efficiency, voltage efficiency and energy efficiency in single cell tests, and capacity fade during cycling. Increasing the IEC of the QA-Radel membranes increased both the ionic conductivity and VO(2+) permeability. The 1.7 mequiv g(-1) IEC QA-Radel had the highest Coulombic efficiency and best cycling capacity maintenance in the VRFB, while the cell's voltage efficiency was limited by the membrane's low ionic conductivity. Increasing the IEC resulted in higher voltage efficiency for the 2.0 and 2.4 mequiv g(-1) samples, but the cells with these membranes displayed reduced Coulombic efficiency and faster capacity fade. The QA-Radel with an IEC of 2.0 mequiv g(-1) had the best balance of ionic conductivity and VO(2+) permeability, achieving a maximum power density of 218 mW cm(-2) which was higher than the maximum power density of a VRFB assembled with a Nafion N212 membrane in our system. While anion exchange membranes are under study for a variety of VRFB applications, this work demonstrates that the material parameters must be optimized to obtain the maximum cell performance.

Synthesis of novel ICIE16/BSG and ICIE16/BSG-NITRI bioglasses and description of ionic release kinetics upon immersion in SBF fluid: Effect of nitridation

PubMed Central

Orgaz, Felipe; Amat, Daniel; Szycht, Olga; Dzika, Aleksandra; Barba, Flora; Becerra, José; Santos-Ruiz, Leonor

2015-01-01

A novel bioactive glass scaffold ICIE16/BSG has been prepared from a mixture of two different melt-derived glasses: a silicate bioglass (ICIE16) and a borosilicate bioglass (BSG). Combined processing techniques (gel casting and foam replication) were used to form three-dimensional, interconnected porous monolith scaffolds (Orgaz et al., 2016) [1]. They were then nitrided with a hot ammonia flow as described in (Aleixandre et al., 1973) [3] and (Nieto, 1984) [4] to synthesize the ICIE16/BSG-NITRI bioglass (Orgaz et al., 2016) [1]. Herein we present a flow chart summarizing the forming process, plus images of the resulting scaffold after sintering and drying. Bioactivity was characterized in vitro by immersion in simulated body fluid (SBF) for up to seven days. Data of ionic release kinetics upon SBF immersion are presented. PMID:26858981

Synthesis of novel ICIE16/BSG and ICIE16/BSG-NITRI bioglasses and description of ionic release kinetics upon immersion in SBF fluid: Effect of nitridation.

PubMed

Orgaz, Felipe; Amat, Daniel; Szycht, Olga; Dzika, Aleksandra; Barba, Flora; Becerra, José; Santos-Ruiz, Leonor

2016-03-01

A novel bioactive glass scaffold ICIE16/BSG has been prepared from a mixture of two different melt-derived glasses: a silicate bioglass (ICIE16) and a borosilicate bioglass (BSG). Combined processing techniques (gel casting and foam replication) were used to form three-dimensional, interconnected porous monolith scaffolds (Orgaz et al., 2016) [1]. They were then nitrided with a hot ammonia flow as described in (Aleixandre et al., 1973) [3] and (Nieto, 1984) [4] to synthesize the ICIE16/BSG-NITRI bioglass (Orgaz et al., 2016) [1]. Herein we present a flow chart summarizing the forming process, plus images of the resulting scaffold after sintering and drying. Bioactivity was characterized in vitro by immersion in simulated body fluid (SBF) for up to seven days. Data of ionic release kinetics upon SBF immersion are presented.

Effect of Multivalent Ions on Electroosmotic Flow in Micro- and Nano-channels

NASA Astrophysics Data System (ADS)

Zheng, Zhi; Conlisk, A. Terrence

2002-11-01

In this work, the effect of multivalent ions on electroosmotic flow is investigated. Applications in biomedical engineering are numerous, including design of drug delivery systems, rapid molecular analysis and lab-on-a-chip. We specifically consider incorporating Ca^2+ and HPO4^2- and other monovalent ions, such as K^+ and H2PO4^-, into an aqueous NaCl solution. All previous work has been for the case where the mixture contains a pair of ionic species of equal valence. Electrochemical equilibrium considerations are used in determining the boundary conditions. The results can be applied to rectangular channels for which the height is on the nanometer scale up to the micrometer scale. The classical electroosmotic velocity profile is obtained at larger channel heights for fixed electrolyte concentration where an analytic solution for the velocity, potential and mole fractions may be obtained. The theory is valid for an arbitrary number of ionic species.

Measurement of the Onsager coefficients of mixed ionic-electronic conduction in oxides

NASA Astrophysics Data System (ADS)

Lee, Doh-Kwon; Yoo, Han-Ill

2007-06-01

In the phenomenon of mixed ionic-electronic conduction in solid state, a flow of mobile ions (Ji) may be induced not only directly by their own electrochemical potential gradient (∇ηi) , but also indirectly by that of electrons (∇ηe) , and vice versa for a flow of electrons (Je) or Jm=-Lmn∇ηn (m,n=i,e) . We have recently succeeded in determining experimentally all the four Onsager coefficients Lmn on the system of TiO2 , and reported [Phys. Rev. Lett. 97, 255901 (2006)] that the Onsager reciprocity is verified within 1.3% error bound (Lie/Lei=0.993±0.013) and contrary to the general belief, the cross coefficient is not only not negligible but also even larger than a direct one (1.5⩽Lie/Lii⩽3.7) . This paper details the experimental technique which allows one to measure all the Onsager coefficients in a mixed conductor oxide.

Non-scaling behavior of electroosmotic flow in voltage-gated nanopores

DOE PAGES

Lian, Cheng; Gallegos, Alejandro; Liu, Honglai; ...

2016-11-17

Ionic transport through nanopores is of fundamental importance for the design and development of nanofiltration membranes and novel electrochemical devices including supercapacitors, fuel cells and batteries. Recent experiments have shown an unusual variation of electrical conductance with the pore size and the electrolyte parameters that defies conventional scaling relations. Here ionic transport through voltage-gated nanopores was studied by using the classical density functional theory for ion distributions in combination with the Navier–Stokes equation for the electroosmotic flow. We also identified a significant influence of the gating potential on the scaling behavior of the conductance with changes in the pore sizemore » and the salt concentration. Finally, for ion transport in narrow pores with a high gating voltage, the conductivity shows an oscillatory dependence on the pore size owing to the strong overlap of electric double layers.« less

A reversible conductivity modulation of azobenzene-based ionic liquids in aqueous solutions using UV/vis light.

PubMed

Li, Zhiyong; Yuan, Xiaoqing; Feng, Ying; Chen, Yongkui; Zhao, Yuling; Wang, Huiyong; Xu, Qingli; Wang, Jianji

2018-05-09

Photo-induced conductivity modulation of stimuli-responsive materials is of great importance from the viewpoint of fundamental research and technology. In this work, 5 new kinds of azobenzene-based photo-responsive ionic liquids were synthesized and characterized, and UV/vis light modulation of their conductivity was investigated in an aqueous solution. The factors affecting the conductivity modulation of the photo-responsive fluids, such as photo-isomerization efficiency, photo-regulation aggregation, concentration and chemical structure of the ionic liquids, were examined systematically. It was found that the conductivity of the ionic liquids in water exhibited a significant increase upon UV light irradiation and the ionic liquids with a shorter alkyl spacer in the cation showed a more remarkable photo-induced conductivity enhancement with a maximum increase of 150%. In addition, the solution conductivity was restored (or very close) to the initial value upon an alternative irradiation with visible light. Thus, the solution conductivity can be modulated using alternative irradiation with UV and visible light. Although the reversible photo-isomerization of the azobenzene group under UV/vis irradiation is the origin of the conductivity modulation, the photo-regulated aggregation of the ionic liquid in water is indispensable for the maximum degree of conductivity modulation because UV irradiation can weaken, even break the aggregated cis-isomers of the ionic liquids in an aqueous solution.

Label-free biosensing with functionalized nanopipette probes

PubMed Central

Umehara, Senkei; Karhanek, Miloslav; Davis, Ronald W.; Pourmand, Nader

2009-01-01

Nanopipette technology can uniquely identify biomolecules such as proteins based on differences in size, shape, and electrical charge. These differences are determined by the detection of changes in ionic current as the proteins interact with the nanopipette tip coated with probe molecules. Here we show that electrostatic, biotin-streptavidin, and antibody-antigen interactions on the nanopipette tip surface affect ionic current flowing through a 50-nm pore. Highly charged polymers interacting with the glass surface modulated the rectification property of the nanopipette electrode. Affinity-based binding between the probes tethered to the surface and their target proteins caused a change in the ionic current due to a partial blockade or an altered surface charge. These findings suggest that nanopipettes functionalized with appropriate molecular recognition elements can be used as nanosensors in biomedical and biological research. PMID:19264962

Application of an immobilized ionic liquid for the passive sampling of perfluorinated substances in water.

PubMed

Wang, Lei; Gong, Xinying; Wang, Ruonan; Gan, Zhiwei; Lu, Yuan; Sun, Hongwen

2017-09-15

Ionic liquids have been used to efficiently extract a wide range of polar and nonpolar organic contaminants from water. In this study, imidazole ionic liquids immobilized on silica gel were synthesized through a chemical bonding method, and the immobilized dodecylimidazolium ionic liquid was selected as the receiving phase material in a POCIS (polar organic chemical integrative sampler) like passive sampler to monitor five perfluoroalkyl substances (PFASs) in water. Twenty-one days of integrative accumulation was conducted in laboratory scale experiments, and the accumulated PFASs in the samplers were eluted and analyzed by high performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS). The partitioning coefficients of most PFASs between sampler sorbents and water in the immobilized ionic liquid (IIL)-sampler were higher than those in the HLB-sampler, especially for compounds with shorter alkyl chains. The effects of flow velocity, temperature, dissolved organic matter (DOM) and pH on the uptake of these analytes were also evaluated. Under the experimental conditions, the uptake of PFASs in the IIL-sampler slightly increased with the flow velocity and temperature, while different influences of DOM and pH on the uptake of PFAS homologues with short or long chains were observed. The designed IIL-samplers were applied in the influent and effluent of a wastewater treatment plant. All five PFASs could be accumulated in the samplers, with concentrations ranging from 6.5×10 -3 -3.6×10 -1 nmol/L in the influent and from 1.3×10 -2 -2.2×10 -1 nmol/L in the effluent. The calculated time-weighted average concentrations of most PFASs fit well with the detected concentrations of the active sampling, indicating the applicability of the IIL-sampler in monitoring these compounds in water. Copyright © 2017 Elsevier B.V. All rights reserved.

Biodegradation potential of cyano-based ionic liquid anions in a culture of Cupriavidus spp. and their in vitro enzymatic hydrolysis by nitrile hydratase.

PubMed

Neumann, Jennifer; Pawlik, Magdalena; Bryniok, Dieter; Thöming, Jorg; Stolte, Stefan

2014-01-01

Biodegradation tests with bacteria from activated sludge revealed the probable persistence of cyano-based ionic liquid anions when these leave waste water treatment plants. A possible biological treatment using bacteria capable of biodegrading similar compounds, namely cyanide and cyano-complexes, was therefore examined. With these bacteria from the genera Cupriavidus, the ionic liquid anions B(CN)₄(-), C(CN)₃(-), N(CN)₂(-) combined with alkaline cations were tested in different growth media using ion chromatography for the examination of their primary biodegradability. However, no enhanced biodegradability of the tested cyano-based ionic liquids was observed. Therefore, an in vitro enzymatic hydrolysis test was additionally run showing that all tested ionic liquid (IL) anions can be hydrolysed to their corresponding amides by nitrile hydratase, but not by nitrilase under the experimental conditions. The biological stability of the cyano-based anions is an advantage in technological application, but the occurrence of enzymes that are able to hydrolyse the parent compound gives a new perspective on future cyano-based IL anion treatment.

High-Performance, Low-Temperature-Operating, Long-Lifetime Aerospace Lubricants

NASA Technical Reports Server (NTRS)

Bergeron, Bryan; Skyler, David; Roberts, Kyle; Stevens, Amy

2013-01-01

The synthesis and characterization of six new ionic liquids, with fluoroether moeties on the imidazolium ring, each with vapor pressures shown to be <10(exp -7 Torr at 25 C, have been demonstrated. Thermal stability of the ionic liquids up to 250 C was demonstrated. The ionic liquids had no measurable influence upon viscosity upon addition to perfluoropolyether (PFPE) base fluids. They also had no measureable influence upon corrosion on steel substrates upon addition to base fluids. In general, 13 to 34% lower COFs (coefficients of friction), and 30 to 80% higher OK load of base fluids upon addition of the ionic liquids was shown. The compound consists of a 1,3-disubstituted imidazolium cation. The substituents comprise perfluoroether groups. A bis(trifluoromethanesulfonyl) imide anion counterbalances the charge. The fluorinated groups are intended to enhance dispersion of the ionic liquid in the PFPE base fluid. The presence of weak Van der Waals forces associated with fluorine atoms will limit interaction of the substituents on adjacent ions. The longer interionic distances will reduce the heat of melting and viscosity, and will increase dispersion capabilities.

Simulating chemical reactions in ionic liquids using QM/MM methodology.

PubMed

Acevedo, Orlando

2014-12-18

The use of ionic liquids as a reaction medium for chemical reactions has dramatically increased in recent years due in large part to the numerous reported advances in catalysis and organic synthesis. In some extreme cases, ionic liquids have been shown to induce mechanistic changes relative to conventional solvents. Despite the large interest in the solvents, a clear understanding of the molecular factors behind their chemical impact is largely unknown. This feature article reviews our efforts developing and applying mixed quantum and molecular mechanical (QM/MM) methodology to elucidate the microscopic details of how these solvents operate to enhance rates and alter mechanisms for industrially and academically important reactions, e.g., Diels-Alder, Kemp eliminations, nucleophilic aromatic substitutions, and β-eliminations. Explicit solvent representation provided the medium dependence of the activation barriers and atomic-level characterization of the solute-solvent interactions responsible for the experimentally observed "ionic liquid effects". Technical advances are also discussed, including a linear-scaling pairwise electrostatic interaction alternative to Ewald sums, an efficient polynomial fitting method for modeling proton transfers, and the development of a custom ionic liquid OPLS-AA force field.

Thermoelectric Power in Bilayer Graphene Device with Ionic Liquid Gating.

PubMed

Chien, Yung-Yu; Yuan, Hongtao; Wang, Chang-Ran; Lee, Wei-Li

2016-02-08

The quest for materials showing large thermoelectric power has long been one of the important subjects in material science and technology. Such materials have great potential for thermoelectric cooling and also high figure of merit ZT thermoelectric applications. We have fabricated bilayer graphene devices with ionic-liquid gating in order to tune its band gap via application of a perpendicular electric field on a bilayer graphene. By keeping the Fermi level at charge neutral point during the cool-down, we found that the charge puddles effect can be greatly reduced and thus largely improve the transport properties at low T in graphene-based devices using ionic liquid gating. At (Vig, Vbg) = (-1 V, +23 V), a band gap of about 36.6 ± 3 meV forms, and a nearly 40% enhancement of thermoelectric power at T = 120 K is clearly observed. Our works demonstrate the feasibility of band gap tuning in a bilayer graphene using ionic liquid gating. We also remark on the significant influence of the charge puddles effect in ionic-liquid-based devices.

Magnetorheological technology for fabricating tunable solid electrolyte with enhanced conductivity and mechanical property

NASA Astrophysics Data System (ADS)

Peng, Gangrou; Ge, Yu; Ding, Jie; Wang, Caiyun; Wallace, Gordon G.; Li, Weihua

2018-03-01

Ionogels are a new class of hybrid materials where ionic liquids are immobilized by macromolecular support. The excessive amount of crosslinking polymer enhances the mechanical strength but compromises the conductivity. Here, we report an elastomeric magnetorheological (MR) ionogel with an enhanced conductivity and mechanical strength as well. Following the application of magnetic nanoparticles into an ionic liquid containing minimum cross-linking agent, the formation, thus physical properties, of MR ionogels are co-controlled by simultaneously applied UV light and external magnetic field. The application of MR ionogels as solid electrolytes in supercapacitors is also demonstrated to study electrochemical performance. This work opens a new avenue to synthesize robust ionogels with the desired conductivity and controllable mechanical properties for soft flexible electronic devices. Besides, as a new class of conductive MR elastomers, the proposed MR ionogel also possesses the potential for engineering applications, such as sensors and actuators.

Influence of electrical boundary conditions on molecular dynamics simulations of ionic liquid electrosprays.

PubMed

Borner, Arnaud; Wang, Pengxiang; Levin, Deborah A

2014-12-01

Molecular dynamics (MD) simulations are coupled to solutions of Poisson's equation to study the effects of the electrical boundary conditions on the emission modes of an electrospray thruster fed with an ionic liquid. A comparison of a new tip boundary condition with an analytical model based on a semihyperboloidal shape offers good agreement, although the analytical model overestimates the maximum value of the tangential electric field since it does not take into account the space charge that reduces the field at the liquid surface. It is found that a constant electric field model gives similar agreement to the more rigorous and computationally expensive tip boundary condition at lower flow rates. However, at higher mass flow rates the constant electric field produces extruded particles with higher Coulomb energy per ion, consistent with droplet formation. Furthermore, the MD simulations show that ion emission sites differ based on the boundary condition and snapshots offer an explanation as to why some boundary condition models will predict emission in a purely ionic mode, whereas others suggest a mixed ion-droplet regime. Finally, specific impulses and thrusts are compared for the different models and are found to vary up to 30% due to differences in the average charge to mass ratio.

Graphene Nanopore Support System for Simultaneous High-Resolution AFM Imaging and Conductance Measurements

PubMed Central

2015-01-01

Accurately defining the nanoporous structure and sensing the ionic flow across nanoscale pores in thin films and membranes has a wide range of applications, including characterization of biological ion channels and receptors, DNA sequencing, molecule separation by nanoparticle films, sensing by block co-polymers films, and catalysis through metal–organic frameworks. Ionic conductance through nanopores is often regulated by their 3D structures, a relationship that can be accurately determined only by their simultaneous measurements. However, defining their structure–function relationships directly by any existing techniques is still not possible. Atomic force microscopy (AFM) can image the structures of these pores at high resolution in an aqueous environment, and electrophysiological techniques can measure ion flow through individual nanoscale pores. Combining these techniques is limited by the lack of nanoscale interfaces. We have designed a graphene-based single-nanopore support (∼5 nm thick with ∼20 nm pore diameter) and have integrated AFM imaging and ionic conductance recording using our newly designed double-chamber recording system to study an overlaid thin film. The functionality of this integrated system is demonstrated by electrical recording (<10 pS conductance) of suspended lipid bilayers spanning a nanopore and simultaneous AFM imaging of the bilayer. PMID:24581087

Influence of electrical boundary conditions on molecular dynamics simulations of ionic liquid electrosprays

NASA Astrophysics Data System (ADS)

Borner, Arnaud; Wang, Pengxiang; Levin, Deborah A.

2014-12-01

Molecular dynamics (MD) simulations are coupled to solutions of Poisson's equation to study the effects of the electrical boundary conditions on the emission modes of an electrospray thruster fed with an ionic liquid. A comparison of a new tip boundary condition with an analytical model based on a semihyperboloidal shape offers good agreement, although the analytical model overestimates the maximum value of the tangential electric field since it does not take into account the space charge that reduces the field at the liquid surface. It is found that a constant electric field model gives similar agreement to the more rigorous and computationally expensive tip boundary condition at lower flow rates. However, at higher mass flow rates the constant electric field produces extruded particles with higher Coulomb energy per ion, consistent with droplet formation. Furthermore, the MD simulations show that ion emission sites differ based on the boundary condition and snapshots offer an explanation as to why some boundary condition models will predict emission in a purely ionic mode, whereas others suggest a mixed ion-droplet regime. Finally, specific impulses and thrusts are compared for the different models and are found to vary up to 30% due to differences in the average charge to mass ratio.

The Relation between Vaporization Enthalpies and Viscosities: Eyring's Theory Applied to Selected Ionic Liquids.

PubMed

Bonsa, Anne-Marie; Paschek, Dietmar; Zaitsau, Dzmitry H; Emel'yanenko, Vladimir N; Verevkin, Sergey P; Ludwig, Ralf

2017-05-19

Key properties for the use of ionic liquids as electrolytes in batteries are low viscosities, low vapor pressure and high vaporization enthalpies. Whereas the measurement of transport properties is well established, the determination of vaporization enthalpies of these extremely low volatile compounds is still a challenge. At a first glance both properties seem to describe different thermophysical phenomena. However, eighty years ago Eyring suggested a theory which related viscosities and vaporization enthalpies to each other. The model is based on Eyring's theory of absolute reaction rates. Recent attempts to apply Eyring's theory to ionic liquids failed. The motivation of our study is to show that Eyring's theory works, if the assumptions specific for ionic liquids are fulfilled. For that purpose we measured the viscosities of three well selected protic ionic liquids (PILs) at different temperatures. The temperature dependences of viscosities were approximated by the Vogel-Fulcher-Tamann (VFT) relation and extrapolated to the high-temperature regime up to 600 K. Then the VFT-data could be fitted to the Eyring-model. The values of vaporization enthalpies for the three selected PILs predicted by the Eyring model have been very close to the experimental values measured by well-established techniques. We conclude that the Eyring theory can be successfully applied to the chosen set of PILs, if the assumption that ionic pairs of the viscous flow in the liquid and the ionic pairs in the gas phase are similar is fulfilled. It was also noticed that proper transfer of energies can be only derived if the viscosities and the vaporization energies are known for temperatures close to the liquid-gas transition temperature. The idea to correlate easy measurable viscosities of ionic liquids with their vaporization enthalpies opens a new way for a reliable assessment of these thermodynamic properties for a broad range of ionic liquids. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Constitutive expression of a salinity-induced wheat WRKY transcription factor enhances salinity and ionic stress tolerance in transgenic Arabidopsis thaliana

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

Qin, Yuxiang, E-mail: yuxiangqin@126.com; Tian, Yanchen; Han, Lu

Highlights: •A class II WRKY transcription factor, TaWRKY79 was isolated and characterized. •TaWRKY79 was induced by NaCl or abscisic acid. •843 bp regulatory segment was sufficient to respond to ABA or NaCl treatment. •TaWRKY79 enhanced salinity and ionic tolerance while reduced sensitivity to ABA. •TaWRKY79 increased salinity and ionic tolerance in an ABA-dependent pathway. -- Abstract: The isolation and characterization of TaWRKY79, a wheat class II WRKY transcription factor, is described. Its 1297 bp coding region includes a 987 bp long open reading frame. TaWRKY79 was induced by stressing seedlings with either NaCl or abscisic acid (ABA). When a fusionmore » between an 843 bp segment upstream of the TaWRKY79 coding sequence and GUS was introduced into Arabidopsis thaliana, GUS staining indicated that this upstream segment captured the sequence(s) required to respond to ABA or NaCl treatment. When TaWRKY79 was constitutively expressed as a transgene in A. thaliana, the transgenic plants showed an improved capacity to extend their primary root in the presence of either 100 mM NaCl, 10 mM LiCl or 2 μM ABA. The inference was that TaWRKY79 enhanced the level of tolerance to both salinity and ionic stress, while reducing the level of sensitivity to ABA. The ABA-related genes ABA1, ABA2 ABI1 and ABI5 were all up-regulated in the TaWRKY79 transgenic plants, suggesting that the transcription factor operates in an ABA-dependent pathway.« less

Effects of comprehensive function of factors on retention behavior of microparticles in gravitational field-flow fractionation.

PubMed

Guo, Shuang; Qiu, Bai-Ling; Zhu, Chen-Qi; Yang, Ya-Ya Gao; Wu, Di; Liang, Qi-Hui; Han, Nan-Yin

2016-09-15

Gravitational field-flow fractionation (GrFFF) is a useful technique for separation and characterization for micrometer-sized particles. Elution behavior of micrometer-sized particles in GrFFF was researched in this study. Particles in GrFFF channel are subject to hydrodynamic lift forces (HLF), fluid inertial forces and gravity, which drive them to different velocities by carrier flow, resulting in a size-based separation. Effects of ionic strength, flow rate and viscosity as well as methanol were investigated using polystyrene latex beads as model particles. This study is devoted to experimental verification of the effect of every factor and their comprehensive function. All experiments were performed to show isolated influence of every variable factor. The orthogonal design test was used to evaluate various factors comprehensively. Results suggested that retention ratio of particles increases with increasing flow rate or the viscosity of carrier liquid by adjusting external forces acting on particles. In addition, retention ratio increases as ionic strength decreases because of decreased electrostatic repulsion between particles and channel accumulation wall. As far as methanol, there is no general trend due to the change of both density and viscosity. On the basis of orthogonal design test it was found that viscosity of carrier liquid plays a significant role in determining resolution of micrometer-sized particles in GrFFF. Copyright © 2016 Elsevier B.V. All rights reserved.

Improved ionic conductivity of lithium-zinc-tellurite glass-ceramic electrolytes

NASA Astrophysics Data System (ADS)

Widanarto, W.; Ramdhan, A. M.; Ghoshal, S. K.; Effendi, M.; Cahyanto, W. T.; Warsito

An enhancement in the secondary battery safety demands the optimum synthesis of glass-ceramics electrolytes with modified ionic conductivity. To achieve improved ionic conductivity and safer operation of the battery, we synthesized Li2O included zinc-tellurite glass-ceramics based electrolytes of chemical composition (85-x)TeO2·xLi2O·15ZnO, where x = 0, 5, 10, 15 mol%. Samples were prepared using the melt quenching method at 800 °C followed by thermal annealing at 320 °C for 3 h and characterized. The effects of varying temperature, alternating current (AC) frequency and Li2O concentration on the structure and ionic conductivity of such glass-ceramics were determined. The SEM images of the annealed glass-ceramic electrolytes displayed rough surface with a uniform distribution of nucleated crystal flakes with sizes less than 1 μm. X-ray diffraction analysis confirmed the well crystalline nature of achieved electrolytes. Incorporation of Li2O in the electrolytes was found to generate some new crystalline phases including hexagonal Li6(TeO6), monoclinic Zn2Te3O8 and monoclinic Li2Te2O5. The estimated crystallite size of the electrolyte was ranged from ≈40 to 80 nm. AC impedance measurement revealed that the variation in the temperatures, Li2O contents, and high AC frequencies have a significant influence on the ionic conductivity of the electrolytes. Furthermore, electrolyte doped with 15 mol% of Li2O exhibited the optimum performance with an ionic conductivity ≈2.4 × 10-7 S cm-1 at the frequency of 54 Hz and in the temperature range of 323-473 K. This enhancement in the conductivity was attributed to the sizable alteration in the ions vibration and ruptures of covalent bonds in the electrolytes network structures.

Iodopropyl-branched polysiloxane gel electrolytes with improved ionic conductivity upon cross-linking.

PubMed

De Gregorio, G L; Giannuzzi, R; Cipolla, M P; Agosta, R; Grisorio, R; Capodilupo, A; Suranna, G P; Gigli, G; Manca, M

2014-11-21

We here report the implementation of poly[(3-N-methylimidazoliumpropyl)methylsiloxane-co-dimethylsiloxane]iodides as suitable polymeric hosts for a novel class of in situ cross-linkable iodine/iodide-based gel-electrolytes for dye-sensitized solar cells. The polymers are first partially quaternized and then subjected to a thermal cross-linking which allows the formation of a 3D polymeric network which is accompanied by a dramatic enhancement of the ionic conductivity.

Catalytic conversion of cellulose to fuels and chemicals using boronic acids

DOEpatents

Raines, Ronald; Caes, Benjamin; Palte, Michael

2015-10-20

Methods and catalyst compositions for formation of furans from carbohydrates. A carbohydrate substrate is heating in the presence of a 2-substituted phenylboronic acid (or salt or hydrate thereof) and optionally a magnesium or calcium halide salt. The reaction is carried out in a polar aprotic solvent other than an ionic liquid, an ionic liquid or a mixture thereof. Additional of a selected amount of water to the reaction can enhance the yield of furans.

Polarization of gold in nanopores leads to ion current rectification

DOE PAGES

Yang, Crystal; Hinkle, Preston; Menestrina, Justin; ...

2016-10-03

Biomimetic nanopores with rectifying properties are relevant components of ionic switches, ionic circuits, and biological sensors. Rectification indicates that currents for voltages of one polarity are higher than currents for voltages of the opposite polarity. Ion current rectification requires the presence of surface charges on the pore walls, achieved either by the attachment of charged groups or in multielectrode systems by applying voltage to integrated gate electrodes. Here we present a simpler concept for introducing surface charges via polarization of a thin layer of Au present at one entrance of a silicon nitride nanopore. In an electric field applied bymore » two electrodes placed in bulk solution on both sides of the membrane, the Au layer polarizes such that excess positive charge locally concentrates at one end and negative charge concentrates at the other end. Consequently, a junction is formed between zones with enhanced anion and cation concentrations in the solution adjacent to the Au layer. This bipolar double layer together with enhanced cation concentration in a negatively charged silicon nitride nanopore leads to voltage-controlled surface-charge patterns and ion current rectification. The experimental findings are supported by numerical modeling that confirm modulation of ionic concentrations by the Au layer and ion current rectification even in low-aspect ratio nanopores. Lastly, our findings enable a new strategy for creating ionic circuits with diodes and transistors.« less

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

Lian, Cheng; Univ. of California, Riverside, CA; Liu, Honglai

The ionophobicity effect of nanoporous electrodes on the capacitance and the energy storage capacity of nonaqueous-electrolyte supercapacitors is studied by means of the classical density functional theory (DFT). It has been hypothesized that ionophobic nanopores may create obstacles in charging, but they store energy much more efficiently than ionophilic pores. In this paper, we find that, for both ionic liquids and organic electrolytes, an ionophobic pore exhibits a charging behavior different from that of an ionophilic pore, and that the capacitance–voltage curve changes from a bell shape to a two-hump camel shape when the pore ionophobicity increases. For electric-double-layer capacitorsmore » containing organic electrolytes, an increase in the ionophobicity of the nanopores leads to a higher capacity for energy storage. Without taking into account the effects of background screening, the DFT predicts that an ionophobic pore containing an ionic liquid does not enhance the supercapacitor performance within the practical voltage ranges. However, by using an effective dielectric constant to account for ion polarizability, the DFT predicts that, like an organic electrolyte, an ionophobic pore with an ionic liquid is also able to increase the energy stored when the electrode voltage is beyond a certain value. We find that the critical voltage for an enhanced capacitance in an ionic liquid is larger than that in an organic electrolyte. Finally, our theoretical predictions provide further understanding of how chemical modification of porous electrodes affects the performance of supercapacitors.« less

Optimization of enzymatic esterification of dihydrocaffeic acid with hexanol in ionic liquid using response surface methodology.

PubMed

Gholivand, Somayeh; Lasekan, Ola; Tan, Chin Ping; Abas, Faridah; Wei, Leong Sze

2017-05-26

Developing an efficient lipophilization reaction system for phenolic derivatives could enhance their applications in food processing. Low solubility of phenolic acids reduces the efficiency of phenolic derivatives in most benign enzyme solvents. The conversion of phenolic acids through esterification alters their solubility and enhances their use as food antioxidant additives as well as their application in cosmetics. This study has shown that lipase-catalyzed esterification of dihydrocaffeic acid with hexanol in ionic liquid (1-butyl-3-methylimidazoliumbis (trifluoromethylsulfonyl) imide) was the best approach for esterification reaction. In order to achieve the maximum yield, the process was optimized by response surface methodology (RSM) based on a five-level and four independent variables such as: dosage of enzyme; hexanol/dihydrocaffeic acid mole ratio; temperature and reaction time. The optimum esterification condition (Y = 84.4%) was predicted to be obtained at temperature of 39.4 °C, time of 77.5 h dosage of enzyme at 41.6% and hexanol/dihydrocaffeic acid mole ratio of 2.1. Finally, this study has produced an efficient enzymatic esterification method for the preparation of hexyl dihydrocaffeate in vitro using a lipase in an ionic liquid system. Concentration of hexanol was the most significant (p < 0.05) independent variable that influenced the yield of hexyl dihydrocaffeate. Graphical abstract Synthesis of different Hexyl dihydrocaffeates in ionic liquid.

Transformation of CuO Nanoparticles in the Aquatic Environment: Influence of pH, Electrolytes and Natural Organic Matter

PubMed Central

Peng, Cheng; Shen, Chensi; Zheng, Siyuan; Yang, Weiling; Hu, Hang; Liu, Jianshe; Shi, Jiyan

2017-01-01

Many studies have shown the effect of solution chemistry on the environmental behavior of metal-based nanoparticles (NPs), except CuO NPs. Here, we investigated the agglomeration, sedimentation, dissolution, and speciation of CuO NPs by varying pH, ionic strength, ionic valence, and natural organic matter (NOM). The results showed that as the pH moved away from 6, the size of CuO agglomerates decreased, along with the enhanced NP suspension stabilization, due to the increase of electrostatic repulsive force. Increasing ionic strength and valence intensified the agglomeration and sedimentation of CuO NPs because of the compression of electrical double layers. The presence of humic acid and citric acid enhanced the dispersion and stabilization of CuO NP suspension, but l-cysteine showed a different impact. Decreasing pH, increasing ionic strength and all NOM improved the dissolution of CuO NPs, but the divalent electrolyte (CaCl2) inhibited the Cu2+ release from CuO NPs compared to the monovalent electrolyte (NaCl). In addition, X-ray absorption near edge structure (XANES) analysis demonstrated that the presence of l-cysteine transformed more than 30% of CuO NPs to Cu(I)-cysteine by coordinating with thiol group. This study can give us an in-depth understanding on the environmental behavior and fate of CuO NPs in the aquatic environment. PMID:29036921

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

Perriot, Romain; Dholabhai, Pratik P.; Uberuaga, Blas P.

In this paper, we use molecular dynamics simulations to investigate the role of grain boundaries (GBs) on ionic diffusion in pyrochlores, as a function of the GB type, chemistry of the compound, and level of cation disorder. We observe that the presence of GBs promotes oxygen transport in ordered and low-disordered systems, as the GBs are found to have a higher concentration of mobile carriers with higher mobilities than in the bulk. Thus, in ordered samples, the ionic diffusion is 2D, localized along the grain boundary. When cation disorder is introduced, bulk carriers begin to contribute to the overall diffusion,more » while the GB contribution is only slightly enhanced. In highly disordered samples, the diffusive behavior at the GBs is bulk-like, and the two contributions (bulk vs. GB) can no longer be distinguished. There is thus a transition from 2D/GB dominated oxygen diffusivity to 3D/bulk dominated diffusivity versus disorder in pyrochlores. Finally, these results provide new insights into the possibility of using internal interfaces to enhance ionic conductivity in nanostructured complex oxides.« less

Adsorption of Eu(III) onto TiO2: effect of pH, concentration, ionic strength and soil fulvic acid.

PubMed

Tan, Xiaoli; Fang, Ming; Li, Jiaxing; Lu, Yi; Wang, Xiangke

2009-08-30

The effects of pH, initial Eu(III) concentration, ionic strength and fulvic acid (FA) on the adsorption of Eu(III) on TiO(2) are investigated by using batch techniques. The results indicate that the presence of FA strongly enhances the adsorption of Eu(III) on TiO(2) at low pH values. Besides, the adsorption of Eu(III) on TiO(2) is significantly dependent on pH values and independent of ionic strength. The adsorption of Eu(III) on TiO(2) is attributed to inner-sphere surface complexation. The diffuse layer model (DLM) is applied to simulate the adsorption data, and fits the experimental data well with the aid of FITEQL 3.2. X-ray photoelectron spectroscopy (XPS) is performed to study the species of Eu(III) adsorbed on the surfaces of TiO(2)/FA-TiO(2) hybrids at a molecular level, which suggest that FA act as "bridge" between Eu(III) and TiO(2) particles to enhance the ability to adsorb Eu(III) in solution.

Visualization of TlBr ionic transport mechanism by the Accelerated Device Degradation technique

NASA Astrophysics Data System (ADS)

Datta, Amlan; Becla, Piotr; Motakef, Shariar

2015-06-01

Thallium Bromide (TlBr) is a promising gamma radiation semiconductor detector material. However, it is an ionic semiconductor and suffers from polarization. As a result, TlBr devices degrade rapidly at room temperature. Polarization is associated with the flow of ionic current in the crystal under electrical bias, leading to the accumulation of charged ions at the device's electrical contacts. We report a fast and reliable direct characterization technique to identify the effects of various growth and post-growth process modifications on the polarization process. The Accelerated Device Degradation (ADD) characterization technique allows direct observation of nucleation and propagation of ionic transport channels within the TlBr crystals under applied bias. These channels are observed to be initiated both directly under the electrode as well as away from it. The propagation direction is always towards the anode indicating that Br- is the mobile diffusing species within the defect channels. The effective migration energy of the Br- ions was calculated to be 0.33±0.03 eV, which is consistent with other theoretical and experimental results.

Thermo-Rheometric Studies of New Class Ionic Liquid Lubricants

NASA Astrophysics Data System (ADS)

Bakhtiyarov, Sayavur; Street, Kenneth; Scheiman, Daniel; van Dyke, Alan

2010-11-01

Due to their specific properties, such as small volatility, nonflammability, extreme thermal stability, low melting point, wide liquid range, and good miscibility with organic materials, ionic liquids attracted particular interest in various industrial processes. Recently, the unique properties of ionic liquids caught the attention of space tribologists. The traditional lubricating materials used in space have limited lifetimes in vacuum due to the catalytic degradation on metal surfaces, high vaporization at high temperatures, dewetting, and other disadvantages. The lubricants for the space applications must have vacuum stability, high viscosity index, low creep tendency, good elastohydrodynamic and boundary lubrication properties, radiation atomic oxygen resistance, optical or infrared transparency. Unfortunately, the properties such as heat flow, heat capacity, thermogravimetric weight loss, and non-linearity in the rheological behavior of the lubricants are not studied well for newly developed systems. These properties are crucial to analyzing thermodynamic and energy dissipative aspects of the lubrication process. In this paper we will present the rheological and heat and mass transfer measurements for the ionic liquid lubricants, their mixtures with and without additive.

Osmotic Pressure in Ionic Microgel Dispersions

NASA Astrophysics Data System (ADS)

Denton, Alan R.; Tang, Qiyun

2015-03-01

Microgels are microscopic gel particles, typically 10-1000 nm in size, that are swollen by a solvent. Hollow microgels (microcapsules) can encapsulate cargo, such as dye molecules or drugs, in their solvent-filled cavities. Their sensitive response to environmental conditions (e.g., temperature, pH) and influence on flow properties suit microgels to widespread applications in the chemical, pharmaceutical, food, and consumer care industries. When dispersed in water, polyelectrolyte gels become charged through dissociation of counterions. The electrostatic contribution to the osmotic pressure inside and outside of ionic microgels influences particle swelling and bulk materials properties, including thermodynamic, structural, optical, and rheological properties. Within the primitive and cell models of polyelectrolyte solutions, we derive an exact statistical mechanical formula for the contribution of mobile microions to the osmotic pressure within ionic microgels. Using Poisson-Boltzmann theory, we validate this result by explicitly calculating ion distributions across the surface of an ionic microgel and the electrostatic contribution to the osmotic pressure. Within a coarse-grained one-component model, we further chart the limits of the cell model for salty dispersions. This work was supported by the National Science Foundation under Grant No. DMR-1106331.

Training and shape retention in conducting polymer artificial muscles

NASA Astrophysics Data System (ADS)

Tominaga, Kazuo; Hashimoto, Hikaru; Takashima, Wataru; Kaneto, Keiichi

2011-12-01

Electrochemomechanical deformation (ECMD) of the conducting polymer polyaniline film is studied to investigate the behaviour of actuation under tensile loads. The ECMD was induced by the strains due to the insertion of ionic species (cyclic strain) and a creep due to applied loads during the redox cycle. The cyclic strain was enhanced by the experience of high tensile loads, indicating a training effect. The training effect was explained by the enhanced electrochemical activity of the film. The creep was recovered by removal of the tensile load and several electrochemical cycles. This fact indicates that the creep results from the one-dimensional anisotropic deformation, and is retained (shape retention) by the ionic crosslink. The recovery of creep results from the elastic relaxation of the polymer conformation.

Application of ionic liquids based enzyme-assisted extraction of chlorogenic acid from Eucommia ulmoides leaves.

PubMed

Liu, Tingting; Sui, Xiaoyu; Li, Li; Zhang, Jie; Liang, Xin; Li, Wenjing; Zhang, Honglian; Fu, Shuang

2016-01-15

A new approach for ionic liquid based enzyme-assisted extraction (ILEAE) of chlorogenic acid (CGA) from Eucommia ulmoides is presented in which enzyme pretreatment was used in ionic liquids aqueous media to enhance extraction yield. For this purpose, the solubility of CGA and the activity of cellulase were investigated in eight 1-alkyl-3-methylimidazolium ionic liquids. Cellulase in 0.5 M [C6mim]Br aqueous solution was found to provide better performance in extraction. The factors of ILEAE procedures including extraction time, extraction phase pH, extraction temperatures and enzyme concentrations were investigated. Moreover, the novel developed approach offered advantages in term of yield and efficiency compared with other conventional extraction techniques. Scanning electronic microscopy of plant samples indicated that cellulase treated cell wall in ionic liquid solution was subjected to extract, which led to more efficient extraction by reducing mass transfer barrier. The proposed ILEAE method would develope a continuous process for enzyme-assisted extraction including enzyme incubation and solvent extraction process. In this research, we propose a novel view for enzyme-assisted extraction of plant active component, besides concentrating on enzyme facilitated cell wall degradation, focusing on improvement of bad permeability of ionic liquids solutions. Copyright © 2015 Elsevier B.V. All rights reserved.

Self-Assembled Polymeric Ionic Liquid-Functionalized Cellulose Nano-crystals: Constructing 3D Ion-conducting Channels Within Ionic Liquid-based Composite Polymer Electrolytes.

PubMed

Shi, Qing Xuan; Xia, Qing; Xiang, Xiao; Ye, Yun Sheng; Peng, Hai Yan; Xue, Zhi Gang; Xie, Xiao Lin; Mai, Yiu-Wing

2017-09-04

Composite polymeric and ionic liquid (IL) electrolytes are some of the most promising electrolyte systems for safer battery technology. Although much effort has been directed towards enhancing the transport properties of polymer electrolytes (PEs) through nanoscopic modification by incorporating nano-fillers, it is still difficult to construct ideal ion conducting networks. Here, a novel class of three-dimensional self-assembled polymeric ionic liquid (PIL)-functionalized cellulose nano-crystals (CNC) confining ILs in surface-grafted PIL polymer chains, able to form colloidal crystal polymer electrolytes (CCPE), is reported. The high-strength CNC nano-fibers, decorated with PIL polymer chains, can spontaneously form three-dimensional interpenetrating nano-network scaffolds capable of supporting electrolytes with continuously connected ion conducting networks with IL being concentrated in conducting domains. These new CCPE have exceptional ionic conductivities, low activation energies (close to bulk IL electrolyte with dissolved Li salt), high Li + transport numbers, low interface resistances and improved interface compatibilities. Furthermore, the CCPE displays good electrochemical properties and a good battery performance. This approach offers a route to leak-free, non-flammable and high ionic conductivity solid-state PE in energy conversion devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fundamental Insights into the Dissolution and Precipitation of Cellulosic Biomass from Ionic Liquid Mixtures

NASA Astrophysics Data System (ADS)

Minnick, David L.

Lignocellulose is the most abundant biopolymer on earth making it a promising feedstock for the production of renewable chemicals and fuels. However, utilization of biomass remains a challenge as recalcitrance of cellulose and hemicellulose hinder separation and conversion of these carbohydrates. For instance, the complex inter- and intra- molecular hydrogen bonding network of cellulose renders it insoluble in nearly all aqueous and organic solvents. Alternatively, select ionic liquids (ILs) dissolve significant quantities. Through an ionic liquid mediated dissolution and precipitation process cellulose crystallinity is significantly reduced consequently enhancing subsequent chemical and biochemical reaction processes. Therefore, understanding the thermodynamics of ionic liquid - cellulose mixtures is imperative to developing an IL based biomass processing system. This dissertation illustrates solid-liquid phase equilibrium results for the dissolution and precipitation of cellulose in various IL/cosolvent, IL/antisolvent, and IL/mixed solvent systems with the ionic liquid 1-ethyl-3-methylimidazolium diethyl phosphate ([EMIm][DEP]). Molecular interactions between the ionic liquid, organic solvents, and cellulose are assessed by spectroscopic techniques including Kamlet-Taft solvatochromic analysis, FTIR, and NMR. Additionally, this dissertation discusses how preferential solvation of the IL cation and anion by co- and anti-solvents impact the ability of IL ions to interact with cellulose thus affecting the cellulose dissolution capacity of the various IL-solvent mixtures.

The use of natural isotopes for identifying the origins of groundwater flows: Drentsche Aa Brook Valley, The Netherlands.

NASA Astrophysics Data System (ADS)

Elshehawi, Samer; Grootjans, Ab; Bregman, Enno

2017-04-01

This paper investigates the origin of various groundwater flows in a small brook valley reserve Drentsche Aa Valley in the northern part of the Netherlands. The aim was also to validate a hydrological model that simulated coupled particle flow in this area and also incorporated different scenarios for groundwater abstraction in order to predict future implications of groundwater abstraction on ecological values. Water samples from various sites and depths were analysed for macro-ionic composition, stable isotopes (2H and 18O) and also 14C. Three sites have 14C activities over 100%, indicating very recent water. The main groundwater discharge areas showed inflow of old groundwater up to 5000 years. Inflow of different groundwater flows of various ages could be detected most clearly from the 14C data. Downstream area that were affected by groundwater abstraction showed distinct infiltration characteristics, both in macro-ionic composition and contents of natural isotopes, to a depth of 6m below surface In the main exfiltration areas, we found that at 95 meters below the surface, the groundwater was characterized by a NaCl type groundwater facies. But the absolute concentrations were not high enough to conclude that double diffusive convection (DDC) near a salt diapir was responsible for this effect.

Electro-hydrodynamic force field and flow patterns generated by a DC corona discharge in the air

NASA Astrophysics Data System (ADS)

Monrolin, Nicolas; Plouraboue, Franck; Praud, Olivier

2016-11-01

Ionic wind refers to the electro-convection of ionised air between high voltage electrodes. Microscopic ion-neutral collisions are responsible for momentum transfer from accelerated ions, subjected to the electric field, to the neutral gas molecules resulting in a macroscopic airflow acceleration. In the past decades it has been investigated for various purposes from food drying through aerodynamic flow control and eventually laptop cooling. One consequence of air acceleration between the electrodes is thrust generation, often referred to as the Biefeld-Brown effect or electro-hydrodynamic thrust. In this experimental study, the ionic wind velocity field is measured with the PIV method. From computing the acceleration of the air we work out the electrostatic force field for various electrodes configurations. This enables an original direct evaluation of the force distribution as well as the influence of electrodes shape and position. Thrust computation based on the flow acceleration are compared with digital scale measurements. Complex flow features are highlighted such as vortex shedding, indicating that aerodynamic effects may play a significant role. Furthermore, the aerodynamic drag force exerted on the electrodes is quantified by choosing an appropriate control volume. Authors thank Region Midi-Pyrenee and CNES Launcher Directorate for financial support.

Nanoscale Bio-engineering Solutions for Space Exploration: The Nanopore Sequencer

NASA Technical Reports Server (NTRS)

Stolc, Viktor; Cozmuta, Ioana

2004-01-01

Characterization of biological systems at the molecular level and extraction of essential information for nano-engineering design to guide the nano-fabrication of solid-state sensors and molecular identification devices is a computational challenge. The alpha hemolysin protein ion channel is used as a model system for structural analysis of nucleic acids like DNA. Applied voltage draws a DNA strand and surrounding ionic solution through the biological nanopore. The subunits in the DNA strand block ion flow by differing amounts. Atomistic scale simulations are employed using NASA supercomputers to study DNA translocation, with the aim to enhance single DNA subunit identification. Compared to protein channels, solid-state nanopores offer a better temporal control of the translocation of DNA and the possibility to easily tune its chemistry to increase the signal resolution. Potential applications for NASA missions, besides real-time genome sequencing include astronaut health, life detection and decoding of various genomes.

Phosphorus-doped glass proton exchange membranes for low temperature direct methanol fuel cells

NASA Astrophysics Data System (ADS)

Prakash, Shruti; Mustain, William E.; Park, SeongHo; Kohl, Paul A.

Phosphorus-doped silicon dioxide thin films were used as ion exchange membranes in low temperature proton exchange membrane fuel cells. Phosphorus-doped silicon dioxide glass (PSG) was deposited via plasma-enhanced chemical vapor deposition (PECVD). The plasma deposition of PSG films allows for low temperature fabrication that is compatible with current microelectronic industrial processing. SiH 4, PH 3 and N 2O were used as the reactant gases. The effect of plasma deposition parameters, substrate temperature, RF power, and chamber pressure, on the ionic conductivity of the PSG films is elucidated. PSG conductivities as high as 2.54 × 10 -4 S cm -1 were realized, which is 250 times higher than the conductivity of pure SiO 2 films (1 × 10 -6 S cm -1) under identical deposition conditions. The higher conductivity films were deposited at low temperature, moderate pressure, limited reactant gas flow rate, and high RF power.

Nanoscale Bioengineering Solutions for Space Exploration the Nanopore Sequencer

NASA Technical Reports Server (NTRS)

Ioana, Cozmuta; Viktor, Stoic

2005-01-01

Characterization of biological systems at the molecular level and extraction of essential information for nano-engineering design to guide the nano-fabrication of solid-state sensors and molecular identification devices is a computational challenge. The alpha hemolysin protein ion channel is used as a model system for structural analysis of nucleic acids like DNA. Applied voltage draws a DNA strand and surrounding ionic solution through the biological nanopore. The subunits in the DNA strand block ion flow by differing amounts. Atomistic scale simulations are employed using NASA supercomputers to study DNA translocation. with the aim to enhance single DNA subunit identification. Compared to protein channels, solid-state nanopores offer a better temporal control of the translocation of DNA and the possibility to easily tune its chemistry to increase the signal resolution. Potential applications for NASA missions, besides real-time genome sequencing include astronaut health, life detection and decoding of various genomes. http://phenomrph.arc.nasa.gov/index.php

Differential impact of ionic and coordinate covalent chromium (Cr)-DNA binding on DNA replication.

PubMed

Fornsaglio, Jamie L; O'Brien, Travis J; Patierno, Steven R

2005-11-01

The reactive species produced by the reduction of Cr(VI), particularly Cr(III), can form both ionic and coordinate covalent complexes with DNA. These Cr(III)-DNA interactions consist of Cr-DNA monoadducts, Cr-DNA ternary adducts, and Cr-DNA interstrand cross-links (Cr-ICLs), the latter of which are DNA polymerase arresting lesions (PALs). We sought to determine the impact of Cr-DNA interactions on the formation of replication blocking lesions in S. cerevisiae using a PCR-based method. We found that target sequence (TS) amplification using DNA isolated from Cr(VI)-treated yeast actually increased as a function of Cr(VI) concentration. Moreover, the enhanced TS amplification was reproduced in vitro using Cr(III)-treated DNA. In contrast, PCR amplification of TS from DNA isolated from yeast exposed to equitoxic doses of the inorganic DNA cross-linking agent cisplatin (CDDP), was decreased in a concentration-dependent manner. This paradox suggested that a specific Cr-DNA interaction, such as an ionic Cr-DNA complex, was responsible for the enhanced TS amplification, thereby masking the replication-blocking effect of certain ternary Cr-DNA adducts (i.e. interstrand cross-links). To test this possibility, we removed ionically associated Cr from the DNA using salt extraction prior to PCR analysis. This procedure obviated the increased amplification and revealed a dose-dependent decrease in TS amplification and an increase in Cr-PALs. These data from DNA analyzed ex vivo after treatment of intact cells indicate that ionic interactions of Cr with DNA result in increased DNA amplification whereas coordinate-covalent Cr-DNA complexes lead to formation of Cr-PALs. Thus, these results suggest that treatment of living cells with Cr(VI) leads to two modes of Cr-binding, which may have conflicting effects on DNA replication.

Phytoremediation of Ionic and Methyl Mercury Pollution

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

Meagher, Richard B.

Phytoremediation is defined as the use of plants to extract, resist, detoxify, and/or sequester toxic environmental pollutants. The long-term goal of the proposed research is to develop and test highly productive, field-adapted plant species that have been engineered for the phytoremediation of mercury. A variety of different genes, which should enable plants to clean mercury polluted sites are being tested as tools for mercury phytoremediation, first in model laboratory plants and then in potential field species. Several of these genes have already been shown to enhance mercury phytoremediation. Mercury pollution is a serious, world-wide problem affecting the health of humanmore » and wildlife populations. Environmentally, the most serious mercury threat is the production of methylmercury (CH3Hg+) by native bacteria at mercury contaminated wetland sites. Methylmercury is inherently more toxic than metallic (Hg(0)) or ionic (Hg(II)) mercury, and because methylmercury is prolifically biomagnified up the food chain, it poses the most immediate danger to animal populations. We have successfully engineered two model plants, Arabidopsis and tobacco, to use the bacterial merB gene to convert methylmercury to less toxic ionic mercury and to use the bacterial merA gene to further detoxify ionic mercury to the least toxic form of mercury, metallic mercury. Plants expressing both MerA and MerB proteins detoxify methylmercury in two steps to the metallic form. These plants germinate, grow, and set seed at normal growth rates on levels of methylmercury or ionic mercury that are lethal to normal plants. Our newest efforts involve engineering plants with several additional bacterial and plant genes that allow for higher levels of mercury resistance and mercury hyperaccumulation. The potential for these plants to hyperaccumulate mercury was further advanced by developing constitutive, aboveground, and root-specific gene expression systems. Our current strategy is to engineer plants to control the chemical speciation, electrochemical state, transport, and aboveground binding of mercury in order to manage this toxicant. To advance this mercury phytoremediation strategy, our planned research focuses on the following Specific Aims: (1) to increase the transport of mercury to aboveground tissue; (2) to identify small mercury binding peptides that enhance hyperaccumulation aboveground; (3) to test the ability of multiple genes acting together to enhance resistance and hyperaccumulation; (4) to construct a simple molecular system for creating male/female sterility, allowing engineered grass, shrub, and tree species to be released indefinitely at contaminated sites; (5) to test the ability of transgenic cottonwood and rice plants to detoxify ionic mercury and prevent methylmercury release from contaminated sediment; and (6) to initiate field testing with transgenic cottonwood and rice for the remediation of methylmercury and ionic mercury. The results of these experiments will enable the phytoremediation of methyl- and ionic mercury by a wide spectrum of deep-rooted, fast-growing plants adapted to diverse environments. We have made significant progress on all six of these specific aims as summarized below.« less

Conductivity and Thermal Studies on Plasticized Nano-Composite Solid Polymer Electrolyte, Peo: Ec: LiTf: Al2O3

NASA Astrophysics Data System (ADS)

Pitawala, H. M. J. C.; Dissanayake, M. A. K. L.; Seneviratne, V. A.

2006-06-01

Poly (ethylene oxide)-(PEO)-based composite polymer electrolytes are of great interest for solid-state-electrochemical devices. This paper presents the results of a preliminary study on electrical conductivity and thermal behavior (DSC) of composite polymer electrolytes (CPEs) containing PEO: LiCF3SO3 complexed with plasticizer (EC) and incorporating nano-sized particles of the ceramic filler Al2O3. Ionic conductivity enhancement in these electrolytes has been obtained by optimizing the combined effect of the plasticizer and the ceramic filler. Nano-composite, plasticized polymer electrolyte films (400-600μm) were prepared by common solvent casting method. It was revealed that the presence of the Al2O3 filler in PEO: LiTf polymer electrolyte significantly enhanced the ionic conductivity in the temperature range of interest, giving the maximum conductivity for (PEO)9LiTf+15 wt.% Al2O3 CPE [σRT (max)=2×10-5 S cm-1]. It was also observed that the addition of plasticizer (EC) to this electrolyte up to a concentration of 50 wt. % EC, showed a further conductivity enhancement [σRT (max) = 1.5×10-4 S cm-1]. It is suggested that the conductivity is enhanced mainly by two mechanisms. The plasticizer (EC) would directly contribute by reducing the crystallinity and increasing the amorphous phase content of the polymer electrolytes. The ceramic filler (Al2O3) would contribute to conductivity enhancement by creating additional sites to migrating ionic species through transient bonding with O/OH groups in the filler surface. The decrease of Tg values of plasticized CPE systems seen in the DSC thermograms points towards the improved segmental flexibility of polymer chains, increasing the mobility of conducting ions.

ISOTOPE FRACTIONATION PROCESS

DOEpatents

Clewett, G.H.; Lee, DeW.A.

1958-05-20

A new method is described for isotopic enrichment of uranium. It has been found that when an aqueous acidic solution of ionic tetravalent uraniunn is contacted with chelate complexed tetravalent uranium, the U/sup 238/ preferentially concentrates in the complexed phase while U/sup 235/ concentrates in the ionic phase. The effect is enhanced when the chelate compound is water insoluble and is dissolved in a water-immiscible organic solvent. Cupferron is one of a number of sultable complexing agents, and chloroform is a suitable organic solvent.

Multifunctional Poro-Vascular Composites for UAV Performance Enhancement

DTIC Science & Technology

2012-07-31

structural “skin” materials with surface pores and internal vascular channels filled with an ionic- liquid whose height and shape at the pore exits is...2 V t e e q q          Intrinsic contact angle (zero voltage) Applied potential Interfacial tension (IFT) of ionic liquid Lippmann...Characterization flat plates  single (capillary) pore  PV pore arrays FTA 1000 Drop-Shape Characterization • Microscope lens : 0.5 to 12x magnification • Side

Pycnonuclear reaction rates for binary ionic mixtures

NASA Technical Reports Server (NTRS)

Ichimaru, S.; Ogata, S.; Van Horn, H. M.

1992-01-01

Through a combination of compositional scaling arguments and examinations of Monte Carlo simulation results for the interparticle separations in binary-ionic mixture (BIM) solids, we have derived parameterized expressions for the BIM pycnonuclear rates as generalizations of those in one-component solids obtained previously by Salpeter and Van Horn and by Ogata et al. We have thereby discovered a catalyzing effect of the heavier elements, which enhances the rates of reactions among the lighter elements when the charge ratio exceeds a critical value of approximately 2.3.

High-speed microwave-promoted hetero-Diels-Alder reactions of 2(1H)-pyrazinones in ionic liquid doped solvents.

PubMed

Van Der Eycken, Erik; Appukkuttan, Prasad; De Borggraeve, Wim; Dehaen, Wim; Dallinger, Doris; Kappe, C Oliver

2002-11-01

Inter- and intramolecular hetero-Diels-Alder reactions in a series of functionalized 2(1H)-pyrazinones were investigated under controlled microwave irradiation. The cycloaddition reactions were efficiently performed in sealed tubes, utilizing either a combination of 1,2-dichloroethane and a thermally stable ionic liquid, or 1,2-dichlorobenzene as reaction medium. In all cases, a significant rate-enhancement using microwave flash heating as compared to thermal heating was observed.

Pyrene-Tagged Ionic Liquids: Separable Organic Catalysts for SN2 Fluorination.

PubMed

Taher, Abu; Lee, Kyo Chul; Han, Hye Ji; Kim, Dong Wook

2017-07-07

We prepared pyrene-substituted imidazolium-based ionic liquids (PILs) as organic catalysts for the S N 2 fluorination using alkali metal fluoride (MF). In this system, the PIL significantly enhanced the reactivity of MF due to the phase-transfer catalytic effect of the imidazolium moiety as well as the metal cation-π (pyrene) interactions. Furthermore, this homogeneous catalyst PIL was easily separated from the reaction mixture using reduced graphene oxide by π-π stacking with the pyrene of PIL.

Ultrasonically promoted nitrolysis of DAPT to HMX in ionic liquid.

PubMed

Hua, Qian; Zhiwen, Ye; Chunxu, Lv

2008-04-01

The present work aims at developing a new process to synthesize HMX from DAPT using ultrasound in ionic liquid. Reaction has been carried out in ultrasonic bath, effect of various parameters such as presence and absence of ultrasound, volume and type of solvent, temperature, concentration of nitrating agent has been investigated with an aim of obtaining the optimum conditions for the synthesis of HMX. It was observed that ultrasonically promoted nitroylsis of DAPT to HMX has exhibited significant enhancement in yield at ambient condition.

Performance improvement of IPMC flow sensors with a biologically-inspired cupula structure

NASA Astrophysics Data System (ADS)

Lei, Hong; Sharif, Montassar Aidi; Paley, Derek A.; McHenry, Matthew J.; Tan, Xiaobo

2016-04-01

Ionic polymer-metal composites (IPMCs) have inherent underwater sensing and actuation properties. They can be used as sensors to collect flow information. Inspired by the hair-cell mediated receptor in the lateral line system of fish, the impact of a flexible, cupula-like structure on the performance of IPMC flow sensors is experimentally explored. The fabrication method to create a silicone-capped IPMC sensor is reported. Experiments are conducted to compare the sensing performance of the IPMC flow sensor before and after the PDMS coating under the periodic flow stimulus generated by a dipole source in still water and the laminar flow stimulus generated in a flow tank. Experimental results show that the performance of IPMC flow sensors is significantly improved under the stimulus of both periodic flow and laminar flow by the proposed silicone-capping.

Liquid methanol under a static electric field

NASA Astrophysics Data System (ADS)

Cassone, Giuseppe; Giaquinta, Paolo V.; Saija, Franz; Saitta, A. Marco

2015-02-01

We report on an ab initio molecular dynamics study of liquid methanol under the effect of a static electric field. We found that the hydrogen-bond structure of methanol is more robust and persistent for field intensities below the molecular dissociation threshold whose value (≈0.31 V/Å) turns out to be moderately larger than the corresponding estimate obtained for liquid water. A sustained ionic current, with ohmic current-voltage behavior, flows in this material for field intensities above 0.36 V/Å, as is also the case of water, but the resulting ionic conductivity (≈0.40 S cm-1) is at least one order of magnitude lower than that of water, a circumstance that evidences a lower efficiency of proton transfer processes. We surmise that this study may be relevant for the understanding of the properties and functioning of technological materials which exploit ionic conduction, such as direct-methanol fuel cells and Nafion membranes.

Extraction of acetanilides in rice using ionic liquid-based matrix solid phase dispersion-solvent flotation.

PubMed

Zhang, Liyuan; Wang, Changyuan; Li, Zuotong; Zhao, Changjiang; Zhang, Hanqi; Zhang, Dongjie

2018-04-15

Ionic liquid-based matrix solid phase dispersion-solvent flotation coupled with high performance liquid chromatography was developed for the determination of the acetanilide herbicides, including metazachlor, propanil, alachlor, propisochlor, pretilachlor, and butachlor in rice samples. Some experimental parameters, including the type of dispersant, the mass ratio of dispersant to sample, pH of sample solution, the type of extraction solvent, the type of ionic liquid, flotation time, and flow rate of N 2 were optimized. The average recoveries of the acetanilide herbicides at spiked concentrations of 50, 125, and 250 µg/kg ranged from 89.4% to 108.7%, and relative standard deviations were equal to or lower than 7.1%, the limits of quantification were in the range of 38.0 to 84.7 µg/kg. Copyright © 2017 Elsevier Ltd. All rights reserved.

Understanding the impact of the central atom on the ionic liquid behavior: phosphonium vs ammonium cations.

PubMed

Carvalho, Pedro J; Ventura, Sónia P M; Batista, Marta L S; Schröder, Bernd; Gonçalves, Fernando; Esperança, José; Mutelet, Fabrice; Coutinho, João A P

2014-02-14

The influence of the cation's central atom in the behavior of pairs of ammonium- and phosphonium-based ionic liquids was investigated through the measurement of densities, viscosities, melting temperatures, activity coefficients at infinite dilution, refractive indices, and toxicity against Vibrio fischeri. All the properties investigated are affected by the cation's central atom nature, with ammonium-based ionic liquids presenting higher densities, viscosities, melting temperatures, and enthalpies. Activity coefficients at infinite dilution show the ammonium-based ionic liquids to present slightly higher infinite dilution activity coefficients for non-polar solvents, becoming slightly lower for polar solvents, suggesting that the ammonium-based ionic liquids present somewhat higher polarities. In good agreement these compounds present lower toxicities than the phosphonium congeners. To explain this behavior quantum chemical gas phase DFT calculations were performed on isolated ion pairs at the BP-TZVP level of theory. Electronic density results were used to derive electrostatic potentials of the identified minimum conformers. Electrostatic potential-derived CHelpG and Natural Population Analysis charges show the P atom of the tetraalkylphosphonium-based ionic liquids cation to be more positively charged than the N atom in the tetraalkylammonium-based analogous IL cation, and a noticeable charge delocalization occurring in the tetraalkylammonium cation, when compared with the respective phosphonium congener. It is argued that this charge delocalization is responsible for the enhanced polarity observed on the ammonium based ionic liquids explaining the changes in the thermophysical properties observed.

Understanding the impact of the central atom on the ionic liquid behavior: Phosphonium vs ammonium cations

NASA Astrophysics Data System (ADS)

Carvalho, Pedro J.; Ventura, Sónia P. M.; Batista, Marta L. S.; Schröder, Bernd; Gonçalves, Fernando; Esperança, José; Mutelet, Fabrice; Coutinho, João A. P.

2014-02-01

The influence of the cation's central atom in the behavior of pairs of ammonium- and phosphonium-based ionic liquids was investigated through the measurement of densities, viscosities, melting temperatures, activity coefficients at infinite dilution, refractive indices, and toxicity against Vibrio fischeri. All the properties investigated are affected by the cation's central atom nature, with ammonium-based ionic liquids presenting higher densities, viscosities, melting temperatures, and enthalpies. Activity coefficients at infinite dilution show the ammonium-based ionic liquids to present slightly higher infinite dilution activity coefficients for non-polar solvents, becoming slightly lower for polar solvents, suggesting that the ammonium-based ionic liquids present somewhat higher polarities. In good agreement these compounds present lower toxicities than the phosphonium congeners. To explain this behavior quantum chemical gas phase DFT calculations were performed on isolated ion pairs at the BP-TZVP level of theory. Electronic density results were used to derive electrostatic potentials of the identified minimum conformers. Electrostatic potential-derived CHelpG and Natural Population Analysis charges show the P atom of the tetraalkylphosphonium-based ionic liquids cation to be more positively charged than the N atom in the tetraalkylammonium-based analogous IL cation, and a noticeable charge delocalization occurring in the tetraalkylammonium cation, when compared with the respective phosphonium congener. It is argued that this charge delocalization is responsible for the enhanced polarity observed on the ammonium based ionic liquids explaining the changes in the thermophysical properties observed.

Research progress on ionic plasmas generated in an intense hydrogen negative ion source

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

Takeiri, Y., E-mail: takeiri@nifs.ac.jp; Tsumori, K.; Nagaoka, K.

2015-04-08

Characteristics of ionic plasmas, observed in a high-density hydrogen negative ion source, are investigated with a multi-diagnostics system. The ionic plasma, which consists of hydrogen positive- and negative-ions with a significantly low-density of electrons, is generated in the ion extraction region, from which the negative ions are extracted through the plasma grid. The negative ion density, i.e., the ionic plasma density, as high as the order of 1×10{sup 17}m{sup −3}, is measured with cavity ring-down spectroscopy, while the electron density is lower than 1×10{sup 16}m{sup −3}, which is confirmed with millimeter-wave interferometer. Reduction of the negative ion density is observedmore » at the negative ion extraction, and at that time the electron flow into the ionic plasma region is observed to conserve the charge neutrality. Distribution of the plasma potential is measured in the extraction region in the direction normal to the plasma grid surface with a Langmuir probe, and the results suggest that the sheath is formed at the plasma boundary to the plasma grid to which the bias voltage is applied. The beam extraction should drive the negative ion transport in the ionic plasma across the sheath formed on the extraction surface. Larger reduction of the negative ions at the beam extraction is observed in a region above the extraction aperture on the plasma grid, which is confirmed with 2D image measurement of the Hα emission and cavity ring-down spectroscopy. The electron distribution is also measured near the plasma grid surface. These various properties observed in the ionic plasma are discussed.« less

Electrokinetic motion of a rectangular nanoparticle in a nanochannel

NASA Astrophysics Data System (ADS)

Movahed, Saeid; Li, Dongqing

2012-08-01

This article presents a theoretical study of electrokinetic motion of a negatively charged cubic nanoparticle in a three-dimensional nanochannel with a circular cross-section. Effects of the electrophoretic and the hydrodynamic forces on the nanoparticle motion are examined. Because of the large applied electric field over the nanochannel, the impact of the Brownian force is negligible in comparison with the electrophoretic and the hydrodynamic forces. The conventional theories of electrokinetics such as the Poisson-Boltzmann equation and the Helmholtz-Smoluchowski slip velocity approach are no longer applicable in the small nanochannels. In this study, and at each time step, first, a set of highly coupled partial differential equations including the Poisson-Nernst-Plank equation, the Navier-Stokes equations, and the continuity equation was solved to find the electric potential, ionic concentration field, and the flow field around the nanoparticle. Then, the electrophoretic and hydrodynamic forces acting on the negatively charged nanoparticle were determined. Following that, the Newton second law was utilized to find the velocity of the nanoparticle. Using this model, effects of surface electric charge of the nanochannel, bulk ionic concentration, the size of the nanoparticle, and the radius of the nanochannel on the nanoparticle motion were investigated. Increasing the bulk ionic concentration or the surface charge of the nanochannel will increase the electroosmotic flow, and hence affect the particle's motion. It was also shown that, unlike microchannels with thin EDL, the change in nanochannel size will change the EDL field and the ionic concentration field in the nanochannel, affecting the particle's motion. If the nanochannel size is fixed, a larger particle will move faster than a smaller particle under the same conditions.

Canopy Dynamics in Nanoscale Ionic Materials Probed by NMR

NASA Astrophysics Data System (ADS)

Mirau, Peter

2013-03-01

Nanoscale ionic materials (NIMs) are hybrids prepared from ionically functionalized nanoparticles (NP) neutralized by oligomeric polymer counter-ions. NIMs are designed to behave as liquids under ambient conditions in the absence of solvent and have no volatile organic content, making them useful for a number of applications. We have used NMR relaxation and pulse-field gradient NMR to probe local and collective canopy dynamics in NIMs based on silica nanoparticles (NP), fullerols and proteins in order to understand the relationship between the core and canopy structure and the bulk properties. The NMR studies show that the canopy dynamics depend on the degree of neutralization, the canopy radius of gyration and molecular crowding at the ionically modified NP surface. The viscosity in NIMs can be directly controlled with the addition of ions that enhance the exchange rate for polymers at the NP surface. These results show that NIMs for many applications can be prepared by controlling the dynamics of the NP interface.

Exceptionally High Electric Double Layer Capacitances of Oligomeric Ionic Liquids.

PubMed

Matsumoto, Michio; Shimizu, Sunao; Sotoike, Rina; Watanabe, Masayoshi; Iwasa, Yoshihiro; Itoh, Yoshimitsu; Aida, Takuzo

2017-11-15

Electric double layer (EDL) capacitors are promising as next-generation energy accumulators if their capacitances and operation voltages are both high. However, only few electrolytes can simultaneously fulfill these two requisites. Here we report that an oligomeric ionic liquid such as IL4 TFSI with four imidazolium ion units in its structure provides a wide electrochemical window of ∼5.0 V, similar to monomeric ionic liquids. Furthermore, electrochemical impedance measurements using Au working electrodes demonstrated that IL4 TFSI exhibits an exceptionally high EDL capacitance of ∼66 μF/cm 2 , which is ∼6 times as high as those of monomeric ionic liquids so far reported. We also found that an EDL-based field effect transistor (FET) using IL4 TFSI as a gate dielectric material and SrTiO 3 as a channel material displays a very sharp transfer curve with an enhanced carrier accumulation capability of ∼64 μF/cm 2 , as determined by Hall-effect measurements.

Highly Efficient Plastic Crystal Ionic Conductors for Solid-state Dye-sensitized Solar Cells

PubMed Central

Hwang, Daesub; Kim, Dong Young; Jo, Seong Mu; Armel, Vanessa; MacFarlane, Douglas R.; Kim, Dongho; Jang, Sung-Yeon

2013-01-01

We have developed highly efficient, ambient temperature, solid-state ionic conductors (SSICs) for dye-sensitized solar cells (DSSCs) by doping a molecular plastic crystal, succinonitrile (SN), with trialkyl-substituted imidazolium iodide salts. High performance SSICs with enhanced ionic conductivity (2–4 mScm−1) were obtained. High performance solid-state DSSCs with power conversion efficiency of 7.8% were fabricated using our SSICs combined with unique hierarchically nanostructured TiO2 sphere (TiO2-SP) photoelectrodes; these electrodes have significant macroporosity, which assists penetration of the solid electrolyte into the electrode. The performance of our solid-state DSSCs is, to the best of our knowledge, the highest reported thus far for cells using plastic crystal-based SSICs, and is comparable to that of the state-of-the-art DSSCs which use ionic liquid type electrolytes. This report provides a logical strategy for the development of efficient plastic crystal-based SSICs for DSSCs and other electrochemical devices. PMID:24343425

Direct Observation of Ion Distributions near Electrodes in Ionic Polymer Actuators Containing Ionic Liquids

PubMed Central

Liu, Yang; Lu, Caiyan; Twigg, Stephen; Ghaffari, Mehdi; Lin, Junhong; Winograd, Nicholas; Zhang, Q. M.

2013-01-01

The recent boom of energy storage and conversion devices, exploiting ionic liquids (ILs) to enhance the performance, requires an in-depth understanding of this new class of electrolytes in device operation conditions. One central question critical to device performance is how the mobile ions accumulate near charged electrodes. Here, we present the excess ion depth profiles of ILs in ionomer membrane actuators (Aquivion/1-butyl-2,3-dimethylimidazolium chloride (BMMI-Cl), 27 μm thick), characterized directly by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) at liquid nitrogen temperature. Experimental results reveal that for the IL studied, cations and anions are accumulated at both electrodes. The large difference in the total volume occupied by the excess ions between the two electrodes cause the observed large bending actuation of the actuator. Hence we demonstrate that ToF-SIMS experiment provides great insights on the physics nature of ionic devices. PMID:23512124

Enhanced proton transport in nanostructured polymer electrolyte/ionic liquid membranes under water-free conditions.

PubMed

Kim, Sung Yeon; Kim, Suhan; Park, Moon Jeong

2010-10-05

Proton exchange fuel cells (PEFCs) have the potential to provide power for a variety of applications ranging from electronic devices to transportation vehicles. A major challenge towards economically viable PEFCs is finding an electrolyte that is both durable and easily passes protons. In this article, we study novel anhydrous proton-conducting membranes, formed by incorporating ionic liquids into synthetic block co-polymer electrolytes, poly(styrenesulphonate-b-methylbutylene) (S(n)MB(m)), as high-temperature PEFCs. The resulting membranes are transparent, flexible and thermally stable up to 180 °C. The increases in the sulphonation level of S(n)MB(m) co-polymers (proton supplier) and the concentration of the ionic liquid (proton mediator) produce an overall increase in conductivity. Morphology effects were studied by X-ray scattering and electron microscopy. Compared with membranes having discrete ionic domains (including Nafion 117), the nanostructured membranes revealed over an order of magnitude increase in conductivity with the highest conductivity of 0.045 S cm(-1) obtained at 165 °C.

Titanium dioxide nanoparticles: Impact of increasing ionic strength during synthesis, reflux, and hydrothermal aging

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

Isley, Sara L.; Jordan, David S.; Penn, R. Lee

2009-01-08

This work investigates the role of ionic strength during synthesis, reflux, and hydrothermal aging of sol-gel synthesized titanium dioxide. Research presented here uses X-ray diffraction data and Rietveld refinements to quantify anatase, brookite, and rutile phases as functions of synthetic and aging variables. In addition, the Scherrer equation is used to obtain average crystallite sizes for each phase quantified. Results presented in this work demonstrate that the most control over the sol-gel products can be obtained by modifying the pH during hydrolysis. In addition, while varying the ionic strength during reflux and hydrothermal aging can result in enhanced control overmore » the crystalline phase and crystallite size, the most control can be achieved by varying the ionic strength during synthesis. Finally, sol-gel synthesis at low pH (-0.6) and high-chloride concentration (3 M NaCl) produced a heterogeneous sample composed of nanocrystalline anatase (3.8 nm) and rutile (2.9 nm)« less

New Insights into the Compositional Dependence of Li-Ion Transport in Polymer-Ceramic Composite Electrolytes.

PubMed

Zheng, Jin; Hu, Yan-Yan

2018-01-31

Composite electrolytes are widely studied for their potential in realizing improved ionic conductivity and electrochemical stability. Understanding the complex mechanisms of ion transport within composites is critical for effectively designing high-performance solid electrolytes. This study examines the compositional dependence of the three determining factors for ionic conductivity, including ion mobility, ion transport pathways, and active ion concentration. The results show that with increase in the fraction of ceramic Li 7 La 3 Zr 2 O 12 (LLZO) phase in the LLZO-poly(ethylene oxide) composites, ion mobility decreases, ion transport pathways transit from polymer to ceramic routes, and the active ion concentration increases. These changes in ion mobility, transport pathways, and concentration collectively explain the observed trend of ionic conductivity in composite electrolytes. Liquid additives alter ion transport pathways and increase ion mobility, thus enhancing ionic conductivity significantly. It is also found that a higher content of LLZO leads to improved electrochemical stability of composite electrolytes. This study provides insight into the recurring observations of compositional dependence of ionic conductivity in current composite electrolytes and pinpoints the intrinsic limitations of composite electrolytes in achieving fast ion conduction.

An emerging integration between ionic liquids and nanotechnology: general uses and future prospects in drug delivery.

PubMed

de Almeida, Tânia Santos; Júlio, Ana; Mota, Joana Portugal; Rijo, Patrícia; Reis, Catarina Pinto

2017-06-01

There is a growing need to develop drug-delivery systems that overcome drawbacks such as poor drug solubility/loading/release, systemic side effects and limited stability. Ionic liquids (ILs) offer many advantages and their tailoring represents a valuable tuning tool. Nano-based systems are also prized materials that prevent drug degradation, enhance their transport/distribution and extend their release. Consequently, structures containing ILs and nanoparticles (NPs) have been developed to attain synergistic effects. This overview on the properties of ILs, NPs and of their combined structures, reveals the recent advances in these areas through a review of pertinent literature. The IL-NP structures present enhanced properties and the subsequent performance upgrade proves to be useful in drug delivery, although much is yet to be done.

Evaluations of imidazolium ionic liquids as novel skin permeation enhancers for drug transdermal delivery.

PubMed

Zhang, Ding; Wang, Huai-Ji; Cui, Xiu-Ming; Wang, Cheng-Xiao

2017-06-01

In this work, imidazolium ionic liquids (imidazolium ILs) were employed as the novel chemical permeation enhancers (CPEs) and their performances and mechanisms of action were deeply investigated. Testosterone was used as a model drug to investigate the transdermal delivery enhancement of twenty imdidazolium ILs. The results suggested that the promotion activity connected to the structure and composition of the ILs. The quantitative structure-activity relationship (QSAR) model revealed a good linearity between the electronic properties of ILs and their enhancements. Furthermore, the transepidermal water loss (TEWL) and scanning laser confocal microscope (CLSM) examinations showed the strong improvement of ILs on skin barrier permeability, which were well correlated with the drug penetration profiles. The total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) and atomic force microscope (AFM) evaluations of skins indicated that the ILs can disrupt the regular and compact arrangements of the corneocytes, change the surface properties of stratum corneum, and make the skin structure more permeable. Our work demonstrated the significant skin permeation promotion profiles of the imidazolium ILs, which are of great potential in transdermal drug delivery systems.

Flow-Tube Investigations of Hypergolic Reactions of a Dicyanamide Ionic Liquid Via Tunable Vacuum Ultraviolet Aerosol Mass Spectrometry.

PubMed

Chambreau, Steven D; Koh, Christine J; Popolan-Vaida, Denisia M; Gallegos, Christopher J; Hooper, Justin B; Bedrov, Dmitry; Vaghjiani, Ghanshyam L; Leone, Stephen R

2016-10-07

The unusually high heats of vaporization of room-temperature ionic liquids (RTILs) complicate the utilization of thermal evaporation to study ionic liquid reactivity. Although effusion of RTILs into a reaction flow-tube or mass spectrometer is possible, competition between vaporization and thermal decomposition of the RTIL can greatly increase the complexity of the observed reaction products. In order to investigate the reaction kinetics of a hypergolic RTIL, 1-butyl-3-methylimidazolium dicyanamide (BMIM + DCA - ) was aerosolized and reacted with gaseous nitric acid, and the products were monitored via tunable vacuum ultraviolet photoionization time-of-flight mass spectrometry at the Chemical Dynamics Beamline 9.0.2 at the Advanced Light Source. Reaction product formation at m/z 42, 43, 44, 67, 85, 126, and higher masses was observed as a function of HNO 3 exposure. The identities of the product species were assigned to the masses on the basis of their ionization energies. The observed exposure profile of the m/z 67 signal suggests that the excess gaseous HNO 3 initiates rapid reactions near the surface of the RTIL aerosol. Nonreactive molecular dynamics simulations support this observation, suggesting that diffusion within the particle may be a limiting step. The mechanism is consistent with previous reports that nitric acid forms protonated dicyanamide species in the first step of the reaction.

Noninvasive quantitative measurement of colloid transport in mesoscale porous media using time lapse fluorescence imaging.

PubMed

Bridge, Jonathan W; Banwart, Steven A; Heathwaite, A Louise

2006-10-01

We demonstrate noninvasive quantitative imaging of colloid and solute transport at millimeter to decimeter (meso-) scale. Ultraviolet (UV) excited fluorescent solute and colloid tracers were independently measured simultaneously during co-advection through saturated quartz sand. Pulse-input experiments were conducted at constant flow rates and ionic strengths 10(-3), 10(-2) and 10(-1) M NaCl. Tracers were 1.9 microm carboxylate latex microspheres and disodium fluorescein. Spatial moments analysis was used to quantify relative changes in mass distribution of the colloid and solute tracers over time. The solute advected through the sand at a constant velocity proportional to flow rate and was described well by a conservative transport model (CXTFIT). In unfavorable deposition conditions increasing ionic strength produced significant reduction in colloid center of mass transport velocity over time. Velocity trends correlated with the increasing fraction of colloid mass retained along the flowpath. Attachment efficiencies (defined by colloid filtration theory) calculated from nondestructive retained mass data were 0.013 +/- 0.03, 0.09 +/- 0.02, and 0.22 +/- 0.05 at 10(-3), 10(-2), and 10(-1) M ionic strength, respectively, which compared well with previously published data from breakthrough curves and destructive sampling. Mesoscale imaging of colloid mass dynamics can quantify key deposition and transport parameters based on noninvasive, nondestructive, spatially high-resolution data.

The chemical identity of intervessel pit membranes in Acer challenges hydrogel control of xylem hydraulic conductivity

PubMed Central

Klepsch, Matthias M.; Schmitt, Marco; Paul Knox, J.; Jansen, Steven

2016-01-01

Ion-mediated enhancement of the hydraulic conductivity of xylem tissue (i.e. the ionic effect) has been reported for various angiosperm species. One explanation of the ionic effect is that it is caused by the swelling and shrinking of intervessel pit membranes due to the presence of pectins and/or other cell-wall matrix polymers such as heteroxylans or arabinogalactan–proteins (AGPs) that may contain acidic sugars. Here, we examined the ionic effect for six Acer species and their pit membrane chemistry using immunocytochemistry, including antibodies against glycoproteins. Moreover, anatomical features related to the bordered pit morphology and vessel dimensions were investigated using light and electron microscopy. The ionic effect varied from 18 % (± 9) to 32 % (± 13). Epitopes of homogalacturonan (LM18) and xylan (LM11) were not detected in intervessel pit membranes. Negative results were also obtained for glycoproteins (extensin: LM1, JIM20; AGP glycan: LM2), although AGP (JIM13)-related epitopes were detected in parenchyma cells. The mean vessel length was significantly correlated with the magnitude of the ionic effect, unlike other pit or vessel-related characteristics. Our results suggest that intervessel pit membranes of Acer are unlikely to contain pectic or other acidic polysaccharides. Therefore, alternative explanations should be tested to clarify the ionic effect. PMID:27354661

Effect of Structure on Transport Properties (Viscosity, Ionic Conductivity, and Self-Diffusion Coefficient) of Aprotic Heterocyclic Anion (AHA) Room Temperature Ionic Liquids. 2. Variation of Alkyl Chain Length in the Phosphonium Cation.

PubMed

Sun, Liyuan; Morales-Collazo, Oscar; Xia, Han; Brennecke, Joan F

2016-06-30

A series of room-temperature ionic liquids (ILs) composed of triethyl(alkyl)phosphonium cations paired with three different aprotic heterocyclic anions (AHAs) (alkyl = butyl ([P2224](+)) and octyl ([P2228](+))) were prepared to investigate the effect of cationic alkyl chain length on transport properties. The transport properties and density of these ILs were measured from 283.15 to 343.15 K at ambient pressure. The dependence of the transport properties (viscosity, ionic conductivity, diffusivity, and molar conductivity) on temperature can be described by the Vogel-Fulcher-Tamman (VFT) equation. The ratio of the molar conductivity obtained from the molar concentration and ionic conductivity measurements to that calculated from self-diffusion coefficients (measured by pulsed gradient spin-echo nuclear magnetic resonance spectroscopy) using the Nernst-Einstein equation was used to quantify the ionicity of these ILs. The molar conductivity ratio decreases with increasing number of carbon atoms in the alkyl chain, indicating that the reduced Coulombic interactions resulting from lower density are more than balanced by the increased van der Waals interactions between the alkyl chains. The results of this study may provide insight into the design of ILs with enhanced dynamics that may be suitable as electrolytes in lithium ion batteries and other electrochemical applications.

Frequency-Stable Ionic-Type Hybrid Gate Dielectrics for High Mobility Solution-Processed Metal-Oxide Thin-Film Transistors

PubMed Central

Heo, Jae Sang; Choi, Seungbeom; Jo, Jeong-Wan; Kang, Jingu; Park, Ho-Hyun; Kim, Yong-Hoon; Park, Sung Kyu

2017-01-01

In this paper, we demonstrate high mobility solution-processed metal-oxide thin-film transistors (TFTs) by using a high-frequency-stable ionic-type hybrid gate dielectric (HGD). The HGD gate dielectric, a blend of sol-gel aluminum oxide (AlOx) and poly(4-vinylphenol) (PVP), exhibited high dielectric constant (ε~8.15) and high-frequency-stable characteristics (1 MHz). Using the ionic-type HGD as a gate dielectric layer, an minimal electron-double-layer (EDL) can be formed at the gate dielectric/InOx interface, enhancing the field-effect mobility of the TFTs. Particularly, using the ionic-type HGD gate dielectrics annealed at 350 °C, InOx TFTs having an average field-effect mobility of 16.1 cm2/Vs were achieved (maximum mobility of 24 cm2/Vs). Furthermore, the ionic-type HGD gate dielectrics can be processed at a low temperature of 150 °C, which may enable their applications in low-thermal-budget plastic and elastomeric substrates. In addition, we systematically studied the operational stability of the InOx TFTs using the HGD gate dielectric, and it was observed that the HGD gate dielectric effectively suppressed the negative threshold voltage shift during the negative-illumination-bias stress possibly owing to the recombination of hole carriers injected in the gate dielectric with the negatively charged ionic species in the HGD gate dielectric. PMID:28772972

High Ionic Conductivity of Composite Solid Polymer Electrolyte via In Situ Synthesis of Monodispersed SiO2 Nanospheres in Poly(ethylene oxide).

PubMed

Lin, Dingchang; Liu, Wei; Liu, Yayuan; Lee, Hye Ryoung; Hsu, Po-Chun; Liu, Kai; Cui, Yi

2016-01-13

High ionic conductivity solid polymer electrolyte (SPE) has long been desired for the next generation high energy and safe rechargeable lithium batteries. Among all of the SPEs, composite polymer electrolyte (CPE) with ceramic fillers has garnered great interest due to the enhancement of ionic conductivity. However, the high degree of polymer crystallinity, agglomeration of ceramic fillers, and weak polymer-ceramic interaction limit the further improvement of ionic conductivity. Different from the existing methods of blending preformed ceramic particles with polymers, here we introduce an in situ synthesis of ceramic filler particles in polymer electrolyte. Much stronger chemical/mechanical interactions between monodispersed 12 nm diameter SiO2 nanospheres and poly(ethylene oxide) (PEO) chains were produced by in situ hydrolysis, which significantly suppresses the crystallization of PEO and thus facilitates polymer segmental motion for ionic conduction. In addition, an improved degree of LiClO4 dissociation can also be achieved. All of these lead to good ionic conductivity (1.2 × 10(-3) S cm(-1) at 60 °C, 4.4 × 10(-5) S cm(-1) at 30 °C). At the same time, largely extended electrochemical stability window up to 5.5 V can be observed. We further demonstrated all-solid-state lithium batteries showing excellent rate capability as well as good cycling performance.

Fluorophotometric determination of critical micelle concentration (CMC) of ionic and non-ionic surfactants with carbon dots via Stokes shift.

PubMed

Lavkush Bhaisare, Mukesh; Pandey, Sunil; Shahnawaz Khan, M; Talib, Abou; Wu, Hui-Fen

2015-01-01

A new and facile method for the determination of critical micelle concentration (CMC) of ionic and non-ionic surfactants is proposed in this article. Carbon dots exhibited substantial fluorescence and therefore enhanced the sensitivity of this evaluation. Understanding the formation of surfactant micelles is vital for the applications of biomedicine such as drug fabrication and smart molecular vehicles in delivering therapeutic dosage to various molecular sites. The fluorescence property of carbon dots was utilized for the first time to estimate the critical micelle concentration of surfactants. The central concept of the approach is based on the Stokes shift determination of a system composed of constant amount of carbon dots with varying concentrations of ionic and non-ionic surfactants. The synthesized carbon dots were characterized by FTIR, TEM, XRD, Raman, UV, and fluorescence spectroscope. The carbon dots were excited at 280 nm so as to obtain maximum emission for the Stokes shift measurement. The CMC value of cetyltrimethyl ammonium bromide (CTAB), sodium dodecyl sulfate (SDS), Triton X-100, dodecyldimethyl(3-sulfopropyl)ammonium hydroxide (SB-12) evaluated by this approach was found to be 0.98, 7.3, 0.19, and 3.5mM, respectively. The signals of spectra were assigned and explained in terms of both electron transitions between specific molecular orbital and the interaction with solvent. Copyright © 2014 Elsevier B.V. All rights reserved.

High-performance supercapacitors based on poly(ionic liquid)-modified graphene electrodes.

PubMed

Kim, Tae Young; Lee, Hyun Wook; Stoller, Meryl; Dreyer, Daniel R; Bielawski, Christopher W; Ruoff, Rodney S; Suh, Kwang S

2011-01-25

We report a high-performance supercapacitor incorporating a poly(ionic liquid)-modified reduced graphene oxide (PIL:RG-O) electrode and an ionic liquid (IL) electrolyte (specifically, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide or EMIM-NTf(2)). PIL:RG-O provides enhanced compatibility with the IL electrolyte, thereby increasing the effective electrode surface area accessible to electrolyte ions. The supercapacitor assembled with PIL:RG-O electrode and EMIM-NTf(2) electrolyte showed a stable electrochemical response up to 3.5 V operating voltage and was capable of yielding a maximum energy density of 6.5 W·h/kg with a power density of 2.4 kW/kg. These results demonstrate the potential of the PIL:RG-O material as an electrode in high-performance supercapacitors.

Inclusion complex formation of ionic liquids with 4-sulfonatocalixarenes studied by competitive binding of berberine alkaloid fluorescent probe

NASA Astrophysics Data System (ADS)

Miskolczy, Zsombor; Biczók, László

2009-07-01

A clinically important natural isoquinoline alkaloid, berberine, was used as a fluorescent probe to study the encapsulation of 1-alkyl-3-methylimidazolium (C nMIm +) type ionic liquids in 4-sulfonato-substituted calix[4]arene (SCX4) and calix[6]arene (SCX6) at pH 2. Addition of ionic liquids to the aqueous solution of berberine-SCXn inclusion complexes brought about considerable fluorescence intensity diminution due to the extrusion of berberine from the macrocycle into the aqueous phase by the competitive inclusion of C nMIm + cation. The lengthening of the aliphatic side chain of the imidazolium moiety diminished the equilibrium constant of complexation with SCX4, but enhanced the stability of SCX6 complexes. Larger binding strength was found for SCX4.

Dual functions of imidazole-based polymeric ionic liquid (PIL) on the anticorrosive performance of graphene-based waterborne epoxy coatings

NASA Astrophysics Data System (ADS)

Liu, Chengbao; Du, Peng; Nan, Feng; Zhao, Haichao; Wang, Liping

2018-06-01

Dispersion of graphene nanosheets in a water and polymer matrix has been rarely achieved due to graphene’s hydrophobicity, which thus impedes its potential anticorrosive application. In this study, stable graphene aqueous dispersion was obtained by using imidazole-based polymeric ionic liquid (PIL) as the dispersant with ultrasonic vibration. Stacked graphene sheets were exfoliated to a few layers via cation-π interaction between PIL and graphene nanosheets. Electrochemical impedance measurements were taken to investigate the anticorrosion performance of epoxy coatings with or without polymeric ionic liquid–graphene (PIL–G) hybrids. Results indicated that the PIL–G hybrid significantly enhanced the long-term protective performance of epoxy coatings, which was attributed to the synergistic effects of the corrosion-inhibitive PIL and impermeable graphene nanosheets.

Ionic solubility and solutal advection governed augmented evaporation kinetics of salt solution pendant droplets

NASA Astrophysics Data System (ADS)

Jaiswal, Vivek; Harikrishnan, A. R.; Khurana, Gargi; Dhar, Purbarun

2018-01-01

The presence of dispersed inclusions is known to modify the interfacial characteristics in liquids by adsorption-desorption of the ions at interfaces. The present article reports the influencing role of dissolved ions in a polar fluid on its evaporation dynamics. The evaporation dynamics of pendant droplets of aqueous solutions of variant simple salts and concentrations have been experimentally studied. The presence of salts is observed to enhance the evaporation rate (obeying the classical D2 law), and the enhancement has been found to hold a direct proportionality to the concentration of the dissolved salt. Furthermore, it is observed that the degree of enhancement in the evaporation rate is also directly proportional to the solubility of the salt in question. The phenomenon is explained based on the chemical kinetics and thermodynamics of hydration of the ionic species in the polar fluid. The classical evaporation rate constant formulation is found to be inadequate in modeling the enhanced species transport. Additional probing via particle image velocimetry reveals augmented internal circulation within the evaporating salt based drops compared to pure water. Mapping the dynamic surface tension reveals that a salt concentration gradient is generated between the bulk and periphery of the droplet and it could be responsible for the internal advection cells visualized. A thermo-solutal Marangoni and Rayleigh convection based mathematical formulation has been put forward, and it is shown that the enhanced solute-thermal convection could play a major role in enhanced evaporation. The internal circulation mapped from experiments is found to be in good quantitative agreement with the model predictions. Scaling analysis further reveals that the stability of the solutal Marangoni convection surpasses the thermal counterpart with higher salt concentration and solubility. The present article sheds insight into the possible domineering role of conjugate thermohydraulic and mass transport phenomena on the evaporation kinetics aqueous droplets with ionic inclusions.

Ionic strength dependence of the oxidation of SO2 by H2O2 in sodium chloride particles

NASA Astrophysics Data System (ADS)

Ali, H. M.; Iedema, M.; Yu, X.-Y.; Cowin, J. P.

2014-06-01

The reaction of sulfur dioxide and hydrogen peroxide in the presence of deliquesced (>75% RH) sodium chloride (brine) particles was studied by utilizing a cross flow mini-reactor. The reaction kinetics were followed by observing chloride depletion in particles by computer-controlled scanning electron microscope with energy dispersive X-ray analysis, namely CCSEM/EDX. The reactions take place in concentrated mixed salt brine aerosols, for which no complete kinetic equilibrium data previously existed. We measured the Henry's law solubility of H2O2 in brine solutions to close that gap. We also calculated the reaction rate as the particle transforms continuously from concentrated NaCl brine to, eventually, a mixed NaHSO4 plus H2SO4 brine solution. The reaction rate of the SO2 oxidation by H2O2 was found to be influenced by the change in ionic strength as the particle undergoes compositional transformation, following closely the dependence of the third order rate constant on ionic strength as predicted using established rate equations. This is the first study that has measured the ionic strength dependence of sulfate formation (in non-aqueous media) from oxidation of mixed salt brine aerosols in the presence of H2O2. It also gives the first report of the dependence of the Henry's law constant of H2O2 on ionic strength.

New Insights into Mechanism of Surface Reactions of ZnO Nanorods During Electrons Beam Irradiation.

PubMed

Cho, Youngseung; Ji, Hyunjin; Kim, Hyoungsub; Yoon, Jinsuop; Choi, Byoungdeog

2018-09-01

This study provides new insight into mechanisms of ionic reactions on the surface of ZnO nanorod networks, which could result in enhanced performance in optical or molecular sensors. The current- voltage characteristics of ZnO nanorod network devices exhibit typical nonlinear behavior in air, which implies the formation of a Schottky barrier when metals are used as contacts. The conductance of the device increased significantly in vacuum, which can be explained by the desorption of hydroxyl groups at very low pressure. While physisorbed water or oxygen-related ions can detach from the ZnO surface during evacuation, exposure to high energy in the electron beam is believed to detach the chemisorbed anions of O- and O-2 from the surface of ZnO nanorods, which releases more electrons into the channel. The increase in available electrons enhances the conductance of the ZnO nanorods. Slow initialization of the conductance under ambient conditions indicates that the ionic re-adsorption is inactive under these conditions. Thus, the electron irradiation process can be used to reset the surface ionic molecules on metal oxide nano-structures by tuning the surface potential prior to the passivation process.

Metallosalen-Based Ionic Porous Polymers as Bifunctional Catalysts for the Conversion of CO2 into Valuable Chemicals.

PubMed

Luo, Rongchang; Chen, Yaju; He, Qian; Lin, Xiaowei; Xu, Qihang; He, Xiaohui; Zhang, Wuying; Zhou, Xiantai; Ji, Hongbing

2017-04-10

A series of new metallosalen-based ionic porous organic polymers (POPs) were synthesized for the first time using a simple unique strategy based on the free-radical copolymerization reaction. Various techniques were used to characterize the physicochemical properties of these catalysts. These well-designed materials endowed high surface area, hierarchical porous structures, and enhanced CO 2 /N 2 adsorptive selectivity. Moreover, these POPs having both metal centers (Lewis acid) and ionic units (nucleophile) could serve as bifunctional catalysts in the catalytic conversion of CO 2 into high value-added chemicals without any additional co-catalyst under mild and solvent-free conditions, for example, CO 2 /epoxides cycloaddition and Nformylation of amines from CO 2 and hydrosilanes. The results demonstrated that the irregular porous structure was very favorable for the diffusion of substrates and products, and the microporous structural property resulted in the enrichment of CO 2 near the catalytic centers in the CO 2 -involved transformations. Additionally, the superhydrophobic property could not only enhance the chemoselectivity of products but also promote the stability and recyclability of catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of ionic liquid properties on lipase stabilization under microwave irradiation

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

Zhao, Hua; Baker, Gary A; Song, Zhiyan

2009-01-01

Ionic liquids (ILs) as neoteric solvents and microwave irradiation as alternative energy source are becoming two important tools for many enzymatic reactions. However, it is not well understood what properties of ILs govern the enzyme stabilization, and whether the microwave irradiation could activate enzymes in ILs. To tackle these two important issues, the synthetic activities of immobilized Candida antarctica lipase B (Novozyme 435) were examined in more than twenty ILs through microwave heating. Under microwave irradiation, enhanced enzyme activities were observed when the enzyme was surrounded by a layer of water molecules. However, such enhancement diminished when the reaction systemmore » was dried. To understand the effect of IL properties, the enzyme activities under microwave irradiation were correlated with the viscosity, polarity and hydrophobicity (log P) of ILs, respectively. The initial reaction rates bear no direct relationship with the viscosity and polarity (in terms of dielectric constant and EN T ) of ILs, but have a loose correlation (a bell curve) with log P values. The enzyme stabilization by ILs was explained from aspects of hydrogen-bond basicity of anions, dissolution of the enzyme, ionic association strength of anions, and substrate ground-state stabilization by ILs.« less

[Distribution of chemical elements in whole blood and plasma].

PubMed

Barashkov, G K; Zaĭtseva, L I; Kondakhchan, M A; Konstantinova, E A

2003-01-01

The distribution factor (Fd) of 35 elements of plasma and whole blood in 26 healthy men and women was detected by ICP-OES. Usilig this parameter the elements were subdivided in 3 pools. 9 of them have Fd higher than 1.5 ("elements of plasma"-Ag, Ca, Cu, In, Li, Na, Se, Si, Sr); 6 have lower than 0.5 ("elements of blood cells"-Fe, K, Mn, Ni, V, Zn), other 20-about 1 ("blood elements"). Fd of all elements depends on ionic radius. Elements of 2nd sub-groups of all groups of Mendeleev's periodic table ("heavy metals") depend on the similar law: "with growing of ionic radius the concentration of elements in plasma enhances". In alkaline metals Fd depends on the opposite law:" with growing of ionic radius of alkaline metal the quantity of elements in blood cells enhance". Dependence of Fd on the value of atomic mass in periods or in exterior electronic cloud (s-, p-, d-, f-) was not established. The table of distribution of all detected elements in whole blood in relation to 8 macroelements (Ca, Mg, K, Na, S, P, Fe, Zn,) is presented, as a basic diagnostic criteria in metal-ligand homeostasis disturbance.

Method and apparatus for confinement of ions in the presence of a neutral gas

DOEpatents

Peurrung, Anthony J.; Barlow, Stephan E.

1999-01-01

The present invention is an apparatus and method for combining ions with a neutral gas and flowing the mixture with a radial flow component through a magnetic field so that the weakly ionized gas is confined by the neutral gas. When the weakly ionized gas is present in sufficient density, a weakly ionized non-neutral plasma is formed that may be trapped in accordance with the present invention. Applications for a weakly ionized non-neutral plasma exploit the trap's ability to store and manipulate ionic species in the presence of neutral gas. The trap may be connected to a mass spectrometer thereby permitting species identification after a fixed period of time. Delicate and/or heavy particles such as clusters may be held and studied in a "gentle" environment. In addition, the trap can provide a relatively intense, low-energy source of a particular ion species for surface implantation or molecular chemistry. Finally, a long trap may permit spectroscopy of unprecedented accuracy to be performed on ionic species.

Through thick and thin: a microfluidic approach for continuous measurements of biofilm viscosity and the effect of ionic strength.

PubMed

Paquet-Mercier, F; Parvinzadeh Gashti, M; Bellavance, J; Taghavi, S M; Greener, J

2016-11-29

Continuous, non-intrusive measurements of time-varying viscosity of Pseudomonas sp. biofilms are made using a microfluidic method that combines video tracking with a semi-empirical viscous flow model. The approach uses measured velocity and height of tracked biofilm segments, which move under the constant laminar flow of a nutrient solution. Following a low viscosity growth stage, rapid thickening was observed. During this stage, viscosity increased by over an order of magnitude in less than ten hours. The technique was also demonstrated as a promising platform for parallel experiments by subjecting multiple biofilm-laden microchannels to nutrient solutions containing NaCl in the range of 0 to 34 mM. Preliminary data suggest a strong relationship between ionic strength and biofilm properties, such as average viscosity and rapid thickening onset time. The technique opens the way for a combinatorial approach to study the response of biofilm viscosity under well-controlled physical, chemical and biological growth conditions.

Novel Applications of Magnetic Fields for Fluid Flow Control and for Simulating Variable Gravity Conditions

NASA Technical Reports Server (NTRS)

Ramachandran, N.

2005-01-01

Static and dynamic magnetic fields have been used to control convection in many materials processing applications. In most of the applications, convection control (damping or enhancement) is achieved through the Lorentz force that can be tailored to counteract/assist dominant system flows. This technique has been successfully applied to liquids that are electrically conducting, such as high temperature melts of semiconductors, metals and alloys, etc. In liquids with low electrical conductivity such as ionic solutions of salts in water, the Lorentz force is weak and hence not very effective and alternate ways of flow control are necessary. If the salt in solution is paramagnetic then the variation of magnetic susceptibility with temperature and/or concentration can be used for flow control. For thermal buoyancy driven flows this can be accomplished in a temperature range below the Curie point of the salt. The magnetic force is proportional to the magnetic susceptibility and the product of the magnetic field and its gradient. By suitably positioning the experiment cell in the magnet, system flows can be assisted or countered, as desired. A similar approach can be extended to diamagnetic substances and fluids but the required magnetic force is considerably larger than that required for paramagnetic substances. The presentation will provide an overview of work to date on a NASA fluid physics sponsored project that aims to test the hypothesis of convective flow control using strong magnetic fields in protein crystal growth. The objective is to understand the nature of the various forces that come into play, delineate causative factors for fluid flow and to quantify them through experiments, analysis, and numerical modeling. The seminar will report specifically on the experimental results using paramagnetic salts and solutions in magnetic fields and compare them to analytical predictions. Applications of the concept to protein crystallization studies will be discussed. The use of strong magnetic fields for terrestrially simulating variable gravity environments and applications supporting the NASA Exploration Initiative will also be briefly discussed.

Hofmeister series salts enhance purification of plasmid DNA by non-ionic detergents

PubMed Central

Lezin, George; Kuehn, Michael R.; Brunelli, Luca

2011-01-01

Ion-exchange chromatography is the standard technique used for plasmid DNA purification, an essential molecular biology procedure. Non-ionic detergents (NIDs) have been used for plasmid DNA purification, but it is unclear whether Hofmeister series salts (HSS) change the solubility and phase separation properties of specific NIDs, enhancing plasmid DNA purification. After scaling-up NID-mediated plasmid DNA isolation, we established that NIDs in HSS solutions minimize plasmid DNA contamination with protein. In addition, large-scale NID/HSS solutions eliminated LPS contamination of plasmid DNA more effectively than Qiagen ion-exchange columns. Large-scale NID isolation/NID purification generated increased yields of high quality DNA compared to alkali isolation/column purification. This work characterizes how HSS enhance NID-mediated plasmid DNA purification, and demonstrates that NID phase transition is not necessary for LPS removal from plasmid DNA. Specific NIDs such as IGEPAL CA-520 can be utilized for rapid, inexpensive and efficient laboratory-based large-scale plasmid DNA purification, outperforming Qiagen-based column procedures. PMID:21351074

Peracetic acid-ionic liquid pretreatment to enhance enzymatic saccharification of lignocellulosic biomass.

PubMed

Uju; Abe, Kojiro; Uemura, Nobuyuki; Oshima, Toyoji; Goto, Masahiro; Kamiya, Noriho

2013-06-01

To enhance enzymatic saccharification of pine biomass, the pretreatment reagents peracetic acid (PAA) and ionic liquid (IL) were validated in single reagent pretreatments or combination pretreatments with different sequences. In a 1h saccharification, 5-25% cellulose conversion was obtained from the single pretreatment of PAA or IL. In contrast, a marked enhancement in conversion rates was achieved by PAA-IL combination pretreatments (45-70%). The PAA followed by IL (PAA+IL) pretreatment sequence was the most effective for preparing an enzymatic digestible regenerated biomass with 250-fold higher glucose formation rates than untreated biomass and 2- to 12-fold higher than single pretreatments with PAA or IL alone. Structural analysis confirmed that this pretreatment resulted in biomass with highly porous structural fibers associated with the reduction of lignin content and acetyl groups. Using the PAA+IL sequence, biomass loading in the pretreatment step can be increased from 5% to 15% without significant decrease in cellulose conversion. Copyright © 2013 Elsevier Ltd. All rights reserved.

Selective Label-free Electrokinetic Cell Tracker (SELECT): a novel liquid platform for cell characterization

NASA Astrophysics Data System (ADS)

Taruvai Kalyana Kumar, Rajeshwari; de Mello Gindri, Izabelle; Kinnamon, David; Kanchustambham, Pradyotha; Rodrigues, Danieli; Prasad, Shalini; BiomaterialsOsseointegration; Novel Engineering Lab Collaboration

2015-03-01

Characterization and analysis of rare cells provide critical cues for early diagnosis of diseases. Electrokinetic cell separation has been previously established to have greater efficiency when compared to traditional flow cytometry methods. It has been shown by many researchers that buffer solutions in which cells are suspended in, have enormous effects on producing required dielectrophoretic (DEP) forces to characterize cells. Most commonly used suspension buffers used are deionized water and cell media. However, these solutions exhibit high level of intrinsic noise, which greatly masks the electrokinetic signals from cells under study. Ionic liquids (ILs) show promise towards the creation of conductive fluids with required electrical properties. The goal of this project is to design and test ILs for enhancing DEP forces on cells while creating an environment for preserving their integrity. We analyzed two methylimidazolium based ILs as suspension medium for cell separation. These dicationic ILs possess slight electrical and structural differences with high thermal stability. The two ILs were tested for cytotoxicity using HeLa and bone cells. The effects of electrical neutrality, free charge screening due to ILs towards enhanced electrokinetic signals from cells were studied with improved system resolution and no harmful effects.

Piezoelectric transformers for low-voltage generation of gas discharges and ionic winds in atmospheric air

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

Johnson, Michael J.; Go, David B., E-mail: dgo@nd.edu; Department of Chemical and Biomolecular Engineering, University of Notre Dame, Notre Dame, Indianapolis 46556

To generate a gas discharge (plasma) in atmospheric air requires an electric field that exceeds the breakdown threshold of ∼30 kV/cm. Because of safety, size, or cost constraints, the large applied voltages required to generate such fields are often prohibitive for portable applications. In this work, piezoelectric transformers are used to amplify a low input applied voltage (<30 V) to generate breakdown in air without the need for conventional high-voltage electrical equipment. Piezoelectric transformers (PTs) use their inherent electromechanical resonance to produce a voltage amplification, such that the surface of the piezoelectric exhibits a large surface voltage that can generate corona-like dischargesmore » on its corners or on adjacent electrodes. In the proper configuration, these discharges can be used to generate a bulk air flow called an ionic wind. In this work, PT-driven discharges are characterized by measuring the discharge current and the velocity of the induced ionic wind with ionic winds generated using input voltages as low as 7 V. The characteristics of the discharge change as the input voltage increases; this modifies the resonance of the system and subsequent required operating parameters.« less

Characterization of Gd loaded chitosan-TPP nanohydrogels by a multi-technique approach combining dynamic light scattering (DLS), asymetrical flow-field-flow-fractionation (AF4) and atomic force microscopy (AFM) and design of positive contrast agents for molecular resonance imaging (MRI)

NASA Astrophysics Data System (ADS)

Rigaux, G.; Gheran, C. V.; Callewaert, M.; Cadiou, C.; Voicu, S. N.; Dinischiotu, A.; Andry, M. C.; Vander Elst, L.; Laurent, S.; Muller, R. N.; Berquand, A.; Molinari, M.; Huclier-Markai, S.; Chuburu, F.

2017-02-01

Chitosan CS—tripolyphosphate TPP/hyaluronic acid HA nanohydrogels loaded with gadolinium chelates (GdDOTA ⊂ CS-TPP/HA NGs) synthesized by ionic gelation were designed for lymph node (LN) MRI. In order to be efficiently drained to LNs, nanogels (NGs) needed to exhibit a diameter ϕ < 100 nm. For that, formulation parameters were tuned, using (i) CS of two different molecular weights (51 and 37 kDa) and (ii) variable CS/TPP ratio (2 < CS/TPP < 8). Characterization of NG size distribution by dynamic light scattering (DLS) and asymetrical flow-field-flow-fractionation (AF4) showed discrepancies since DLS diameters were consistently above 200 nm while AF4 showed individual nano-objects with ϕ < 100 nm. Such a difference could be correlated to the presence of aggregates inherent to ionic gelation. This point was clarified by atomic force microscopy (AFM) in liquid mode which highlighted the main presence of individual nano-objects in nanosuspensions. Thus, combination of DLS, AF4 and AFM provided a more precise characterization of GdDOTA ⊂ CS-TPP/HA nanohydrogels which, in turn, allowed to select formulations leading to NGs of suitable mean sizes showing good MRI efficiency and negligible toxicity.

On-line ionic liquid-based preconcentration system coupled to flame atomic absorption spectrometry for trace cadmium determination in plastic food packaging materials.

PubMed

Martinis, Estefanía M; Olsina, Roberto A; Altamirano, Jorgelina C; Wuilloud, Rodolfo G

2009-05-15

A novel on-line preconcentration method based on liquid-liquid (L-L) extraction with room temperature ionic liquids (RTILs) coupled to flame atomic absorption spectrometry (FAAS) was developed for cadmium determination in plastic food packaging materials. The methodology is based on the complexation of Cd with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) reagent after sample digestion followed by extraction of the complex with the RTIL 1-butyl-3-methylimidazolium hexafluorophosphate ([C(4)mim][PF(6)]). The mixture was loaded into a flow injection analysis (FIA) manifold and the RTIL rich-phase was retained in a microcolumn filled with silica gel. The RTIL rich-phase was then eluted directly into FAAS. A enhancement factor of 35 was achieved with 20 mL of sample. The limit of detection (LOD), obtained as IUPAC recommendation, was 6 ng g(-1) and the relative standard deviation (R.S.D.) for 10 replicates at 10 microg L(-1) Cd concentration level was 3.9%, calculated at the peak heights. The calibration graph was linear and a correlation coefficient of 0.9998 was achieved. The accuracy of the method was evaluated by both a recovery study and comparison of results with direct determination by electrothermal atomic absorption spectrometry (ETAAS). The method was successfully applied for Cd determination in plastic food packaging materials and Cd concentrations found were in the range of 0.04-10.4 microg g(-1).

SEPARATION OF THORIUM FROM URANIUM

DOEpatents

Bane, R.W.

1959-09-01

A description is given for the separation of thorium from uranium by forming an aqueous acidic solution containing ionic species of thorium, uranyl uranium, and hydroxylamine, flowing the solution through a column containing the phenol-formaldehyde type cation exchange resin to selectively adsorb substantially all the thorium values and a portion of the uranium values, flowing a dilute solution of hydrochloric acid through the column to desorb the uranium values, and then flowing a dilute aqueous acidic solution containing an ion, such as bisulfate, which has a complexing effect upon thortum through the column to desorb substantially all of the thorium.

Ionic Liquids Can Selectively Change the Conformational Free-Energy Landscape of Sugar Rings.

PubMed

Jarin, Zack; Pfaendtner, Jim

2014-02-11

We investigated the conformational free energy landscape of glucose solvated in water and in the ionic liquids (ILs) 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]) and 1-butyl-3-methylimidazoulim boron tetrafluoride ([Bmim][BF4]). To quantify equilibrium thermodynamic solvent effects, molecular dynamics simulations in conjunction with enhanced sampling based on the metadynamics framework were used. The results show that the solvent choice induces significant differences in the equilibrium ring structures, which may help further resolve the molecular mechanism governing IL-mediated cellulose dissolution.

Organo-redox shuttle promoted protic ionic liquid electrolyte for supercapacitor

NASA Astrophysics Data System (ADS)

Sathyamoorthi, S.; Suryanarayanan, V.; Velayutham, D.

2015-01-01

Performance of activated charcoal based supercapacitor (SC) containing hydroquinone (HQ), as an organic redox shuttle, is evaluated in triethylammonium bis(trifluoromethane)sulfonimide (TEATFSI). Cyclic voltammograms of the SC show pseudocapacitive contribution of HQ and the galvanostatic charge-discharge measurement shows enhanced specific capacitance (72.0 F g-1) and specific energy (31.22 Wh Kg-1). The presence of HQ shows low charge transfer resistance, as confirmed by electrochemical impedance spectroscopy. Cyclic stability of the SC in the redox mediated electrolyte is comparable with that of the protic ionic liquid.

Electroosmotic Mixing in Nanochannels

NASA Astrophysics Data System (ADS)

Conlisk, A. T.; Chen, Lei

2004-11-01

Electroosmotic flow in nanochannels is characterized by low Reynolds number in which flow mixing is difficult because of the dominance of molecular diffusion. Previous work shows that heterogenerous surface potential could generate a circulation region within the bulk flow near the surface. But all of this work requires that the ionic species be pairs of ions of equal and opposite valence and the distribution of ions is not considered. In the present work the electroosmotic flow in a rectangular channel with non-uniform zeta potential is examined. A model for the two dimensional electroosmotic flow problem is established. The distributions of potential, velocity and mole fractions are calculated numerically. Vortex formation is observed within the bulk flow near the the region of non-uniform zeta potential which suggests mixing can be induced.

Non-scaling behavior of electroosmotic flow in voltage-gated nanopores

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

Lian, Cheng; Gallegos, Alejandro; Liu, Honglai

2017-01-01

Ionic size effects and electrostatic correlations result in the non-monotonic dependence of the electrical conductivity on the pore size. For ion transport at a high gating voltage, the conductivity oscillates with the pore size due to a significant overlap of the electric double layers.

Retention and remobilization of stabilized silver nanoparticles in an undisturbed loamy sand soil

USDA-ARS?s Scientific Manuscript database

Column experiments were conducted with undisturbed loamy sand soil under unsaturated conditions (around 90% saturation degree) to investigate the retention of surfactant stabilized silver nanoparticles (AgNPs) with various input concentration (Co), flow velocity, and ionic strength (IS), and the rem...

Stable isotope monitoring of ionic trapping of CO2 in deep brines

NASA Astrophysics Data System (ADS)

Myrttinen, A.; Barth, J. A. C.; Becker, V.; Blum, P.; Grathwohl, P.

2009-04-01

CO2 injection into a depleted gas-reservoir is used as a combined method for Enhanced Gas Recovery (EGR) and CO2 storage. In order to safeguard this process, monitoring the degree of dissolution and potential further precipitation and mineral interactions are a necessity. Here a method is introduced, in which stable isotope and geochemical data can be used as a monitoring technique to quantify ionic trapping of injected CO2. Isotope and geochemical data of dissolved inorganic carbon (DIC) can be used to distinguish between already present and to be injected inorganic carbon. Injected CO2, for instance, is formed during combustion of former plant material and is expected to have a different isotope ratio (δ13C value) than the baseline data of the aquifer. This is because combusted CO2 originates from organic material, such as coal and oil with a predominant C3 plant signature. Mixing the injected CO2 with groundwater is therefore expected to change the isotope, as well as the geochemical composition of the groundwater. Mass balance calculations with stable isotope ratios can serve to quantify ionic trapping of CO2 as DIC in groundwater. However, depending on the composition of the aquifer, weathering of carbonate or silicates may occur. Enhanced weathering processes due to CO2 injection can also further influence the isotopic composition. Such interactions between dissolved CO2 and minerals depend on the temperature and pressure regimes applied. Field data, as well as laboratory experiments are planned to quantify isotope ratios of dissolved inorganic carbon as well as oxygen isotope ratios of the water. These are indicative of geochemical processes before, during and after EGR. The isotope method should therefore provide a new tool to quantify the efficiency of ionic trapping under various temperatures and pressures. Keywords: Enhanced Gas Recovery, monitoring of CO2 dissolution, stable isotopes

Can ionophobic nanopores enhance the energy storage capacity of electric-double-layer capacitors containing nonaqueous electrolytes?

NASA Astrophysics Data System (ADS)

Lian, Cheng; Liu, Honglai; Henderson, Douglas; Wu, Jianzhong

2016-10-01

The ionophobicity effect of nanoporous electrodes on the capacitance and the energy storage capacity of nonaqueous-electrolyte supercapacitors is studied by means of the classical density functional theory (DFT). It has been hypothesized that ionophobic nanopores may create obstacles in charging, but they store energy much more efficiently than ionophilic pores. In this study, we find that, for both ionic liquids and organic electrolytes, an ionophobic pore exhibits a charging behavior different from that of an ionophilic pore, and that the capacitance-voltage curve changes from a bell shape to a two-hump camel shape when the pore ionophobicity increases. For electric-double-layer capacitors containing organic electrolytes, an increase in the ionophobicity of the nanopores leads to a higher capacity for energy storage. Without taking into account the effects of background screening, the DFT predicts that an ionophobic pore containing an ionic liquid does not enhance the supercapacitor performance within the practical voltage ranges. However, by using an effective dielectric constant to account for ion polarizability, the DFT predicts that, like an organic electrolyte, an ionophobic pore with an ionic liquid is also able to increase the energy stored when the electrode voltage is beyond a certain value. We find that the critical voltage for an enhanced capacitance in an ionic liquid is larger than that in an organic electrolyte. Our theoretical predictions provide further understanding of how chemical modification of porous electrodes affects the performance of supercapacitors. The authors are saddened by the passing of George Stell but are pleased to contribute this article in his memory. Some years ago, DH gave a talk at a Gordon Conference that contained an approximation that George had demonstrated previously to be in error in one of his publications. Rather than making this point loudly in the discussion, George politely, quietly, and privately pointed this out later. In 2002, DH shared a room with George at a conference in China. This is remembered fondly.

Universal Scaling of Robust Thermal Hot Spot and Ionic Current Enhancement by Focused Ohmic Heating in a Conic Nanopore

NASA Astrophysics Data System (ADS)

Pan, Zehao; Wang, Ceming; Li, Meng; Chang, Hsueh-Chia

2016-09-01

A stable nanoscale thermal hot spot, with temperature approaching 100 °C , is shown to be sustained by localized Ohmic heating of a focused electric field at the tip of a slender conic nanopore. The self-similar (length-independent) conic geometry allows us to match the singular heat source at the tip to the singular radial heat loss from the slender cone to obtain a self-similar steady temperature profile along the cone and the resulting ionic current conductance enhancement due to viscosity reduction. The universal scaling, which depends only on a single dimensionless parameter Z , collapses the measured conductance data and computed temperature profiles in ion-track conic nanopores and conic nanopipettes. The collapsed numerical data reveal universal values for the hot-spot location and temperature in an aqueous electrolyte.

Universal Scaling of Robust Thermal Hot Spot and Ionic Current Enhancement by Focused Ohmic Heating in a Conic Nanopore.

PubMed

Pan, Zehao; Wang, Ceming; Li, Meng; Chang, Hsueh-Chia

2016-09-23

A stable nanoscale thermal hot spot, with temperature approaching 100 °C, is shown to be sustained by localized Ohmic heating of a focused electric field at the tip of a slender conic nanopore. The self-similar (length-independent) conic geometry allows us to match the singular heat source at the tip to the singular radial heat loss from the slender cone to obtain a self-similar steady temperature profile along the cone and the resulting ionic current conductance enhancement due to viscosity reduction. The universal scaling, which depends only on a single dimensionless parameter Z, collapses the measured conductance data and computed temperature profiles in ion-track conic nanopores and conic nanopipettes. The collapsed numerical data reveal universal values for the hot-spot location and temperature in an aqueous electrolyte.

Ion Transport in Nanostructured Block Copolymer/Ionic Liquid Membranes

NASA Astrophysics Data System (ADS)

Hoarfrost, Megan Lane

Incorporating an ionic liquid into one block copolymer microphase provides a platform for combining the outstanding electrochemical properties of ionic liquids with a number of favorable attributes provided by block copolymers. In particular, block copolymers thermodynamically self-assemble into well-ordered nanostructures, which can be engineered to provide a durable mechanical scaffold and template the ionic liquid into continuous ion-conducting nanochannels. Understanding how the addition of an ionic liquid affects the thermodynamic self-assembly of block copolymers, and how the confinement of ionic liquids to block copolymer nanodomains affects their ion-conducting properties is essential for predictable structure-property control. The lyotropic phase behavior of block copolymer/ionic liquid mixtures is shown to be reminiscent of mixtures of block copolymers with selective molecular solvents. A variety of ordered microstructures corresponding to lamellae, hexagonally close-packed cylinders, body-centered cubic, and face-centered cubic oriented micelles are observed in a model system composed of mixtures of imidazolium bis(trifluoromethylsulfonyl)imide ([Im][TFSI]) and poly(styrene- b-2-vinyl pyridine) (PS-b-P2VP). In contrast to block copolymer/molecular solvent mixtures, the interfacial area occupied by each PS-b-P2VP chain decreases upon the addition of [Im][TFSI], indicating a considerable increase in the effective segregation strength of the PS-b-P2VP copolymer with ionic liquid addition. The relationship between membrane structure and ionic conductivity is illuminated through the development of scaling relationships that describe the ionic conductivity of block copolymer/ionic liquid mixtures as a function of membrane composition and temperature. It is shown that the dominant variable influencing conductivity is the overall volume fraction of ionic liquid in the mixture, which means there is incredible freedom in designing the block copolymer architecture in order to optimize the mechanical and other properties of the membrane without sacrificing conductivity. The derived scaling relationships are shown to be general for many block copolymer and ionic liquid chemistries. In certain cases, the mechanism of ion conduction in the ionic liquid is affected by block copolymer nanoconfinement. The introduction of excess neutral imidazole to [Im][TFSI] leads to enhanced proton conductivity as well as a high H+ transference number due to facilitated proton hopping between imidazole molecules. We show that there is increased proton hopping when the nonstoichiometric ionic liquid is confined to lamellar block copolymer nanodomains, which we hypothesize is due to changes in the hydrogen bond structure of the ionic liquid under confinement. This, in combination with unique ion aggregation behavior, leads to a lower activation energy for macroscopic ion transport compared to that in a corresponding homopolymer/ionic liquid mixture. Through this work, we further the understanding of the relationship between membrane composition, structure, and ion transport. The findings presented herein portend the rational design of nanostructured membranes having improved mechanical properties and conductivity.

Enhanced ionic conductivity of AgI nanowires/AAO composites fabricated by a simple approach.

PubMed

Liu, Li-Feng; Lee, Seung-Woo; Li, Jing-Bo; Alexe, Marin; Rao, Guang-Hui; Zhou, Wei-Ya; Lee, Jae-Jong; Lee, Woo; Gösele, Ulrich

2008-12-10

AgI nanowires/anodic aluminum oxide (AgI NWs/AAO) composites have been fabricated by a simple approach, which involves the thermal melting of AgI powders on the surface of the AAO membrane, followed by the infiltration of the molten AgI inside the nanochannels. As-prepared AgI nanowires have corrugated outer surfaces and are polycrystalline according to scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations. X-ray diffraction (XRD) shows that a considerable amount of 7H polytype AgI exists in the composites, which is supposed to arise from the interfacial interactions between the embedded AgI and the alumina. AC conductivity measurements for the AgI nanowires/AAO composites exhibit a notable conductivity enhancement by three orders of magnitude at room temperature compared with that of pristine bulk AgI. Furthermore, a large conductivity hysteresis and abnormal conductivity transitions were observed in the temperature-dependent conductivity measurements, from which an ionic conductivity as high as 8.0 × 10(2) Ω(-1) cm(-1) was obtained at around 70 °C upon cooling. The differential scanning calorimetry (DSC) result demonstrates a similar phase transition behavior as that found in the AC conductivity measurements. The enhanced ionic conductivity, as well as the abnormal phase transitions, can be explained in terms of the existence of the highly conducting 7H polytype AgI and the formation of well-defined conduction paths in the composites.

Ionic liquid-based ultrasonic/microwave-assisted extraction combined with UPLC-MS-MS for the determination of tannins in Galla chinensis.

PubMed

Lu, Chunxia; Wang, Hongxin; Lv, Wenping; Ma, Chaoyang; Lou, Zaixiang; Xie, Jun; Liu, Bo

2012-01-01

Ionic liquid was used as extraction solvents and applied to the extraction of tannins from Galla chinensis in the simultaneous ultrasonic- and microwave-assisted extraction (UMAE) technique. Several parameters of UMAE were optimised, and the results were compared with of the conventional extraction techniques. Under optimal conditions, the content of tannins was 630.2 ± 12.1 mg g⁻¹. Compared with the conventional heat-reflux extraction, maceration extraction, regular ultrasound- and microwave-assisted extraction, the proposed approach exhibited higher efficiency (11.7-22.0% enhanced) and shorter extraction time (from 6 h to 1 min). The tannins were then identified by ultraperformance liquid chromatography tandem mass spectrometry. This study suggests that ionic liquid-based UMAE is an efficient, rapid, simple and green sample preparation technique.

Anomalous Capacitance Maximum of the Glassy Carbon-Ionic Liquid Interface through Dilution with Organic Solvents.

PubMed

Bozym, David J; Uralcan, Betül; Limmer, David T; Pope, Michael A; Szamreta, Nicholas J; Debenedetti, Pablo G; Aksay, Ilhan A

2015-07-02

We use electrochemical impedance spectroscopy to measure the effect of diluting a hydrophobic room temperature ionic liquid with miscible organic solvents on the differential capacitance of the glassy carbon-electrolyte interface. We show that the minimum differential capacitance increases with dilution and reaches a maximum value at ionic liquid contents near 5-10 mol% (i.e., ∼1 M). We provide evidence that mixtures with 1,2-dichloroethane, a low-dielectric constant solvent, yield the largest gains in capacitance near the open circuit potential when compared against two traditional solvents, acetonitrile and propylene carbonate. To provide a fundamental basis for these observations, we use a coarse-grained model to relate structural variations at the double layer to the occurrence of the maximum. Our results reveal the potential for the enhancement of double-layer capacitance through dilution.

The lanthanum gallate-based mixed conducting perovskite ceramics

NASA Astrophysics Data System (ADS)

Politova, E. D.; Stefanovich, S. Yu.; Aleksandrovskii, V. V.; Kaleva, G. M.; Mosunov, A. V.; Avetisov, A. K.; Sung, J. S.; Choo, K. Y.; Kim, T. H.

2005-01-01

The structure, microstructure, dielectric, and transport properties of the anion deficient perovskite solid solutions (La,Sr)(Ga,Mg,M)O3- with M=Fe, Ni have been studied. Substitution of iron and nickel for gallium up to about 20 and 40 at.% respectively, leads to the perovskite lattice contraction due to the cation substitutions by the transition elements. The transition from pure ionic to mixed ionic-electronic conductivity was observed for both the systems studied. Both the enhancement of total conductivity and increasing in the thermal expansion coefficient values has been proved to correlate with the increasing amount of weakly bounded oxygen species in the Fe or Ni-doped ceramics. The oxygen ionic conductivity has been estimated from the kinetic experiments using the dc-conductivity and dilatometry methods under the condition of the stepwise change of the atmosphere from nitrogen to oxygen.

Photoinduced electron transfer in an imidazolium ionic liquid and in its binary mixtures with water, methanol, and 2-propanol: appearance of Marcus-type of inversion.

PubMed

Sarkar, Souravi; Mandal, Sarthak; Ghatak, Chiranjib; Rao, Vishal Govind; Ghosh, Surajit; Sarkar, Nilmoni

2012-02-02

The photoinduced electron transfer (PET) reaction has been investigated in a room temperature imidazolium ionic liquid (RTIL), 1-ethyl-3-methylimidazolium ethyl sulfate ([Emim][EtSO(4)]) and also in [Emim][EtSO(4)]-co-solvents mixtures from N,N-dimethyl aniline (DMA) to different Coumarin dyes using steady state and time-resolved fluorescence quenching measurements. We have used water and methanol and 2-propanol as the cosolvents of RTILs for the PET study. On going from neat ionic liquid to the RTIL-co-solvents mixtures the electron transfer rate has been largely enhanced. In neat RTIL as well as in [Emim][EtSO(4)]-co-solvents mixtures, a Marcus type of inversion in the PET rate have been observed.

Self-healing guar gum and guar gum-multiwalled carbon nanotubes nanocomposite gels prepared in an ionic liquid.

PubMed

Sharma, Mukesh; Mondal, Dibyendu; Mukesh, Chandrakant; Prasad, Kamalesh

2013-10-15

Guar gum is a galactomannan extracted from the seed of the leguminous shrub Cyamopsis tetragonoloba. It was found to form a soft viscoelastic gel in 1-butyl-3-methylimidazolium chloride, an ionic liquid at an optimized concentration of 10%w/v. A nanocomposite gel of the gum with enhanced strength could be prepared with 0.2%w/v of multiwalled carbon nanotubes (MWCNTs) in the ionic liquid. When the gels thus prepared were subjected to surface fractures or bisected completely, they found to self-heal at room temperature without any external interventions. The self-healing process could be repeated several times. These viscoelastic gel systems showed thixotropic nature and recovery of the storage modulus with time for several cycles was observed upon rheological investigations. The interaction took place between ionic liquid, guar gum and MWCNT was studied by SEM, TEM, FT-IR, powder XRD and rheometry. The results suggested that, upon standing at room temperature development of electrostatic interactions and the van der Waals interactions among the ionic liquid molecules facilitated the formation of reversible noncovalent bonds and eventually activated the self-healing in the gel systems through appropriate chain entanglements. Copyright © 2013 Elsevier Ltd. All rights reserved.

Current rectification for transport of room-temperature ionic liquids through conical nanopores

DOE PAGES

Jiang, Xikai; Liu, Ying; Qiao, Rui

2016-02-09

Here, we studied the transport of room-temperature ionic liquids (RTILs) through charged conical nanopores using a Landau-Ginzburg-type continuum model that takes steric effect and strong ion-ion correlations into account. When the surface charge is uniform on the pore wall, weak current rectification is observed. When the charge density near the pore base is removed, the ionic current is greatly suppressed under negative bias voltage while nearly unchanged under positive bias voltage, thereby leading to enhanced current rectification. These predictions agree qualitatively with prior experimental observations, and we elucidated them by analyzing the different components of the ionic current and themore » structural changes of electrical double layers (EDLs) at the pore tip under different bias voltages and surface charge patterns. These analyses reveal that the different modifications of the EDL structure near the pore tip by the positive and negative bias voltages cause the current rectification and the observed dependence on the distribution of surface charge on the pore wall. The fact that the current rectification phenomena are captured qualitatively by the simple model originally developed for describing EDLs at equilibrium conditions suggests that this model may be promising for understanding the ionic transport under nonequilibrium conditions when the EDL structure is strongly perturbed by external fields.« less

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.

Nanoscale lubrication of ionic surfaces controlled via a strong electric field

DOE PAGES

Strelcov, Evgheni; Bocharova, Vera; Sumpter, Bobby G.; ...

2015-01-27

Frictional forces arise whenever objects around us are set in motion. Controlling them in a rational manner means gaining leverage over mechanical energy losses and wear. This paper presents a way of manipulating nanoscale friction by means of in situ lubrication and interfacial electrochemistry. Water lubricant is directionally condensed from the vapor phase at a moving metal-ionic crystal interface by a strong confined electric field, thereby allowing friction to be tuned up or down via an applied bias. The electric potential polarity and ionic solid solubility are shown to strongly influence friction between the atomic force microscope (AFM) tip andmore » salt surface. An increase in friction is associated with the AFM tip digging into the surface, whereas reducing friction does not influence its topography. No current flows during friction variation, which excludes Joule heating and associated electrical energy losses. Lastly, the demonstrated novel effect can be of significant technological importance for controlling friction in nano- and micro-electromechanical systems.« less

Physicochemical factors influencing the preferential transport of Escherichia coli in soils

USDA-ARS?s Scientific Manuscript database

Laboratory and numerical studies were conducted to investigate the transport and release of Escherichia coli D21g in preferential flow systems with artificial macropores under different ionic strength (IS) conditions. Macropores were created by embedding coarse sand lenses in a fine sand matrix and ...

Colloid release and clogging in porous media: Effects of solution ionic strength and flow velocity

USDA-ARS?s Scientific Manuscript database

The release and retention of in-situ colloids in aquifers play an important role in the sustainable operation of managed aquifer recharge (MAR) schemes. The processes of colloid release, retention, and associated permeability changes in consolidated aquifer sediments were studied by displacing nativ...

The effect of humic acid on uranyl sorption onto bentonite at trace uranium levels.

PubMed

Ivanov, Peter; Griffiths, Tamara; Bryan, Nick D; Bozhikov, Gospodin; Dmitriev, Serguei

2012-11-01

The effect of humic acid (HA) on U(VI) sorption on bentonite was studied in batch experiments at room temperature and ambient atmosphere at a (237)U(VI) concentration of 8.4 × 10(-11) M and HA concentration of 100 mg L(-1). The distribution of U(VI) between the liquid and solid phases was studied as a function of pH and ionic strength both in the absence and presence of HA. It was shown that the uranyl sorption on bentonite is strongly dependent on pH and the presence of humics, and the effect of the addition order was negligible. In the absence of HA an enhancement in the uptake with increasing pH was observed and a sharp sorption edge was found to take place between pH 3.2 and 4.2. The presence of HA slightly increases uranium(VI) sorption at low pH and curtails it at moderate pH, compared to the absence of HA. In the basic pH range for both the presence and absence of HA the sorption of uranium is significantly reduced, which could be attributed to the formation of soluble uranyl carbonate complexes. The influence of ionic strength on U(VI) and HA uptake by bentonite were investigated in the range of 0.01-1.0 M, and while there was an enhancement in the sorption of humic acid with increasing ionic strength, no significant effect of the ionic strength on the U(VI) sorption was observed in both the absence and presence of HA.

In-situ ionic liquid dispersive liquid-liquid microextraction using a new anion-exchange reagent combined Fe3O4 magnetic nanoparticles for determination of pyrethroid pesticides in water samples.

PubMed

Fan, Chen; Liang, You; Dong, Hongqiang; Ding, Guanglong; Zhang, Wenbing; Tang, Gang; Yang, Jiale; Kong, Dandan; Wang, Deng; Cao, Yongsong

2017-07-04

In this work, in-situ ionic liquid dispersive liquid-liquid microextraction combined ultrasmall Fe 3 O 4 magnetic nanoparticles was developed as a kind of pretreatment method to detect pyrethroid pesticides in water samples. New anion-exchange reagents including Na[DDTC] and Na[N(CN) 2 ] were optimized for in-situ extraction pyrethroids, which showed enhanced microextraction performance. Pyrethroids were enriched by hydrophilic ionic liquid [P 4448 ][Br] (aqueous solution, 200 μL, 0.2 mmol mL -1 ) reaction in-situ with anion-exchange reagent Na[N(CN) 2 ] (aqueous solution, 300 μL, 0.2 mmol mL -1 ) forming hydrophobic ionic liquid as extraction agent in water sample (10 mL). Ultrasmall superparamagnetic iron oxide nanoparticles (30 mg) were used to collect the mixture of ionic liquid and pyrethroids followed by elution with acetonitrile. The extraction of ionic liquid strategies was unique and efficiently fulfilled with high enrichment factors (176-213) and good recoveries (80.20-117.31%). The method was successively applied to the determination of pyrethroid pesticides in different kinds of water samples with the limits of detection ranged from 0.16 to 0.21 μg L -1 . The proposed method is actually nanometer-level microextraction (average size 80 nm) with the advantages of simplicity, rapidity, and sensitivity. Copyright © 2017 Elsevier B.V. All rights reserved.

High ionic conductivity P(VDF-TrFE)/PEO blended polymer electrolytes for solid electrochromic devices.

PubMed

Nguyen, Chien A; Xiong, Shanxin; Ma, Jan; Lu, Xuehong; Lee, Pooi See

2011-08-07

Solid polymer electrolytes with excellent ionic conductivity (above 10(-4) S cm(-1)), which result in high optical modulation for solid electrochromic (EC) devices are presented. The combination of a polar host matrix poly(vinylidene fluoride-trifluoroethylene) P(VDF-TrFE) and a solid plasticized of a low molecular weight poly(ethylene oxide) (PEO) (M(w)≤ 20,000) blended polymer electrolyte serves to enhance both the dissolution of lithium salt and the ionic transport. Calorimetric measurement shows a reduced crystallization due to a better intermixing of the polymers with small molecular weight PEO. Vibrational spectroscopy identifies the presence of free ions and ion pairs in the electrolytes with PEO of M(w)≤ 8000. The ionic dissolution is improved using PEO as a plasticizer when compared to liquid propylene carbonate, evidently shown in the transference number analysis. Ionic transport follows the Arrhenius equation with a low activation energy (0.16-0.2 eV), leading to high ionic conductivities. Solid electrochromic devices fabricated with the blended P(VDF-TrFE)/PEO electrolytes and polyaniline show good spectroelectrochemical performance in the visible (300-800 nm) and near-infrared (0.9-2.4 μm) regions with a modulation up to 60% and fast switching speed of below 20 seconds. The successful introduction of the solid polymer electrolytes with its best harnessed qualities helps to expedite the application of various electrochemical devices. This journal is © the Owner Societies 2011

Use of Ionic Liquids in Rod-Coil Block Copolyimides for Improved Lithium Ion Conduction

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B.; Tigelaar, Dean M.; Chapin, Kara; Bennett, William R.

2007-01-01

Solvent-free, solid polymer electrolytes (SPE) have the potential to improve safety, increase design flexibility and enhance performance of rechargeable lithium batteries. Solution based electrolytes are flammable and typically incompatible with lithium metal anodes, limiting energy density. We have previously demonstrated use of polyimide rod coil block copolymers doped with lithium salts as electrolytes for lithium polymer batteries. The polyimide rod blocks provide dimensional stability while the polyethylene oxide (PEO) coil portions conduct ions. Phase separation of the rods and coils in these highly branched polymers provide channels with an order of magnitude improvement in lithium conduction over polyethylene oxide itself at room temperature. In addition, the polymers have been demonstrated in coin cells to be compatible with lithium metal. For practical use at room temperature and below, however, at least an order of magnitude improvement in ion conduction is still required. The addition of nonvolatile, room temperature ionic liquids has been shown to improve the ionic conductivity of high molecular weight PEO. Herein we describe use of these molten salts to improve ionic conductivity in the rod-coil block copolymers.

Effects of Dopant Ionic Radius on Cerium Reduction in Epitaxial Cerium Oxide Thin Films

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

Yang, Nan; Orgiani, Pasquale; Di Bartolomeo, Elisabetta

The role of trivalent rare-earth dopants in ceria epitaxial films on surface ion exchange reactivity and ion conductivity has been systematically studied. Single-crystal epitaxial films with unique crystal orientation and micro-structure nature have allowed us to rule out the influence of structural defects on both transport and surface ion exchange properties. The films conductivities were larger than those reported in literature for both polycrystalline ceramic pellets and crystalline films. An increase in oxygen vacancies and Ce 3+ concentration while decreasing the dopant ionic radius from La 3+ to Yb 3+ was observed, thus explaining the measured increased activation energy andmore » enhanced surface reactivity. The more significant ability of smaller dopant ionic radius in releasing the stress strength induced by the larger Ce 3+ ionic radius allows promoting the formation of oxygen vacancies and Ce 3+, which are two precious species in determining the efficiency of ion transport and surface ion exchange processes. This can open new perspectives in designing ceria-based materials in tailoring functional properties, either ion migration or surface reactivity, by rational cation substitutions.« less

Mixed Ionic Liquid Improves Electrolyte Dynamics in Supercapacitors

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

Osti, Naresh C.; Gallegos, Alejandro; Dyatkin, Boris

Well-tailored mixtures of distinct ionic liquids can act as optimal electrolytes that extend the operating electrochemical window and improve charge storage density in supercapacitors. Here, we explore two room-temperature ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimTFSI) and 1-ethyl-3-methylimidazolium tetrafluoroborate (EmimBF 4). We study their electric double-layer behavior in the neat state and as binary mixtures on the external surfaces of onion-like carbon electrodes using quasielastic neutron scattering (QENS) and classical density functional theory techniques. Computational results reveal that a mixture with 4:1 EmimTFSI/EmimBF 4 volume ratio displaces the larger [TFSI –] anions with smaller [BF 4 –] ions, leading to an excessmore » adsorption of [Emim +] cations near the electrode surface. These findings are corroborated by the manifestation of nonuniform ion diffusivity change, complementing the description of structural modifications with changing composition, from QENS measurements. In conclusion, molecular-level understanding of ion packing near electrodes provides insight for design of ionic liquid formulations that enhance the performance of electrochemical energy storage devices.« less

Ion transport and structural dynamics in homologous ammonium and phosphonium-based room temperature ionic liquids

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

Griffin, Philip J., E-mail: pgrif@seas.upenn.edu; Holt, Adam P.; Tsunashima, Katsuhiko

2015-02-28

Charge transport and structural dynamics in a homologous pair of ammonium and phosphonium based room temperature ionic liquids (ILs) have been characterized over a wide temperature range using broadband dielectric spectroscopy and quasi-elastic light scattering spectroscopy. We have found that the ionic conductivity of the phosphonium based IL is significantly enhanced relative to the ammonium homolog, and this increase is primarily a result of a lower glass transition temperature and higher ion mobility. Additionally, these ILs exhibit pronounced secondary relaxations which are strongly influenced by the atomic identity of the cation charge center. While the secondary relaxation in the phosphoniummore » IL has the expected Arrhenius temperature dependence characteristic of local beta relaxations, the corresponding relaxation process in the ammonium IL was found to exhibit a mildly non-Arrhenius temperature dependence in the measured temperature range—indicative of molecular cooperativity. These differences in both local and long-range molecular dynamics are a direct reflection of the subtly different inter-ionic interactions and mesoscale structures found in these homologous ILs.« less

Structural control of mixed ionic and electronic transport in conducting polymers

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

Rivnay, Jonathan; Inal, Sahika; Collins, Brian A.

Poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate), PEDOT:PSS, has been utilized for over two decades as a stable, solution-processable hole conductor. While its hole transport properties have been the subject of intense investigation, recent work has turned to PEDOT:PSS as a mixed ionic/electronic conductor in applications including bioelectronics, energy storage and management, and soft robotics. Conducting polymers can efficiently transport both holes and ions when sufficiently hydrated, however, little is known about the role of morphology on mixed conduction. Here, we show that bulk ionic and electronic mobilities are simultaneously affected by processing-induced changes in nano- and meso-scale structure in PEDOT:PSS films. Wemore » quantify domain composition, and find that domain purification on addition of dispersion co-solvents limits ion mobility, even while electronic conductivity improves. We show that an optimal morphology allows for the balanced ionic and electronic transport that is critical for prototypical mixed conductor devices. As a result, these findings may pave the way for the rational design of polymeric materials and processing routes to enhance devices reliant on mixed conduction.« less

Aluminium electrodeposition in chloroaluminate ionic liquid.

PubMed

Zhang, Lipeng; Wang, Enqi; Mu, Jiechen; Yu, Xianjin; Wang, Qiannan; Yang, Lina; Zhao, Zengdian

2014-08-01

An efficient microwave enhanced synthesis of ambient temperature chloroaluminate ionic liquid ([EMIM]Br) that preceeds reaction of 1-methylimidazolium with bromoethane in a closed vessel, was described in our work. The reaction time was drastically reduced as compared to the conventional methods. The electrochemical techniques of impedance spectroscopy, cyclic voltammetry and chronoamperometry were used to investigate the mechanism of Al electrodeposition from 2:1 (molar ratio) AlCl3/[EMIM]Br ionic liquid at room temperature. Results indicated that Al electrode- position from this ionic liqud was a quasi-reversible process, and the kinetic complications during the reaction was probably attributed to the electron transfer or mass transport cooperative controlled processes, instantaneous nucleation with diffusion-controlled growth was also investigated. Electrodepositon experiment was conducted using constant current density of 40 mA·cm(-2) for 20 minutes at room temperature and the qualitative analysis of the deposits were performed using X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and energy dispersive spectroscope (EDS). The deposits obtained on copper cathode were dense and compact and most Al crystal shows granular structure spherical with high purity.

Aggregate-mediated charge transport in ionomeric electrolytes

NASA Astrophysics Data System (ADS)

Lu, Keran; Maranas, Janna; Milner, Scott

Polymers such PEO can conduct ions, and have been studied as possible replacements for organic liquid electrolytes in rechargeable metal-ion batteries. More generally, fast room-temperature ionic conduction has been reported for a variety of materials, from liquids to crystalline solids. Unfortunately, polymer electrolytes generally have limited conductivity; these polymers are too viscous to have fast ion diffusion like liquids, and too unstructured to promote cooperative transport like crystalline solids. Ionomers are polymer electrolytes in which ionic groups are covalently bound to the polymer backbone, neutralized by free counterions. These materials also conduct ions, and can exhibit strong ionic aggregation. Using coarse-grained molecular dynamics, we explore the forces driving ionic aggregation, and describe the role ion aggregates have in mediating charge transport. The aggregates are string-like such that ions typically have two neighbors. We find ion aggregates self-assemble like worm-like micelles. Excess charge, or free ions, occasionally coordinate with aggregates and are transported along the chain in a Grotthuss-like mechanism. We propose that controlling ionomer aggregate structure through materials design can enhance cooperative ion transport.

Mixed Ionic Liquid Improves Electrolyte Dynamics in Supercapacitors

DOE PAGES

Osti, Naresh C.; Gallegos, Alejandro; Dyatkin, Boris; ...

2018-04-19

Well-tailored mixtures of distinct ionic liquids can act as optimal electrolytes that extend the operating electrochemical window and improve charge storage density in supercapacitors. Here, we explore two room-temperature ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimTFSI) and 1-ethyl-3-methylimidazolium tetrafluoroborate (EmimBF 4). We study their electric double-layer behavior in the neat state and as binary mixtures on the external surfaces of onion-like carbon electrodes using quasielastic neutron scattering (QENS) and classical density functional theory techniques. Computational results reveal that a mixture with 4:1 EmimTFSI/EmimBF 4 volume ratio displaces the larger [TFSI –] anions with smaller [BF 4 –] ions, leading to an excessmore » adsorption of [Emim +] cations near the electrode surface. These findings are corroborated by the manifestation of nonuniform ion diffusivity change, complementing the description of structural modifications with changing composition, from QENS measurements. In conclusion, molecular-level understanding of ion packing near electrodes provides insight for design of ionic liquid formulations that enhance the performance of electrochemical energy storage devices.« less

Effects of Dopant Ionic Radius on Cerium Reduction in Epitaxial Cerium Oxide Thin Films

DOE PAGES

Yang, Nan; Orgiani, Pasquale; Di Bartolomeo, Elisabetta; ...

2017-04-17

The role of trivalent rare-earth dopants in ceria epitaxial films on surface ion exchange reactivity and ion conductivity has been systematically studied. Single-crystal epitaxial films with unique crystal orientation and micro-structure nature have allowed us to rule out the influence of structural defects on both transport and surface ion exchange properties. The films conductivities were larger than those reported in literature for both polycrystalline ceramic pellets and crystalline films. An increase in oxygen vacancies and Ce 3+ concentration while decreasing the dopant ionic radius from La 3+ to Yb 3+ was observed, thus explaining the measured increased activation energy andmore » enhanced surface reactivity. The more significant ability of smaller dopant ionic radius in releasing the stress strength induced by the larger Ce 3+ ionic radius allows promoting the formation of oxygen vacancies and Ce 3+, which are two precious species in determining the efficiency of ion transport and surface ion exchange processes. This can open new perspectives in designing ceria-based materials in tailoring functional properties, either ion migration or surface reactivity, by rational cation substitutions.« less

Structural control of mixed ionic and electronic transport in conducting polymers

DOE PAGES

Rivnay, Jonathan; Inal, Sahika; Collins, Brian A.; ...

2016-04-19

Poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate), PEDOT:PSS, has been utilized for over two decades as a stable, solution-processable hole conductor. While its hole transport properties have been the subject of intense investigation, recent work has turned to PEDOT:PSS as a mixed ionic/electronic conductor in applications including bioelectronics, energy storage and management, and soft robotics. Conducting polymers can efficiently transport both holes and ions when sufficiently hydrated, however, little is known about the role of morphology on mixed conduction. Here, we show that bulk ionic and electronic mobilities are simultaneously affected by processing-induced changes in nano- and meso-scale structure in PEDOT:PSS films. Wemore » quantify domain composition, and find that domain purification on addition of dispersion co-solvents limits ion mobility, even while electronic conductivity improves. We show that an optimal morphology allows for the balanced ionic and electronic transport that is critical for prototypical mixed conductor devices. As a result, these findings may pave the way for the rational design of polymeric materials and processing routes to enhance devices reliant on mixed conduction.« less

Ion transport and structural dynamics in homologous ammonium and phosphonium-based room temperature ionic liquids

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

Griffin, Phillip J.; Holt, Adam P.; Tsunashima, Katsuhiko

2015-02-01

Charge transport and structural dynamics in a homologous pair of ammonium and phosphonium based room temperature ionic liquids (ILs) have been characterized over a wide temperature range using broadband dielectric spectroscopy and quasi-elastic light scattering spectroscopy. We have found that the ionic conductivity of the phosphonium based IL is significantly enhanced relative to the ammonium homolog, and this increase is primarily a result of a lower glass transition temperature and higher ion mobility. Additionally, these ILs exhibit pronounced secondary relaxations which are strongly influenced by the atomic identity of the cation charge center. While the secondary relaxation in the phosphoniummore » IL has the expected Arrhenius temperature dependence characteristic of local beta relaxations, the corresponding relaxation process in the ammonium IL was found to exhibit a mildly non-Arrhenius temperature dependence in the measured temperature range-indicative of molecular cooperativity. These differences in both local and long-range molecular dynamics are a direct reflection of the subtly different inter-ionic interactions and mesoscale structures found in these homologous ILs.« less

Toward full spectrum speciation of silver nanoparticles and ionic silver by on-line coupling of hollow fiber flow field-flow fractionation and minicolumn concentration with multiple detectors.

PubMed

Tan, Zhi-Qiang; Liu, Jing-Fu; Guo, Xiao-Ru; Yin, Yong-Guang; Byeon, Seul Kee; Moon, Myeong Hee; Jiang, Gui-Bin

2015-08-18

The intertransformation of silver nanoparticles (AgNPs) and ionic silver (Ag(I)) in the environment determines their transport, uptake, and toxicity, demanding methods to simultaneously separate and quantify AgNPs and Ag(I). For the first time, hollow fiber flow field-flow fractionation (HF5) and minicolumn concentration were on-line coupled together with multiple detectors (including UV-vis spectrometry, dynamic light scattering, and inductively coupled plasma mass spectrometry) for full spectrum separation, characterization, and quantification of various Ag(I) species (i.e., free Ag(I), weak and strong Ag(I) complexes) and differently sized AgNPs. While HF5 was employed for filtration and fractionation of AgNPs (>2 nm), the minicolumn packed with Amberlite IR120 resin functioned to trap free Ag(I) or weak Ag(I) complexes coming from the radial flow of HF5 together with the strong Ag(I) complexes and tiny AgNPs (<2 nm), which were further discriminated in a second run of focusing by oxidizing >90% of tiny AgNPs to free Ag(I) and trapped in the minicolumn. The excellent performance was verified by the good agreement of the characterization results of AgNPs determined by this method with that by transmission electron microscopy, and the satisfactory recoveries (70.7-108%) for seven Ag species, including Ag(I), the adduct of Ag(I) and cysteine, and five AgNPs with nominal diameters of 1.4 nm, 10 nm, 20 nm, 40 nm, and 60 nm in surface water samples.

Towards the Rational Design of Ionic Liquid Matrices for Secondary Ion Mass Spectrometry: Role of the Anion

NASA Astrophysics Data System (ADS)

Dertinger, Jennifer J.; Walker, Amy V.

2013-08-01

The role of the ionic liquid (IL) anion structure on analyte signal enhancements has been systematically investigated in secondary ion mass spectrometry (SIMS) using a variety of samples, including lipids, sterols, polymers, and peptides. Twenty-four ILs were synthesized. The 12 matrix acids were cinnamic acid derivatives. Two bases were employed: 1-methylimidazole and tripropylamine. Three matrices, methylimmidazolium o-coumarate, tripropylammonium o-coumarate, and tripropylammonium 3,4,5-trimethoxycinnamate, were "universal" matrices enhancing all analytes tested. The pKa of the matrix acid does not appear to have a strong effect on analyte ion intensities. Rather, it is observed that a single hydroxyl group on the anion aromatic ring leads to significantly increased molecular ion intensities. No analyte signal enhancements were observed for -CH3, -CF3 and -OCH3 groups present on the aromatic ring. The position of the -OH group on the aromatic ring also alters molecular ion intensity enhancements. As well as the chemical identity and position of substituents, the number of moieties on the aromatic ring may affect the analyte signal enhancements observed. These observations suggest that the activation of the IL anion aromatic ring is important for optimizing analyte signal intensities. The implications for SIMS imaging of complex structures, such as biological samples, are discussed.

Divalent cation and ionic strength effects on Vinca alkaloid-induced tubulin self-association.

PubMed

Lobert, S; Boyd, C A; Correia, J J

1997-01-01

We present here a systematic study of ionic strength and divalent cation effects on Vinca alkaloid-induced tubulin spiral formation. We used sedimentation velocity experiments and quantitative fitting of weight-average sedimentation coefficients versus free drug concentrations to obtain thermodynamic parameters under various solution conditions. The addition of 50-150 mM NaCl to our standard buffer (10 mM piperazine-N,N'-bis(2-ethanesulfonic acid), 1 mM Mg, 50 microM GDP or GTP, pH 6.9) enhances overall vinblastine- or vincristine-induced tubulin self-association. As demonstrated in previous studies, GDP enhances overall self-association more than GTP, although in the presence of salt, GDP enhancement is reduced. For example, in 150 mM NaCl, GDP enhancement is 0.24 kcal/mol for vinblastine and 0.36 kcal/mol for vincristine versus an average enhancement of 0.87 (+/- 0.34) kcal/mol for the same drugs in the absence of salt. Wyman linkage analysis of experiments with vinblastine or vincristine over a range of NaCl concentrations showed a twofold increase in the change in NaCl bound to drug-induced spirals in the presence of GTP compared to GDP. These data indicate that GDP enhancement of Vinca alkaloid-induced tubulin self-association is due in part to electrostatic inhibition in the GTP state. In the absence of NaCl, we found that vinblastine and 1 mM Mn2+ or Ca2+ causes immediate condensation of tubulin. The predominant aggregates observed by electron microscopy are large sheets. This effect was not found with 1 mM Mg2+. At 100 microM cation concentrations (Mn2+, Mg2+, or Ca2+), GDP enhances vinblastine-induced spiral formation by 0.55 (+/- 0.26) kcal/mol. This effect is found only in K2, the association of liganded heterodimers at the ends of growing spirals. There is no GDP enhancement of K1, the binding of drug to heterodimer, although K1 is dependent upon the divalent cation concentration. NaCl diminishes tubulin condensation, probably by inhibiting lateral association, and allows an investigation of higher divalent cation concentrations. In the presence of 150 mM NaCl plus 1 mM divalent cations (Mn2+, Mg2+, or Ca2+) GDP enhances vinblastine-induced spiral formation by 0.35 (+/- 0.21) kcal/mol. Relaxation times determined by stopped-flow light scattering experiments in the presence of 150 mM NaCl and vincristine are severalfold longer than those in the presence of vinblastine, consistent with a mechanism involving the redistribution of longer polymers. Unlike previous results in the absence of NaCl, relaxation times in the presence of NaCl are only weekly protein concentration dependent, suggesting the absence of annealing or an additional rate-limiting step in the mechanism.

Modulation of Molecular Flux Using a Graphene Nanopore Capacitor.

PubMed

Shankla, Manish; Aksimentiev, Aleksei

2017-04-20

Modulation of ionic current flowing through nanoscale pores is one of the fundamental biological processes. Inspired by nature, nanopores in synthetic solid-state membranes are being developed to enable rapid analysis of biological macromolecules and to serve as elements of nanofludic circuits. Here, we theoretically investigate ion and water transport through a graphene-insulator-graphene membrane containing a single, electrolyte-filled nanopore. By means of all-atom molecular dynamics simulations, we show that the charge state of such a graphene nanopore capacitor can regulate both the selectivity and the magnitude of the nanopore ionic current. At a fixed transmembrane bias, the ionic current can be switched from being carried by an equal mixture of cations and anions to being carried almost exclusively by either cationic or anionic species, depending on the sign of the charge assigned to both plates of the capacitor. Assigning the plates of the capacitor opposite sign charges can either increase the nanopore current or reduce it substantially, depending on the polarity of the bias driving the transmembrane current. Facilitated by the changes of the nanopore surface charge, such ionic current modulations are found to occur despite the physical dimensions of the nanopore being an order of magnitude larger than the screening length of the electrolyte. The ionic current rectification is accompanied by a pronounced electro-osmotic effect that can transport neutral molecules such as proteins and drugs across the solid-state membrane and thereby serve as an interface between electronic and chemical signals.

Effects of rare earth ionic doping on microstructures and electrical properties of CaCu{sub 3}Ti{sub 4}O{sub 12} ceramics

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

Xue, Renzhong; Department of Technology and Physics, Zhengzhou University of Light Industry, Zhengzhou 450002; Chen, Zhenping, E-mail: xrzbotao@163.com

2015-06-15

Graphical abstract: The dielectric constant decreases monotonically with reduced RE doping ion radius and is more frequency independent compared with that of pure CCTO sample. - Highlights: • The mean grain sizes decrease monotonically with reduced RE doping ionic radius. • Doping gives rise to the monotonic decrease of ϵ{sub r} with reduced RE ionic radius. • The nonlinear coefficient and breakdown field increase with RE ionic doping. • α of all the samples is associated with the potential barrier width rather than Φ{sub b}. - Abstract: Ca{sub 1–x}R{sub x}Cu{sub 3}Ti{sub 4}O{sub 12}(R = La, Nd, Eu, Gd, Er; xmore » = 0 and 0.005) ceramics were prepared by the conventional solid-state method. The influences of rare earth (RE) ion doping on the microstructure, dielectric and electrical properties of CaCu{sub 3}Ti{sub 4}O{sub 12} (CCTO) ceramics were investigated systematically. Single-phase formation is confirmed by XRD analyses. The mean grain size decreases monotonically with reduced RE ion radius. The EDS results reveal that RE ionic doping reduces Cu-rich phase segregation at the grain boundaries (GBs). Doping gives rise to the monotonic decrease of dielectric constant with reduced RE ionic radius but significantly improves stability with frequency. The lower dielectric loss of doped samples is obtained due to the increase of GB resistance. In addition, the nonlinear coefficient and breakdown field increase with RE ionic doping. Both the fine grains and the enhancement of potential barrier at GBs are responsible for the improvement of the nonlinear current–voltage properties in doped CCTO samples.« less

Size determination and quantification of engineered cerium oxide nanoparticles by flow field-flow fractionation coupled to inductively coupled plasma mass spectrometry.

PubMed

Sánchez-García, L; Bolea, E; Laborda, F; Cubel, C; Ferrer, P; Gianolio, D; da Silva, I; Castillo, J R

2016-03-18

Facing the lack of studies on characterization and quantification of cerium oxide nanoparticles (CeO2 NPs), whose consumption and release is greatly increasing, this work proposes a method for their sizing and quantification by Flow Field-flow Fractionation (FFFF) coupled to Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). Two modalities of FFFF (Asymmetric Flow- and Hollow Fiber-Flow Field Flow Fractionation, AF4 and HF5, respectively) are compared, and their advantages and limitations discussed. Experimental conditions (carrier composition, pH, ionic strength, crossflow and carrier flow rates) are studied in detail in terms of NP separation, recovery, and repeatability. Size characterization of CeO2 NPs was addressed by different approaches. In the absence of feasible size standards of CeO2 NPs, suspensions of Ag, Au, and SiO2 NPs of known size were investigated. Ag and Au NPs failed to show a comparable behavior to that of the CeO2 NPs, whereas the use of SiO2 NPs provided size estimations in agreement to those predicted by the theory. The latter approach was thus used for characterizing the size of CeO2 NPs in a commercial suspension. Results were in adequate concordance with those achieved by transmission electron microscopy, X-ray diffraction and dynamic light scattering. The quantification of CeO2 NPs in the commercial suspension by AF4-ICP-MS required the use of a CeO2 NPs standards, since the use of ionic cerium resulted in low recoveries (99 ± 9% vs. 73 ± 7%, respectively). A limit of detection of 0.9 μg L(-1) CeO2 corresponding to a number concentration of 1.8 × 1012 L(-1) for NPs of 5 nm was achieved for an injection volume of 100 μL. Copyright © 2016 Elsevier B.V. All rights reserved.

Mechanism-Based Enhanced Delivery of Drug-Loaded Targeted Nanoparticles for Breast Cancer Therapy

DTIC Science & Technology

2014-02-01

Enhanced Delivery of Drug-Loaded Targeted Nanoparticles for Breast Cancer Therapy” 5a. CONTRACT NUMBER 5b. GRANT NUMBER W81XWH-11-1-0166 5c... Nanotechnologies in Living Systems”, Moscow Region, Russia, September, 2011. 3. “Ionic nanogels for drug delivery in cancer ”. NanoDDS’12; Atlantic City, New...AD Award Number: W81XWH-11-1-0166 TITLE: Mechanism-Based Enhanced Delivery of Drug-Loaded Targeted Nanoparticles for Breast

Mechanism-Based Enhanced Delivery of Drug-Loaded Targeted Nanoparticles for Breast Cancer Therapy

DTIC Science & Technology

2014-02-01

Based Enhanced Delivery of Drug-Loaded Targeted Nanoparticles for Breast Cancer Therapy” 5a. CONTRACT NUMBER 5b. GRANT NUMBER W81XWH-11-1-0167 5c... Nanotechnologies in Living Systems”, Moscow Region, Russia, September, 2011. 3. “Ionic nanogels for drug delivery in cancer ”. NanoDDS’12; Atlantic City, New...AD Award Number: W81XWH-11-1-0167 TITLE: Mechanism-Based Enhanced Delivery of Drug-Loaded Targeted Nanoparticles for Breast

Impact of Surfactants on Skin Penetration of Dexpanthenol.

PubMed

Laffleur, Flavia; Pschick, Stefan; Barthelmes, Jan; Hauptstein, Sabine; Bernkop-Schnurch, Andreas

2018-01-01

It was the aim of this study to evaluate the impact of nonionic and ionic surfactants on skin penetration of dexpanthenol. The relative potency of three surfactants (two nonionic and one ionic) as enhancers in the permeability of a series of compounds was investigated. The influence of the enhancers was also studied. For this purpose, porcine abdominal skin was prepared and mounted on Franz diffusion cells, while different mixtures of Dexpanthenol containing Tween®85, SDS and Span®80 in concentrations of 0.5%, 1%, 2%, 5% (m/V) were evaluated in terms of their permeation enhancing effect. The amount of permeated drug was determined via HPLC analysis. Moreover, the cytotoxicity and skin irritating effect of the compounds were tested on Caco-2 cells. The cytotoxicity profile of Dexpanthenol showed no toxicity to the cells over 1 and 3 h of incubation. The permeation was evaluated over a time period of 180 min, whereas a ranking of SDS> Span>Tween could be determined as permeation enhancer. Taking these findings into consideration, concentration of 1% (w/w) surfactant showed the most promising results. The increase in flux based on low concentrations of enhancer was ascribed to their ability to reduce skin´s barrier and improve drug permeation. The results showed that the nature of enhancer greatly impacts cutaneous barrier impairment. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Microfabrication of IPMC cilia for bio-inspired flow sensing

NASA Astrophysics Data System (ADS)

Lei, Hong; Li, Wen; Tan, Xiaobo

2012-04-01

As the primary flow sensing organ for fishes, the lateral line system plays a critical role in fish behavior. Analogous to its biological counterpart, an artificial lateral line system, consisting of arrays of micro flow sensors, is expected to be instrumental in the navigation and control of underwater robots. In this paper we investigate the microfabrication of ionic polymer-metal composite (IPMC) cilia for the purpose of flow sensing. While existing macro- and microfabrication methods for IPMCs have predominantly focused on planar structures, we propose a device where micro IPMC beams stand upright on a substrate to effectively interact with the flow. Challenges in the casting of 3D Nafion structure and selective formation of electrodes are discussed, and potential solutions for addressing these challenges are presented together with preliminary microfabrication results.

Comparison of the Nernst-Planck model and the Poisson-Boltzmann model for electroosmotic flows in microchannels.

PubMed

Park, H M; Lee, J S; Kim, T W

2007-11-15

In the analysis of electroosmotic flows, the internal electric potential is usually modeled by the Poisson-Boltzmann equation. The Poisson-Boltzmann equation is derived from the assumption of thermodynamic equilibrium where the ionic distributions are not affected by fluid flows. Although this is a reasonable assumption for steady electroosmotic flows through straight microchannels, there are some important cases where convective transport of ions has nontrivial effects. In these cases, it is necessary to adopt the Nernst-Planck equation instead of the Poisson-Boltzmann equation to model the internal electric field. In the present work, the predictions of the Nernst-Planck equation are compared with those of the Poisson-Boltzmann equation for electroosmotic flows in various microchannels where the convective transport of ions is not negligible.

Polyaniline-coated cigarette filters as a solid-phase extraction sorbent for the extraction and enrichment of polycyclic aromatic hydrocarbon in water samples.

PubMed

Bunkoed, Opas; Rueankaew, Thanaschaphorn; Nurerk, Piyaluk; Kanatharana, Proespichaya

2016-06-01

Polyaniline coated cigarette filters were successfully synthesized and used as a solid-phase extraction sorbent for the extraction and preconcentration of polycyclic aromatic hydrocarbons in water samples. The polyaniline helped to enhance the adsorption ability of polycyclic aromatic hydrocarbons on the sorbent through π-π interactions. The high porosity and large surface area of the cigarette filters helped to reduce backpressure and can be operated with high sample flow rate without loss of extraction efficiency. The developed sorbent was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The parameters that affected the extraction efficiencies, i.e. polymerization time, type of desorption solvent and its volume, sample flow rate, sample volume, sample pH, ionic strength, and organic modifier were investigated. Under the optimal conditions, the method was linear over the range of 0.5-10 μg/L and a detection limit of 0.5 ng/L. This simple, rapid, and cost-effective method was successfully applied to the preconcentration of polycyclic aromatic hydrocarbons from water samples. The developed method provided a high enrichment factor with good extraction efficiency (85-98%) and a relative standard deviation <10%. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hybrid composite membranes of chitosan/sulfonated polyaniline/silica as polymer electrolyte membrane for fuel cells.

PubMed

Vijayakumar, Vijayalekshmi; Khastgir, Dipak

2018-01-01

A series of novel ionic cross-linked chitosan (CS) based hybrid nanocomposites were prepared by using polyaniline/nano silica (PAni/SiO 2 ) as inorganic filler and sulfuric acid as an ionic cross-linking agent. The CS-PAni/SiO 2 nanocomposites show enhanced mechanical properties and improved oxidative stabilities. These nanocomposites can be effectively used as environmental friendly proton exchange membranes. Incorporation of PAni/SiO 2 into CS matrix enhances water uptake and facilitates the phase separation which enables the formation of hydrophilic domains and improves the proton transport. Moreover, the doped polyaniline also provides some additional pathways for proton conduction. The membrane containing 3wt% loading of PAni/SiO 2 in chitosan (CS-PAni/SiO 2 -3) exhibits high proton conductivity at 80°C (8.39×10 -3 Scm -1 ) in fully hydrated state due to its excellent water retention properties. Moreover, methanol permeability of the ionic cross-linked CS-PAni/SiO 2 nanocomposite membranes significantly reduces with the addition of PAni/SiO 2 nano particles. The CS-PAni/SiO 2 -3 composite membrane displays the best overall performance as a polymer electrolyte membrane. Copyright © 2017 Elsevier Ltd. All rights reserved.

Destabilization of Human Serum Albumin by Ionic Liquids Studied Using Enhanced Molecular Dynamics Simulations.

PubMed

Jaeger, Vance W; Pfaendtner, Jim

2016-12-01

Ionic liquid (IL) containing solvents can change the structure, dynamics, function, and stability of proteins. In order to investigate the mechanisms by which ILs induce structural changes in a large multidomain protein, we study the interactions of human serum albumin (HSA) with two different ILs, 1-butyl-3-methylimidazolium tetrafluoroborate and choline dihydrogen phosphate. Root mean square deviation and fluctuation calculations indicate that high concentrations of ILs in mixtures with water lead to protein structures that remain close to their crystallographic structures on time scales of hundreds of nanoseconds. To overcome potential time scale limitations due to the high viscosity of the solvent, we employed enhanced sampling techniques to estimate the free energy of an experimentally determined important transition within the protein structure. Metadynamics simulations show that the free energy landscape of the unfolding of loop 1 of domain I is different in the presence of ILs than it is in water, consistent with previously published experimental evidence. We then apply essential dynamics coarse graining to systematically predict differences in the dynamics of proteins solvated in IL-water mixtures versus pure water systems. We also demonstrate that the presence of ionic liquids changes the distribution of intermolecular distances among several ligands, indicating that the protein structure swells in the presence of certain ILs, consistent with experimental evidence.

Controllable Spatial Configuration on Cathode Interface for Enhanced Photovoltaic Performance and Device Stability.

PubMed

Li, Jiangsheng; Duan, Chenghao; Wang, Ning; Zhao, Chengjie; Han, Wei; Jiang, Li; Wang, Jizheng; Zhao, Yingjie; Huang, Changshui; Jiu, Tonggang

2018-05-08

The molecular structure of cathode interface modification materials can affect the surface morphology of the active layer and key electron transfer processes occurring at the interface of polymer solar cells in inverted structures mostly due to the change of molecular configuration. To investigate the effects of spatial configuration of the cathode interfacial modification layer on polymer solar cells device performances, we introduced two novel organic ionic salts (linear NS2 and three-dimensional (3D) NS4) combined with the ZnO film to fabricate highly efficient inverted solar cells. Both organic ionic salts successfully decreased the surface traps of the ZnO film and made its work function more compatible. Especially NS4 in three-dimensional configuration increased the electron mobility and extraction efficiency of the interfacial film, leading to a significant improvement of device performance. Power conversion efficiency (PCE) of 10.09% based on NS4 was achieved. Moreover, 3D interfacial modification could retain about 92% of its initial PCE over 160 days. It is proposed that 3D interfacial modification retards the element penetration-induced degradation without impeding the electron transfer from the active layer to the ZnO film, which significantly improves device stability. This indicates that inserting three-dimensional organic ionic salt is an efficient strategy to enhance device performance.

Materials Genomics Screens for Adaptive Ion Transport Behavior by Redox-Switchable Microporous Polymer Membranes in Lithium-Sulfur Batteries.

PubMed

Ward, Ashleigh L; Doris, Sean E; Li, Longjun; Hughes, Mark A; Qu, Xiaohui; Persson, Kristin A; Helms, Brett A

2017-05-24

Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance an analogous strategy for achieving adaptive ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device's active materials when they enter the membrane's pore. This transformation has little influence on the membrane's ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium-sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. The origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development.

Materials Genomics Screens for Adaptive Ion Transport Behavior by Redox-Switchable Microporous Polymer Membranes in Lithium–Sulfur Batteries

PubMed Central

2017-01-01

Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance an analogous strategy for achieving adaptive ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device’s active materials when they enter the membrane’s pore. This transformation has little influence on the membrane’s ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium–sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. The origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development. PMID:28573201

Self-assembly and enhanced photocatalytic properties of BiOI hollow microspheres via a reactable ionic liquid.

PubMed

Xia, Jiexiang; Yin, Sheng; Li, Huaming; Xu, Hui; Yan, Yongsheng; Zhang, Qi

2011-02-01

BiOI uniform flowerlike hollow microspheres with a hole in its surface structures have been successfully synthesized through an EG-assisted solvothermal process in the presence of ionic liquid 1-butyl-3-methylimidazolium iodine ([Bmim]I). The as-prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), nitrogen sorption, and diffuse reflectance spectroscopy (DRS). A possible formation mechanism for the growth of hollow microspheres was discussed. During the reactive process, ionic liquid not only acted as solvents and templates but also as an I source for the fabrication of BiOI hollow microspheres and was vital for the structure of hollow microspheres. Additionally, we evaluated the photocatalytic activities of BiOI on the degradation of methyl orange (MO) under visible light irradiation and found that as-prepared BiOI hollow microspheres exhibited higher photocatalytic activity than BiOI nanoplates and TiO(2) (Degussa, P25) did. On the basis of such analysis, it can be assumed that the enhanced photocatalytic activities of BiOI hollow microspheres could be ascribed to its energy band structure, high BET surface area, high surface-to-volume ratios, and light absorbance.

Thickness dependence of curvature, strain, and response time in ionic electroactive polymer actuators fabricated via layer-by-layer assembly

NASA Astrophysics Data System (ADS)

Montazami, Reza; Liu, Sheng; Liu, Yang; Wang, Dong; Zhang, Qiming; Heflin, James R.

2011-05-01

Ionic electroactive polymer (IEAP) actuators containing porous conductive network composites (CNCs) and ionic liquids can result in high strain and fast response times. Incorporation of spherical gold nanoparticles in the CNC enhances conductivity and porosity, while maintaining relatively small thickness. This leads to improved mechanical strain and bending curvature of the actuators. We have employed the layer-by-layer self-assembly technique to fabricate a CNC with enhanced curvature (0.43 mm-1) and large net intrinsic strain (6.1%). The results demonstrate that curvature and net strain of IEAP actuators due to motion of the anions increase linearly with the thickness of the CNC as a result of the increased volume in which the anions can be stored. In addition, after subtracting the curvature of a bare Nafion actuator without a CNC, it is found that the net intrinsic strain of the CNC layer is independent of thickness for the range of 20-80 nm, indicating that the entire CNC volume contributes equivalently to the actuator motion. Furthermore, the response time of the actuator due to anion motion is independent of CNC thickness, suggesting that traversal through the Nafion membrane is the limiting factor in the anion motion.

Towards understanding the effects of van der Waals strengths on the electric double-layer structures and capacitive behaviors

NASA Astrophysics Data System (ADS)

Yang, Huachao; Bo, Zheng; Yang, Jinyuan; Yan, Jianhua; Cen, Kefa

2017-10-01

Solid-liquid interactions are considered to play a crucial role in charge storage capability of electric double-layer capacitors (EDLCs). In this work, effects of van der Waals (VDW) strengths on the EDL structures and capacitive performances within two representative electrolytes of solvated aqueous solutions and solvent-free ionic liquids are illuminated by molecular dynamics simulations. Single crystalline metals with similar lattice constant but diverse VDW potentials are employed as electrodes. Upon enhancing VDW strengths, capacitance of aqueous electrolytes first increases conspicuously by ∼34.0% and then descends, manifesting a non-monotonic trend, which goes beyond traditional perspectives. Such unusual observation is interpreted by the excluded-volume effects stemmed from ion-solvent competitions. Stimulated by predominant coulombic interactions, more ions are aggregated at the interface despite of the increasing VDW potentials, facilitating superior screening efficiency and capacitance. However, further enhancing strengths preferentially attracts more solvents instead of ions to the electrified surface, which in turn strikingly repels ions from Helmholtz layers, deteriorating electrode capacitance. An essentially similar feather is also recognized for ionic liquids, while the corresponding mechanisms are prominently ascribed to the suppressed ionic separations issued from cation-anion competitions. We highlight that constructing electrode materials with a moderate-hydrophilicity could further advance the performances of EDLCs.

Universal Scaling of Robust Thermal Hot Spot and Ionic Current Enhancement by Focused Ohmic Heating in a Conic Nanopore

PubMed Central

Pan, Zehao; Wang, Ceming; Li, Meng; Chang, Hsueh-Chia

2017-01-01

A stable nanoscale thermal hot spot, with temperature approaching 100 °C, is shown to be sustained by localized Ohmic heating of a focused electric field at the tip of a slender conic nanopore. The self-similar (length-independent) conic geometry allows us to match the singular heat source at the tip to the singular radial heat loss from the slender cone to obtain a self-similar steady temperature profile along the cone and the resulting ionic current conductance enhancement due to viscosity reduction. The universal scaling, which depends only on a single dimensionless parameter Z, collapses the measured conductance data and computed temperature profiles in ion-track conic nanopores and conic nanopipettes. The collapsed numerical data reveal universal values for the hot-spot location and temperature in an aqueous electrolyte. PMID:27715110

Aqueous solutions of acidic ionic liquids for enhanced stability of polyoxometalate-carbon supercapacitor electrodes

NASA Astrophysics Data System (ADS)

Hu, Chenchen; Zhao, Enbo; Nitta, Naoki; Magasinski, Alexandre; Berdichevsky, Gene; Yushin, Gleb

2016-09-01

Nanocomposites based on polyoxometalates (POMs) nanoconfined in microporous carbons have been synthesized and used as electrodes for supercapacitors. The addition of the pseudocapacitance from highly reversible redox reaction of POMs to the electric double-layer capacitance of carbon lead to an increase in specific capacitance of ∼90% at 1 mV s-1. However, high solubility of POM in traditional aqueous electrolytes leads to rapid capacity fading. Here we demonstrate that the use of aqueous solutions of protic ionic liquids (P-IL) as electrolyte instead of aqueous sulfuric acid solutions offers an opportunity to significantly improve POM cycling stability. Virtually no degradation in capacitance was observed in POM-based positive electrode after 10,000 cycles in an asymmetric capacitor with P-IL aqueous electrolyte. As such, POM-based carbon composites may now present a viable solution for enhancing energy density of electrical double layer capacitors (EDLC) based on pure carbon electrodes.

High Electromechanical Response of Ionic Polymer Actuators with Controlled-Morphology Aligned Carbon Nanotube/Nafion Nanocomposite Electrodes

PubMed Central

Liu, Sheng; Liu, Yang; Cebeci, Hülya; de Villoria, Roberto Guzmán; Lin, Jun-Hong

2011-01-01

Recent advances in fabricating controlled-morphology vertically aligned carbon nanotubes (VA-CNTs) with ultrahigh volume fraction create unique opportunities for markedly improving the electromechanical performance of ionic polymer conductor network composite (IPCNC) actuators. Continuous paths through inter-VA-CNT channels allow fast ion transport, and high electrical conduction of the aligned CNTs in the composite electrodes lead to fast device actuation speed (>10% strain/second). One critical issue in developing advanced actuator materials is how to suppress the strain that does not contribute to the actuation (unwanted strain) thereby reducing actuation efficiency. Here our experiments demonstrate that the VA-CNTs give an anisotropic elastic response in the composite electrodes, which suppresses the unwanted strain and markedly enhances the actuation strain (>8% strain under 4 volts). The results reported here suggest pathways for optimizing the electrode morphology in IPCNCs using ultra-high volume fraction VA-CNTs to further enhanced performance. PMID:21765822

Protic ionic liquid modified electrocatalyst enables robust anode under cell reversal condition

NASA Astrophysics Data System (ADS)

Zhu, Zhengyu; Yan, Xiaocong; Tang, Haolin; Cai, Haopeng; Pan, Mu; Zhang, Haining; Luo, Jiangshui

2017-05-01

Pt/C has been commercially used as anode electrocatalyst for fuel cells but generally exhibits limited durability under conditions of fuel starvation and subsequent cell reversal. Herein we report an improved scaffold concept to simultaneously stabilize the catalyst against particle growth and reduce the adverse effects of cell reversal by modifying Pt/C with suitable protic ionic liquids (PILs). The modified Pt/C catalysts show enhanced cell reversal tolerance because of their high activity towards oxygen evolution reaction (OER), up to 300 mV lower overpotential compared to the unmodified Pt/C. Moreover, the PIL modified catalysts show better resistance to the loss of electrochemical surface area (ECSA) under simulated cell reversal conditions. The results indicate that modification of Pt/C catalysts with PILs is a promising strategy to enhance the stability and durability of electrocatalysts in fuel cell applications with the risk of frequent fuel starvation events, such as automotive fuel cells.

Substitution effect in reversible gel-liquid phase transformation polyoxometalate ionic liquid compounds.

PubMed

Wu, Xuefei; Cai, Huaxue; Wu, Qingyin; Yan, Wenfu

2016-07-28

The substitution effect in a series of POM-type reversible gel-liquid phase transformation ionic liquid compounds, [MIMPS]8P2W16V2O62, [MIMPS]6H2P2W16V2O62 and [MIMPS]4H4P2W16V2O62, has been investigated. Interestingly, there is an obvious substitution effect on the physicochemical properties of these compounds. When protons are substituted in place of ammonium, both the conductivity and the thermo-stability of the compounds can be increased a lot, and more protons can enhance this tendency.

Enhancing Natural Attenuation through Bioaugmentation with Aerobic Bacteria that Degrade cis-1,2-Dichloroethene

DTIC Science & Technology

2010-01-01

mg/L; low ionic strength (conductivity ᝿ milliSiemens per centimeter [mS/cm]); a pH of 6.5 to 8; and relatively low concentrations of TCE, 1,2-DCA...include: • Groundwater dissolved oxygen (DO) levels as low as 0.01 mg/L and as high as 8 mg/L; • Groundwater with low ionic strength (conductivity ᝿...held at 980°C. The chlorinated ethene was oxidized in the oven to CO2 and water. The water was removed via a Nafion ™ membrane water trap and the CO2

Yield stress and scaling of polyelectrolyte multilayer modified suspensions: effect of polyelectrolyte conformation during multilayer assembly.

PubMed

Hess, Andreas; Aksel, Nuri

2013-09-10

The yield stress of polyelectrolyte multilayer modified suspensions exhibits a surprising dependence on the polyelectrolyte conformation of multilayer films. The rheological data scale onto a universal master curve for each polyelectrolyte conformation as the particle volume fraction, φ, and the ionic strength of the background fluid, I, are varied. It is shown that rough films with highly coiled, brushy polyelectrolytes significantly enhance the yield stress. Moreover, via the ionic strength I of the background fluid, the dynamic yield stress of brushy polyelectrolyte multilayers can be finely adjusted over 2 decades.

Durable electrooptic devices comprising ionic liquids

DOEpatents

Agrawal, Anoop; Cronin, John P.; Tonazzi, Juan C. L.; Warner, Benjamin P.; McCleskey, T. Mark; Burrell, Anthony K.

2005-11-01

Electrolyte solutions for electrochromic devices such as rear view mirrors and displays with low leakage currents are prepared using inexpensive, low conductivity conductors. Preferred electrolytes include bifunctional redox dyes and molten salt solvents with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF3SO3-), bis(trifluoromethylsulfonyl)imide ((CF3SO2)2N-), bis(perfluoroethylsulfonyl)imide ((CF3CF2SO2)2N-) and tris(trifluoromethylsulfonyl)methide ((CF3SO2)3C-). Electroluminescent, electrochromic and photoelectrochromic devices with nanostructured electrodes include ionic liquids with bifunctional redox dyes.

Fluid Characteristics and Evolution of Chelungpu fault of Taiwan

NASA Astrophysics Data System (ADS)

Song, S. R.

2017-12-01

We analyzed geochemical characteristics, such as hydrogen and oxygen isotopes, and ionic concentrations, of fluid samples retrieved from various depth along boreholes of the Hole A and Hole B of Taiwan Chelungpu fault Drilling Project(TCDP) to trace the fluid sources. The results show that the source of fluid in the Hole B is mainly the tap water, while there are two probable sources in the Hole A owing to the abrupt shift of ionic concentrations at the depth of 200-300 m. The shallower fluid might be from the leakage above the depth of 300 m and is characteristic of lower ionic concentrations and the isotopic ratios are close to those of adjacent river water. However, the deeper fluid should be the thermal water from Kueichulin formation because of high ionic concentrations, especially HCO3-, and higher oxygen isotope, which suggests higher temperature and more isotope exchange. Two sources of fluid of the Hole A are representative of the fluid systems in the hanging wall and foot wall respectively. The characteristics of fluids in the Hole A imply that the fault zone serves as a barrier in the inter-seismic period, resulting in distinctly different fluid between the Hanging wall and the foot wall. The frequent occurrence and the distribution of calcite veins provide the evidence of the upwelling of HCO3-rich fluid of Kueichulin formation and indicate that the fault served as fluid conduit during faulting and allowed the fluid flow across the fault zone to precipitate calcite veins in fractures of the hanging wall. Thus, we can deduce the mechanism of local groundwater flow during different stages of fault development by evidences such as calcite veins distribution, regional groundwater geology, and fluids characteristics in boreholes of the Hole-A and Hole B. During inter-seismic period, groundwater flows below and above the fault zone are separated by the impermeable fault gouge layer. In co-seismic time, faulting breaks the gouge layer, providing openings that let the over-pressured thermal water which contained high concentration of bicarbonate ion to surge up. After co-seismic period, the gouge layer is sealed again, residual thermal water which contained high concentration of bicarbonate ion in the hanging wall gradually precipitated calcite in fractures and the closer precipitation took place, the more calcite veins.

Conductance valve and pressure-to-conductance transducer method and apparatus

DOEpatents

Schoeniger, Joseph S.; Cummings, Eric B.; Brennan, James S.

2005-01-18

A device for interrupting or throttling undesired ionic transport through a fluid network is disclosed. The device acts as a fluid valve by reversibly generating a fixed "bubble" in the conducting solvent solution carried by the network. The device comprises a porous hydrophobic structure filling a portion of a connecting channel within the network and optionally incorporates flow restrictor elements at either end of the porous structure that function as pressure isolation barriers, and a fluid reservoir connected to the region of the channel containing the porous structure. Also included is a pressure pump connected to the fluid reservoir. The device operates by causing the pump to vary the hydraulic pressure to a quantity of solvent solution held within the reservoir and porous structure. At high pressures, most or all of the pores of the structure are filled with conducting liquid so the ionic conductance is high. At lower pressures, only a fraction of the pores are filled with liquid, so ionic conductivity is lower. Below a threshold pressure, the porous structure contains only vapor, so there is no liquid conduction path. The device therefore effectively throttles ionic transport through the porous structure and acts as a "conductance valve" or "pressure-to-conductance" transducer within the network.

Gas chromatography with mass spectrometry for the determination of phthalates preconcentrated by microextraction based on an ionic liquid.

PubMed

Cacho, Juan Ignacio; Campillo, Natalia; Viñas, Pilar; Hernández-Córdoba, Manuel

2017-03-01

A new procedure is proposed for the analysis of migration test solutions obtained from plastic bottles used in the packaging of edible oils. Ultrasound-assisted emulsification microextraction with ionic liquids was applied for the preconcentration of six phthalate esters: dimethylphthalate, diethylphthalate, di-n-butylphthalate, n-butylbenzylphthalate, di-2-ethylhexylphthalate, and di-n-octylphthalate. The enriched ionic liquid was directly analyzed by gas chromatography and mass spectrometry using direct insert microvial thermal desorption. The different factors affecting the microextraction efficiency, such as volume of the extracting phase (30 μL of the ionic liquid) and ultrasound application time (25 s), and the thermal desorption step, such as desorption temperature and time, and gas flow rate, were studied. Under the selected conditions, detection limits for the analytes were in the 0.012-0.18 μg/L range, while recovery assays provided values ranging from 80 to 112%. The use of butyl benzoate as internal standard increased the reproducibility of the analytical procedure. When the release of the six phthalate esters from the tested plastic bottles to liquid simulants was monitored using the optimized procedure, analyte concentrations of between 1.0 and 273 μg/L were detected. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Impact of non-ideal analyte behavior on the separation of protein aggregates by asymmetric flow field-flow fractionation.

PubMed

Boll, Björn; Josse, Lena; Heubach, Anja; Hochenauer, Sophie; Finkler, Christof; Huwyler, Jörg; Koulov, Atanas V

2018-04-25

Asymmetric flow field-flow fractionation is a valuable tool for the characterization of protein aggregates in biotechnology owing to its broad size range and unique separation principle. However, in practice asymmetric flow field-flow fractionation is non-trivial to use due to the major deviations from theory and the influence on separation by various factors that are not fully understood. Here we report methods to assess the non-ideal effects that influence asymmetric flow field-flow fractionation separation and for the first time identify experimentally the main factors that impact it. Furthermore, we propose new approaches to minimize such non-ideal behavior, showing that by adjusting the mobile phase composition (pH and ionic strength) the resolution of asymmetric flow field-flow fractionation separation can be drastically improved. Additionally, we propose a best practice method for new proteins. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Electro-osmosis of nematic liquid crystals under weak anchoring and second-order surface effects

NASA Astrophysics Data System (ADS)

Poddar, Antarip; Dhar, Jayabrata; Chakraborty, Suman

2017-07-01

Advent of nematic liquid crystal flows has attracted renewed attention in view of microfluidic transport phenomena. Among various transport processes, electro-osmosis stands as one of the efficient flow actuation mechanisms through narrow confinements. In the present study, we explore the electrically actuated flow of an ordered nematic fluid with ionic inclusions, taking into account the influences from surface-induced elasticity and electrical double layer (EDL) phenomena. Toward this, we devise the coupled flow governing equations from fundamental free-energy analysis, considering the contributions from first- and second-order elastic, dielectric, flexoelectric, charged surface polarization, ionic and entropic energies. The present study focuses on the influence of surface charge and elasticity effects in the resulting linear electro-osmosis through a slit-type microchannel whose surfaces are chemically treated to display a homeotropic-type weak anchoring state. An optical periodic stripe configuration of the nematic director has been observed, especially for higher electric fields, wherein the Ericksen number for the dynamic study is restricted to the order of unity. Contrary to the isotropic electrolytes, the EDL potential in this case was found to be dependent on the external field strength. Through a systematic investigation, we brought out the fact that the wavelength of the oscillating patterns is dictated mainly by the external field, while the amplitude depends on most of the physical variables ranging from the anchoring strength and the flexoelectric coefficients to the surface charge density and electrical double layer thickness.

Polyetherimide/bucky gels nanocomposites with superior conductivity and thermal stability.

PubMed

Chen, Ye; Tao, Jing; Deng, Lin; Li, Liang; Li, Jun; Yang, Yang; Khashab, Niveen M

2013-08-14

Polyetherimide (PEI) nanocomposites comprising bucky gels of industrial-grade multiwalled carbon nanotubes (MWCNTs) and ionic liquid (IL, 1-butyl-3-methyl imidazolium hexafluorophosphate ([BMIM][PF6])) were prepared. The processing framework for this nanocomposite is simple, reproducible, and easily scalable. The strong interaction between IL and MWCNTs caused the latter to uniformly disperse in the PEI matrix while IL flowed into the gaps between the nanotubes' walls. The nanocomposite exhibited an enhanced conductivity of 2.01 × 10(4) Ω·cm volume resistivity at room temperature; the value decreased dramatically by 12 orders of magnitude, compared to pristine PEI. The IL free ions and MWCNTs networks provided excellent channels for electron transfer. PEI/bucky gels nanocomposites also showed improved thermal stability and high tensile strength. Other than having antiwear properties, this material can have numerous applications in the aerospace and electronics industries. Moreover, our work presents a "green" method toward modified nanocomposites industrial production as IL is environmentally safe and is easily recyclable.

Switchable silver mirrors with long memory effects.

PubMed

Park, Chihyun; Seo, Seogjae; Shin, Haijin; Sarwade, Bhimrao D; Na, Jongbeom; Kim, Eunkyoung

2015-01-01

An electrochemically stable and bistable switchable mirror was achieved for the first time by introducing (1) a thiol-modified indium tin oxide (ITO) electrode for the stabilization of the metallic film and (2) ionic liquids as an anion-blocking layer, to achieve a long memory effect. The growth of the metallic film was denser and faster at the thiol-modified ITO electrode than at a bare ITO electrode. The electrochemical stability of the metallic film on the thiol-modified ITO was enhanced, maintaining the metallic state without rupture. In the voltage-off state, the metal film maintained bistability for a long period (>2 h) when ionic liquids were introduced as electrolytes for the switchable mirror. The electrical double layer in the highly viscous ionic liquid electrolyte seemed to effectively form a barrier to the bromide ions, to protect the metal thin film from them when in the voltage-off state.

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

Lee, Shinbuhm; Zhang, Wenrui; Khatkhatay, Fauzia

Fast ion transport channels at interfaces in thin films have attracted great attention due to a range of potential applications for energy materials and devices, for, solid oxide fuel cells, sensors, and memories. Here, it is shown that in vertical nanocomposite heteroepitaxial films of SrZrO 3–RE 2O 3 (RE = Sm, Eu, Gd, Dy, and Er) the ionic conductivity of the composite can be tuned and strongly enhanced using embedded, stiff, and vertical nanopillars of RE 2O 3. With increasing lattice constant of RE 2O 3 from Er 2O 3 to Sm 2O 3, it is found that the tensilemore » strain in the SrZrO 3 increases proportionately, and the ionic conductivity of the composite increases accordingly, by an order of magnitude. Lastly, the results here conclusively show, for the first time, that strain in films can be effectively used to tune the ionic conductivity of the materials.« less

Enhanced photophysics of conjugated polymers

DOEpatents

Chen, Liaohai [Argonne, IL; Xu, Su [Santa Clara, CA; McBranch, Duncan [Santa Fe, NM; Whitten, David [Santa Fe, NM

2003-05-27

The addition of oppositely charged surfactant to fluorescent ionic conjugated polymer forms a polymer-surfactant complex that exhibits at least one improved photophysical property. The conjugated polymer is a fluorescent ionic polymer that typically has at least one ionic side chain or moiety that interacts with the specific surfactant selected. The photophysical property improvements may include increased fluorescence quantum efficiency, wavelength-independent emission and absorption spectra, and more stable fluorescence decay kinetics. The complexation typically occurs in a solution of a polar solvent in which the polymer and surfactant are soluble, but it may also occur in a mixture of solvents. The solution is commonly prepared with a surfactant molecule:monomer repeat unit of polymer ratio ranging from about 1:100 to about 1:1. A polymer-surfactant complex precipitate is formed as the ratio approaches 1:1. This precipitate is recoverable and usable in many forms.

Eco-friendly Energy Storage System: Seawater and Ionic Liquid Electrolyte.

PubMed

Kim, Jae-Kwang; Mueller, Franziska; Kim, Hyojin; Jeong, Sangsik; Park, Jeong-Sun; Passerini, Stefano; Kim, Youngsik

2016-01-08

As existing battery technologies struggle to meet the requirements for widespread use in the field of large-scale energy storage, novel concepts are urgently needed concerning batteries that have high energy densities, low costs, and high levels of safety. Here, a novel eco-friendly energy storage system (ESS) using seawater and an ionic liquid is proposed for the first time; this represents an intermediate system between a battery and a fuel cell, and is accordingly referred to as a hybrid rechargeable cell. Compared to conventional organic electrolytes, the ionic liquid electrolyte significantly enhances the cycle performance of the seawater hybrid rechargeable system, acting as a very stable interface layer between the Sn-C (Na storage) anode and the NASICON (Na3 Zr2 Si2 PO12) ceramic solid electrolyte, making this system extremely promising for cost-efficient and environmentally friendly large-scale energy storage. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Directed Synthesis of Nanoporous Carbons from Task-Specific Ionic Liquid Precursors for the Adsorption of CO 2

DOE PAGES

Mahurin, Shannon M.; Fulvio, Pasquale F.; Hillesheim, Patrick C.; ...

2014-07-31

Postcombustion CO 2 capture has become a key component of greenhouse-gas reduction as anthropogenic emissions continue to impact the environment. In this paper, we report a one-step synthesis of porous carbon materials using a series of task-specific ionic liquids for the adsorption of CO 2. By varying the structure of the ionic liquid precursor, we were able to control pore architecture and surface functional groups of the carbon materials in this one-step synthesis process leading to adsorbents with high CO 2 sorption capacities (up to 4.067 mmol g -1) at 0 °C and 1 bar. Finally, added nitrogen functional groupsmore » led to high CO 2/N 2 adsorption-selectivity values ranging from 20 to 37 whereas simultaneously the interaction energy was enhanced relative to carbon materials with no added nitrogen.« less

Manipulation of Spin-Torque Generation Using Ultrathin Au

NASA Astrophysics Data System (ADS)

An, Hongyu; Haku, Satoshi; Kanno, Yusuke; Nakayama, Hiroyasu; Maki, Hideyuki; Shi, Ji; Ando, Kazuya

2018-06-01

The generation and the manipulation of current-induced spin-orbit torques are of essential interest in spintronics. However, in spite of the vital progress in spin orbitronics, electric control of the spin-torque generation still remains elusive and challenging. We report on electric control of the spin-torque generation using ionic-liquid gating of ultrathin Au. We show that by simply depositing a SiO2 capping layer on an ultrathin-Au /Ni81Fe19 bilayer, the spin-torque generation efficiency is drastically enhanced by a maximum of 7 times. This enhancement is verified to be originated from the rough ultrathin-Au /Ni81Fe19 interface induced by the SiO2 deposition, which results in the enhancement of the interface spin-orbit scattering. We further show that the spin-torque generation efficiency from the ultrathin Au film can be reversibly manipulated by a factor of 2 using the ionic gating with an external electric field within a small range of 1 V. These results pave a way towards the efficient control of the spin-torque generation in spintronic applications.

Spectroscopic Study of Local Interactions of Platinum in Small [CexOy]Ptx' - Clusters

NASA Astrophysics Data System (ADS)

Ray, Manisha; Kafader, Jared O.; Chick Jarrold, Caroline

2016-06-01

Cerium oxide is a good ionic conductor, and the conductivity can be enhanced with oxygen vacancies and doping. This conductivity may play an important role in the enhancement of noble or coinage metal toward the water-gas shift reaction when supported by cerium oxide. The ceria-supported platinum catalyst in particular has received much attention because of higher activity at lower temperatures (LT) compared to the most common commercial LT-WGS catalyst. We have used a combination of anion photoelectron spectroscopy and density functional theory calculations to study the interesting molecular and electronic structures and properties of cluster models of ceria-supported platinum. [CexOy]Ptx' - (x,x'=1,2 ; y≤2x') clusters exhibit evidence of ionic bonding possible because of the high electron affinity of Pt and the low ionization potential of cerium oxide clusters. In addition, Pt- is a common daughter ion resulting from photodissociation of [CexOy]Ptx' - clusters. Finally, several of the anion and neutral clusters have profoundly different structures. These features may play a role in the enhancement of catalytic activity toward the water-gas shift reaction.

Probing the Interaction of Ionic Liquids with CO2: A Raman Spectroscopy and Ab Initio Study

DTIC Science & Technology

2008-05-05

called physisorption. Regardless of the sorption mechanism, a few quantitative parameters can be used to describe a gas-liquid interaction at a...Controllers (I and II) I II 22 and tube fittings, 0.062 inch perfluoroalkoxy ( PFA ) tubing, Tylan General Model FC-128 Flow Controllers

A transient electrochemical model incorporating the Donnan effect for all-vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Lei, Y.; Zhang, B. W.; Bai, B. F.; Zhao, T. S.

2015-12-01

In a typical all-vanadium redox flow battery (VRFB), the ion exchange membrane is directly exposed in the bulk electrolyte. Consequently, the Donnan effect occurs at the membrane/electrolyte (M/E) interfaces, which is critical for modeling of ion transport through the membrane and the prediction of cell performance. However, unrealistic assumptions in previous VRFB models, such as electroneutrality and discontinuities of ionic potential and ion concentrations at the M/E interfaces, lead to simulated results inconsistent with the theoretical analysis of ion adsorption in the membrane. To address this issue, this work proposes a continuous-Donnan effect-model using the Poisson equation coupled with the Nernst-Planck equation to describe variable distributions at the M/E interfaces. A one-dimensional transient VRFB model incorporating the Donnan effect is developed. It is demonstrated that the present model enables (i) a more realistic simulation of continuous distributions of ion concentrations and ionic potential throughout the membrane and (ii) a more comprehensive estimation for the effect of the fixed charge concentration on species crossover across the membrane and cell performance.

Random quaternary ammonium Diels-Alder poly(phenylene) copolymers for improved vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Largier, Timothy D.; Cornelius, Chris J.

2017-06-01

This study analyzes the effect of quaternary ammonium homopolymer (AmPP) and ionic and non-ionic random unit copolymerization (AmPP-PP) of Diels-Alder poly(phenylene)s on electrochemical and transport properties, vanadium redox flow battery performance, and material stability. AmPP-PP materials were synthesized with IEC's up to 2.2 meq/g, displaying a carbonate form ion conductivity of 17.3 mS/cm and water uptake of 57.3%. Vanadium ion permeability studies revealed that the random copolymers possess superior charge carrier selectivity. For materials of comparable ion content, at 10 mA/cm2 the random copolymer displayed a 14% increase in coulombic efficiency (CE) corresponding to a 7% increase in energy efficiency. All quaternary ammonium materials displayed ex situ degradation in a 0.5 M V5+ + 5 M H2SO4 solution, with the rate of degradation appearing to increase with IEC. Preliminary studies reveal that the neutralizing counter-ion has a significant effect on VRB performance, proportional to changes in vanadium ion molecular diffusion.

Prediction of fundamental properties of ionic liquid electrospray thrusters using molecular dynamics.

PubMed

Borner, Arnaud; Li, Zheng; Levin, Deborah A

2013-06-06

Molecular dynamics (MD) simulations are performed to model an electrospray thruster for the ionic liquid (IL) EMIM-BF4 using two coarse-grained (CG) potentials. Different equilibrium properties were obtained for the two potentials and then both were used to study the electrical extrusion of the IL for different electric field strengths and mass flow rates. The MD simulations provide the first insight into the atomistic modeling of a capillary-tip-extractor system, the basic elements of an electrospray thruster. One of the CG potentials was found to predict the formation of the Taylor cone, the cone-jet, and other extrusion modes for similar electric fields and mass flow rates observed in experiments of a IL fed capillary-tip-extractor system. Current distributions and anion and cation behavior were characterized and estimates of thrust and specific impulse are presented and compare reasonably well with measurements. Moreover, the role of inhomogeneities in the electric field as well as that of the IL space-charge most likely will improve agreement between modeling and experiment.

A study of single and binary ion plasma expansion into laboratory-generated plasma wakes

NASA Technical Reports Server (NTRS)

Wright, Kenneth Herbert, Jr.

1988-01-01

Plasma expansion into the wake of a large rectangular plate immersed in a collisionless, supersonic plasma was investigated in laboratory experiments. The experimental conditions address both single ion and binary ion plasma flows for the case of a body whose size is large in comparison with the Debye length, when the potential difference between the body and the plasma is relatively small. A new plasma source was developed to generate equi-velocity, binary ion plasma flows, which allows access to new parameter space that have previously been unavailable for laboratory studies. Specifically, the new parameters are the ionic mass ratio and the ionic component density ratio. In a series of experiments, a krypton-neon plasma is employed where the ambient density ratio of neon to krypton is varied more than an order of magnitude. The expansion in both the single ion and binary ion plasma cases is limited to early times, i.e., a few ion plasma periods, by the combination of plasma density, plasma drift speed, and vacuum chamber size, which prevented detailed comparison with self-similar theory.

Method and apparatus for confinement of ions in the presence of a neutral gas

DOEpatents

Peurrung, A.J.; Barlow, S.E.

1999-08-03

The present invention is an apparatus and method for combining ions with a neutral gas and flowing the mixture with a radial flow component through a magnetic field so that the weakly ionized gas is confined by the neutral gas. When the weakly ionized gas is present in sufficient density, a weakly ionized non-neutral plasma is formed that may be trapped in accordance with the present invention. Applications for a weakly ionized non-neutral plasma exploit the trap`s ability to store and manipulate ionic species in the presence of neutral gas. The trap may be connected to a mass spectrometer thereby permitting species identification after a fixed period of time. Delicate and/or heavy particles such as clusters may be held and studied in a ``gentle`` environment. In addition, the trap can provide a relatively intense, low-energy source of a particular ion species for surface implantation or molecular chemistry. Finally, a long trap may permit spectroscopy of unprecedented accuracy to be performed on ionic species. 4 figs.

Source of Sustained Voltage Difference between the Xylem of a Potted Ficus benjamina Tree and Its Soil

PubMed Central

Love, Christopher J.; Zhang, Shuguang; Mershin, Andreas

2008-01-01

It has long been known that there is a sustained electrical potential (voltage) difference between the xylem of many plants and their surrounding soil, but the mechanism behind this voltage has remained controversial. After eliminating any extraneous capacitive or inductive couplings and ground-mediated electric current flows, we have measured sustained differences of 50–200 mV between the xylem region of a Faraday-caged, intact, potted Ficus benjamina tree and its soil, as well as between its cut branches and soils and ionic solutions standardized to various pH values. Using identical platinum electrodes, no correlation between the voltage and time of day, illumination, sap flow, electrode elevation, or ionic composition of soil was found, suggesting no direct connection to simple dissimilar-metal redox reactions or transpirational activity. Instead, a clear relationship between the voltage polarity and magnitude and the pH difference between xylem and soil was observed. We attribute these sustained voltages to a biological concentration cell likely set up by the homeostatic mechanisms of the tree. Potential applications of this finding are briefly explored. PMID:18698415

Thermodynamics, electrostatics, and ionic current in nanochannels grafted with pH-responsive end-charged polyelectrolyte brushes.

PubMed

Chen, Guang; Das, Siddhartha

2017-03-01

In this paper, we study the thermodynamics, electrostatics, and an external electric field driven ionic current in a pH-responsive, end-charged polyelectrolyte (PE) brush grafted nanochannel. By employing a mean field theory, we unravel a highly nonintuitive interplay of pH and electrolyte salt concentration in dictating the height of the end-charged PE brush. Larger pH or weak hydrogen ion concentration leads to maximum ionization of the charge-producing group-as a consequence, the resulting the electric double layer (EDL) energy get maximized causing a maximum deviation of the brush height from the value (d 0 ) of the uncharged brush. This deviation may result in enhancement or lowering of the brush height as compared to d 0 depending on whether the PE end locates lower or higher than h/2 (h is the nanochannel half height) and the salt concentration. Subsequently, we use this combined PE-brush-configuration-EDL-electrostatics framework to compute the ionic current in the nanochannel. We witness that the ionic current for smaller pH is much larger despite the corresponding magnitude of the EDL electrostatic potential being much smaller-this stems from the presence of a much larger concentration of H+ ions at small pH and the fact that H+ ions have very large mobilities. In fact, this ionic current shows a steep variation with pH that can be useful in exploring new designs for applications involving quantification and characterization of ionic current in PE-brush-grafted nanochannels. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Poly(vinylidene fluoride-hexafluoropropylene) polymer electrolyte for paper-based and flexible battery applications

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

Aliahmad, Nojan; Shrestha, Sudhir; Varahramyan, Kody

2016-06-15

Paper-based batteries represent a new frontier in battery technology. However, low-flexibility and poor ionic conductivity of solid electrolytes have been major impediments in achieving practical mechanically flexible batteries. This work discuss new highly ionic conductive polymer gel electrolytes for paper-based battery applications. In this paper, we present a poly(vinylidene fluoride-hexafluoropropylene) (PVDH-HFP) porous membrane electrolyte enhanced with lithium bis(trifluoromethane sulphone)imide (LiTFSI) and lithium aluminum titanium phosphate (LATP), with an ionic conductivity of 2.1 × 10{sup −3} S cm{sup −1}. Combining ceramic (LATP) with the gel structure of PVDF-HFP and LiTFSI ionic liquid harnesses benefits of ceramic and gel electrolytes in providingmore » flexible electrolytes with a high ionic conductivity. In a flexibility test experiment, bending the polymer electrolyte at 90° for 20 times resulted in 14% decrease in ionic conductivity. Efforts to further improving the flexibility of the presented electrolyte are ongoing. Using this electrolyte, full-cell batteries with lithium titanium oxide (LTO) and lithium cobalt oxide (LCO) electrodes and (i) standard metallic current collectors and (ii) paper-based current collectors were fabricated and tested. The achieved specific capacities were (i) 123 mAh g{sup −1} for standard metallic current collectors and (ii) 99.5 mAh g{sup −1} for paper-based current collectors. Thus, the presented electrolyte has potential to become a viable candidate in paper-based and flexible battery applications. Fabrication methods, experimental procedures, and test results for the polymer gel electrolyte and batteries are presented and discussed.« less

Torsten Almén (1931-2016): the father of non-ionic iodine contrast media.

PubMed

Nyman, Ulf; Ekberg, Olle; Aspelin, Peter

2016-09-01

The Swedish radiologist Torsten Almén is the first clinical radiologist ever to have made a fundamental contribution to intravascular contrast medium design, the development of non-ionic contrast media. He became emotionally triggered by the patients' severe pain each time he injected the ionic "high-osmolar" contrast media when performing peripheral arteriographies in the early 1960s. One day he got a flash of genius that combined the observation of pain, a pathophysiological theory and how to eliminate it with suitable contrast media chemistry. After self-studies in chemistry he developed the concept of iodine contrast media not dissociating into ions in solution to reduce their osmolality and even reach plasma isotonicity. He offered several pharmaceutical companies his concept of mono- and polymeric non-ionic agents but without response, since it was considered against the chemical laws of that time. Contrast media constructed as salts and dissociating into ions in solution was regarded an absolute necessity to achieve high enough water solubility and concentration for diagnostic purposes. Finally a small Norwegian company, Nyegaard & Co., took up his idea 1968 and together they developed the essentially painless "low-osmolar" monomeric non-ionic metrizamide (Amipaque) released in 1974 and iohexol (Omipaque) in 1982 followed by the "iso-osmolar" dimeric non-ionic iodixanol (Visipaque) released in 1993. This has implied a profound paradigm shift with regard to reduction of both hypertonic and chemotoxic side effects, which have been a prerequisite for the today's widespread use of contrast medium-enhanced CT and advanced endovascular interventional techniques even in fragile patients. © The Foundation Acta Radiologica 2016.

Optimization of ionic conductivity in doped ceria

PubMed Central

Andersson, David A.; Simak, Sergei I.; Skorodumova, Natalia V.; Abrikosov, Igor A.; Johansson, Börje

2006-01-01

Oxides with the cubic fluorite structure, e.g., ceria (CeO2), are known to be good solid electrolytes when they are doped with cations of lower valence than the host cations. The high ionic conductivity of doped ceria makes it an attractive electrolyte for solid oxide fuel cells, whose prospects as an environmentally friendly power source are very promising. In these electrolytes, the current is carried by oxygen ions that are transported by oxygen vacancies, present to compensate for the lower charge of the dopant cations. Ionic conductivity in ceria is closely related to oxygen-vacancy formation and migration properties. A clear physical picture of the connection between the choice of a dopant and the improvement of ionic conductivity in ceria is still lacking. Here we present a quantum-mechanical first-principles study of the influence of different trivalent impurities on these properties. Our results reveal a remarkable correspondence between vacancy properties at the atomic level and the macroscopic ionic conductivity. The key parameters comprise migration barriers for bulk diffusion and vacancy–dopant interactions, represented by association (binding) energies of vacancy–dopant clusters. The interactions can be divided into repulsive elastic and attractive electronic parts. In the optimal electrolyte, these parts should balance. This finding offers a simple and clear way to narrow the search for superior dopants and combinations of dopants. The ideal dopant should have an effective atomic number between 61 (Pm) and 62 (Sm), and we elaborate that combinations of Nd/Sm and Pr/Gd show enhanced ionic conductivity, as compared with that for each element separately. PMID:16478802

Optimization of ionic conductivity in doped ceria.

PubMed

Andersson, David A; Simak, Sergei I; Skorodumova, Natalia V; Abrikosov, Igor A; Johansson, Börje

2006-03-07

Oxides with the cubic fluorite structure, e.g., ceria (CeO2), are known to be good solid electrolytes when they are doped with cations of lower valence than the host cations. The high ionic conductivity of doped ceria makes it an attractive electrolyte for solid oxide fuel cells, whose prospects as an environmentally friendly power source are very promising. In these electrolytes, the current is carried by oxygen ions that are transported by oxygen vacancies, present to compensate for the lower charge of the dopant cations. Ionic conductivity in ceria is closely related to oxygen-vacancy formation and migration properties. A clear physical picture of the connection between the choice of a dopant and the improvement of ionic conductivity in ceria is still lacking. Here we present a quantum-mechanical first-principles study of the influence of different trivalent impurities on these properties. Our results reveal a remarkable correspondence between vacancy properties at the atomic level and the macroscopic ionic conductivity. The key parameters comprise migration barriers for bulk diffusion and vacancy-dopant interactions, represented by association (binding) energies of vacancy-dopant clusters. The interactions can be divided into repulsive elastic and attractive electronic parts. In the optimal electrolyte, these parts should balance. This finding offers a simple and clear way to narrow the search for superior dopants and combinations of dopants. The ideal dopant should have an effective atomic number between 61 (Pm) and 62 (Sm), and we elaborate that combinations of Nd/Sm and Pr/Gd show enhanced ionic conductivity, as compared with that for each element separately.

Poly(vinylidene fluoride-hexafluoropropylene) polymer electrolyte for paper-based and flexible battery applications

NASA Astrophysics Data System (ADS)

Aliahmad, Nojan; Shrestha, Sudhir; Varahramyan, Kody; Agarwal, Mangilal

2016-06-01

Paper-based batteries represent a new frontier in battery technology. However, low-flexibility and poor ionic conductivity of solid electrolytes have been major impediments in achieving practical mechanically flexible batteries. This work discuss new highly ionic conductive polymer gel electrolytes for paper-based battery applications. In this paper, we present a poly(vinylidene fluoride-hexafluoropropylene) (PVDH-HFP) porous membrane electrolyte enhanced with lithium bis(trifluoromethane sulphone)imide (LiTFSI) and lithium aluminum titanium phosphate (LATP), with an ionic conductivity of 2.1 × 10-3 S cm-1. Combining ceramic (LATP) with the gel structure of PVDF-HFP and LiTFSI ionic liquid harnesses benefits of ceramic and gel electrolytes in providing flexible electrolytes with a high ionic conductivity. In a flexibility test experiment, bending the polymer electrolyte at 90° for 20 times resulted in 14% decrease in ionic conductivity. Efforts to further improving the flexibility of the presented electrolyte are ongoing. Using this electrolyte, full-cell batteries with lithium titanium oxide (LTO) and lithium cobalt oxide (LCO) electrodes and (i) standard metallic current collectors and (ii) paper-based current collectors were fabricated and tested. The achieved specific capacities were (i) 123 mAh g-1 for standard metallic current collectors and (ii) 99.5 mAh g-1 for paper-based current collectors. Thus, the presented electrolyte has potential to become a viable candidate in paper-based and flexible battery applications. Fabrication methods, experimental procedures, and test results for the polymer gel electrolyte and batteries are presented and discussed.

Effects of geometric modulation and surface potential heterogeneity on electrokinetic flow and solute transport in a microchannel

NASA Astrophysics Data System (ADS)

Bera, Subrata; Bhattacharyya, S.

2017-12-01

A numerical investigation is performed on the electroosmotic flow (EOF) in a surface-modulated microchannel to induce enhanced solute mixing. The channel wall is modulated by placing surface-mounted obstacles of trigonometric shape along which the surface potential is considered to be different from the surface potential of the homogeneous part of the wall. The characteristics of the electrokinetic flow are governed by the Laplace equation for the distribution of external electric potential; the Poisson equation for the distribution of induced electric potential; the Nernst-Planck equations for the distribution of ions; and the Navier-Stokes equations for fluid flow simultaneously. These nonlinear coupled set of governing equations are solved numerically by a control volume method over the staggered system. The influence of the geometric modulation of the surface, surface potential heterogeneity and the bulk ionic concentration on the EOF is analyzed. Vortical flow develops near a surface modulation, and it becomes stronger when the surface potential of the modulated region is in opposite sign to the surface potential of the homogeneous part of the channel walls. Vortical flow also depends on the Debye length when the Debye length is in the order of the channel height. Pressure drop along the channel length is higher for a ribbed wall channel compared to the grooved wall case. The pressure drop decreases with the increase in the amplitude for a grooved channel, but increases for a ribbed channel. The mixing index is quantified through the standard deviation of the solute distribution. Our results show that mixing index is higher for the ribbed channel compared to the grooved channel with heterogeneous surface potential. The increase in potential heterogeneity in the modulated region also increases the mixing index in both grooved and ribbed channels. However, the mixing performance, which is the ratio of the mixing index to pressure drop, reduces with the rise in the surface potential heterogeneity.

Effects of geometric modulation and surface potential heterogeneity on electrokinetic flow and solute transport in a microchannel

NASA Astrophysics Data System (ADS)

Bera, Subrata; Bhattacharyya, S.

2018-04-01

A numerical investigation is performed on the electroosmotic flow (EOF) in a surface-modulated microchannel to induce enhanced solute mixing. The channel wall is modulated by placing surface-mounted obstacles of trigonometric shape along which the surface potential is considered to be different from the surface potential of the homogeneous part of the wall. The characteristics of the electrokinetic flow are governed by the Laplace equation for the distribution of external electric potential; the Poisson equation for the distribution of induced electric potential; the Nernst-Planck equations for the distribution of ions; and the Navier-Stokes equations for fluid flow simultaneously. These nonlinear coupled set of governing equations are solved numerically by a control volume method over the staggered system. The influence of the geometric modulation of the surface, surface potential heterogeneity and the bulk ionic concentration on the EOF is analyzed. Vortical flow develops near a surface modulation, and it becomes stronger when the surface potential of the modulated region is in opposite sign to the surface potential of the homogeneous part of the channel walls. Vortical flow also depends on the Debye length when the Debye length is in the order of the channel height. Pressure drop along the channel length is higher for a ribbed wall channel compared to the grooved wall case. The pressure drop decreases with the increase in the amplitude for a grooved channel, but increases for a ribbed channel. The mixing index is quantified through the standard deviation of the solute distribution. Our results show that mixing index is higher for the ribbed channel compared to the grooved channel with heterogeneous surface potential. The increase in potential heterogeneity in the modulated region also increases the mixing index in both grooved and ribbed channels. However, the mixing performance, which is the ratio of the mixing index to pressure drop, reduces with the rise in the surface potential heterogeneity.

Influence of ionic strength, anions, cations, and natural organic matter on the adsorption of pharmaceuticals to silica.

PubMed

Bui, Tung Xuan; Choi, Heechul

2010-08-01

The adsorption of four wide-use pharmaceuticals (carbamazepine, diclofenac, ibuprofen, and ketoprofen) onto a porous silica was investigated under varied ionic strengths, different anions, divalent cations (Ca(2+) and Mg(2+)), trivalent cations (Al(3+) and Fe(3+)), and natural organic matter (NOM). The experiments demonstrated that at a given pH the adsorption was most affected by ionic strength, trivalent cations, and properties of pharmaceuticals. The increase of ionic strength resulted in an increase in the adsorption of ketoprofen, but a decrease in the adsorption of carbamazepine. Trivalent metal cations made intense increases in the adsorption of three acidic pharmaceuticals, which could be due to the formation of inner-sphere complex of the cations on the surface and/or complexation of the pharmaceuticals with both surface and aqueous metal species. It was found that the adsorption of carbamazepine was not affected by divalent and trivalent cations, whereas the adsorption of diclofenac was solely impacted by the presence of Al(3+). Moreover, divalent cations at low concentration could slightly enhance the adsorption of ibuprofen and ketoprofen, whereas NOM caused a reduction in the adsorption of the tested pharmaceuticals except for diclofenac. These results suggest that ionic strength, divalent cations, trivalent cations, and NOM are notable factors affecting the adsorption of pharmaceuticals and thus the ultimate fate of pharmaceuticals in the aqueous environment. Copyright 2010 Elsevier Ltd. All rights reserved.

The Effect of Ionic Liquid Pretreatment on the Bioconversion of Tomato Processing Waste to Fermentable Sugars and Biogas.

PubMed

Allison, Brittany J; Cádiz, Juan Canales; Karuna, Nardrapee; Jeoh, Tina; Simmons, Christopher W

2016-08-01

Tomato pomace is an abundant lignocellulosic waste stream from industrial tomato processing and therefore a potential feedstock for production of renewable biofuels. However, little research has been conducted to determine if pretreatment can enhance release of fermentable sugars from tomato pomace. Ionic liquids (ILs) are an emerging pretreatment technology for lignocellulosic biomass to increase enzymatic digestibility and biofuel yield while utilizing recyclable chemicals with low toxicity. In this study, pretreatment of tomato pomace with the ionic liquid 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) was investigated. Changes in pomace enzymatic digestibility were affected by pretreatment time and temperature. Certain pretreatment conditions significantly improved reducing sugar yield and hydrolysis time compared to untreated pomace. Compositional analyses suggested that pretreatment primarily removed water-soluble compounds and enriched for lignocellulose in pomace, with only subtle changes to the composition of the lignocellulose. While tomato pomace was effectively pretreated with [C2mim][OAc] to improve enzymatic digestibility, as of yet, unknown factors in the pomace caused ionic liquid pretreatment to negatively affect anaerobic digestion of pretreated material. This result, which is unique compared to similar studies on IL pretreatment of grasses and woody biomass, highlights the need for additional research to determine how the unique chemical composition of tomato pomace and other lignocellulosic fruit residues may interact with ionic liquids to generate inhibitors for downstream fermentation to biofuels.

Ionic Conductivity Increased by Two Orders of Magnitude in Micrometer-Thick Vertical Yttria-Stabilized ZrO 2 Nanocomposite Films

DOE PAGES

Lee, Shinbuhm; Zhang, Wenrui; Khatkhatay, Fauzia; ...

2015-09-03

We design and create a unique cell geometry of templated micrometer-thick epitaxial nanocomposite films which contain ~20 nm diameter yttria-stabilized ZrO 2 (YSZ) nanocolumns, strain coupled to a SrTiO 3 matrix. We also enhanced the ionic conductivity of these nanocolumnsby over 2 orders of magnitude compared to plain YSZ films. Concomitant with the higher ionic conduction is the finding that the YSZ nanocolumns in the films have much higher crystallinity and orientation, compared to plain YSZ films. Hence, “oxygen migration highways” are formed in the desired out-of-plane direction. This improved structure is shown to originate from the epitaxial coupling ofmore » the YSZ nanocolumns to the SrTiO 3 film matrix and from nucleation of the YSZ nanocolumns on an intermediate nanocomposite base layer of highly aligned Sm-doped CeO 2 nanocolumns within the SrTiO 3 matrix. Furthermore, this intermediate layer reduces the lattice mismatch between the YSZ nanocolumns and the substrate. Vertical ionic conduction values as high as 10 –2 Ω –1 cm –1 were demonstrated at 360 °C (300 °C lower than plain YSZ films), showing the strong practical potential of these nanostructured films for use in much lower operation temperature ionic devices.« less

Structure and lifetimes in ionic liquids and their mixtures.

PubMed

Gehrke, Sascha; von Domaros, Michael; Clark, Ryan; Hollóczki, Oldamur; Brehm, Martin; Welton, Tom; Luzar, Alenka; Kirchner, Barbara

2018-01-01

With the aid of molecular dynamics simulations, we study the structure and dynamics of different ionic liquid systems, with focus on hydrogen bond, ion pair and ion cage formation. To do so, we report radial distribution functions, their number integrals, and various time-correlation functions, from which we extract well-defined lifetimes by means of the reactive flux formalism. We explore the influence of polarizable force fields vs. non-polarizable ones with downscaled charges (±0.8) for the example of 1-butyl-3-methylimidazolium bromide. Furthermore, we use 1-butyl-3-methylimidazolium trifluoromethanesulfonate to investigate the impact of temperature and mixing with water as well as with the chloride ionic liquid. Smaller coordination numbers, larger distances, and tremendously accelerated dynamics are observed when the polarizable force field is applied. The same trends are found with increasing temperature. Adding water decreases the ion-ion coordination numbers whereas the water-ion and water-water coordination is enhanced. A domain analysis reveals that the nonpolar parts of the ions are dispersed and when more water is added the water clusters increase in size. The dynamics accelerate in general upon addition of water. In the ionic liquid mixture, the coordination number around the cation changes between the two anions, but the number integrals of the cation around the anions remain constant and the dynamics slow down with increasing content of the chloride ionic liquid.

Study on Zinc Oxide-Based Electrolytes in Low-Temperature Solid Oxide Fuel Cells.

PubMed

Xia, Chen; Qiao, Zheng; Feng, Chu; Kim, Jung-Sik; Wang, Baoyuan; Zhu, Bin

2017-12-28

Semiconducting-ionic conductors have been recently described as excellent electrolyte membranes for low-temperature operation solid oxide fuel cells (LT-SOFCs). In the present work, two new functional materials based on zinc oxide (ZnO)-a legacy material in semiconductors but exceptionally novel to solid state ionics-are developed as membranes in SOFCs for the first time. The proposed ZnO and ZnO-LCP (La/Pr doped CeO₂) electrolytes are respectively sandwiched between two Ni 0.8 Co 0.15 Al 0.05 Li-oxide (NCAL) electrodes to construct fuel cell devices. The assembled ZnO fuel cell demonstrates encouraging power outputs of 158-482 mW cm -2 and high open circuit voltages (OCVs) of 1-1.06 V at 450-550 °C, while the ZnO-LCP cell delivers significantly enhanced performance with maximum power density of 864 mW cm -2 and OCV of 1.07 V at 550 °C. The conductive properties of the materials are investigated. As a consequence, the ZnO electrolyte and ZnO-LCP composite exhibit extraordinary ionic conductivities of 0.09 and 0.156 S cm -1 at 550 °C, respectively, and the proton conductive behavior of ZnO is verified. Furthermore, performance enhancement of the ZnO-LCP cell is studied by electrochemical impedance spectroscopy (EIS), which is found to be as a result of the significantly reduced grain boundary and electrode polarization resistances. These findings indicate that ZnO is a highly promising alternative semiconducting-ionic membrane to replace the electrolyte materials for advanced LT-SOFCs, which in turn provides a new strategic pathway for the future development of electrolytes.

Hierarchical micro- and mesoporous carbide-derived carbon as a high-performance electrode material in supercapacitors.

PubMed

Rose, Marcus; Korenblit, Yair; Kockrick, Emanuel; Borchardt, Lars; Oschatz, Martin; Kaskel, Stefan; Yushin, Gleb

2011-04-18

Ordered mesoporous carbide-derived carbon (OM-CDC) materials produced by nanocasting of ordered mesoporous silica templates are characterized by a bimodal pore size distribution with a high ratio of micropores. The micropores result in outstanding adsorption capacities and the well-defined mesopores facilitate enhanced kinetics in adsorption processes. Here, for the first time, a systematic study is presented, in which the effects of synthesis temperature on the electrochemical performance of these materials in supercapacitors based on a 1 M aqueous solution of sulfuric acid and 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid are reported. Cyclic voltammetry shows the specific capacitance of the OM-CDC materials exceeds 200 F g(-1) in the aqueous electrolyte and 185 F g(-1) in the ionic liquid, when measured in a symmetric configuration in voltage ranges of up to 0.6 and 2 V, respectively. The ordered mesoporous channels in the produced OM-CDC materials serve as ion-highways and allow for very fast ionic transport into the bulk of the OM-CDC particles. At room temperature the enhanced ion transport leads to 75% and 90% of the capacitance retention at current densities in excess of ∼10 A g(-1) in ionic liquid and aqueous electrolytes, respectively. The supercapacitors based on 250-300 μm OM-CDC electrodes demonstrate an operating frequency of up to 7 Hz in aqueous electrolyte. The combination of high specific capacitance and outstanding rate capabilities of the OM-CDC materials is unmatched by state-of-the art activated carbons and strictly microporous CDC materials. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Colloid release and clogging in porous media: Effects of solution ionic strength and flow velocity.

PubMed

Torkzaban, Saeed; Bradford, Scott A; Vanderzalm, Joanne L; Patterson, Bradley M; Harris, Brett; Prommer, Henning

2015-10-01

The release and retention of in-situ colloids in aquifers play an important role in the sustainable operation of managed aquifer recharge (MAR) schemes. The processes of colloid release, retention, and associated permeability changes in consolidated aquifer sediments were studied by displacing native groundwater with reverse osmosis-treated (RO) water at various flow velocities. Significant amounts of colloid release occurred when: (i) the native groundwater was displaced by RO-water with a low ionic strength (IS), and (ii) the flow velocity was increased in a stepwise manner. The amount of colloid release and associated permeability reduction upon RO-water injection depended on the initial clay content of the core. The concentration of released colloids was relatively low and the permeability reduction was negligible for the core sample with a low clay content of about 1.3%. In contrast, core samples with about 6 and 7.5% clay content exhibited: (i) close to two orders of magnitude increase in effluent colloid concentration and (ii) more than 65% permeability reduction. Incremental improvement in the core permeability was achieved when the flow velocity increased, whereas a short flow interruption provided a considerable increase in the core permeability. This dependence of colloid release and permeability changes on flow velocity and colloid concentration was consistent with colloid retention and release at pore constrictions due to the mechanism of hydrodynamic bridging. A mathematical model was formulated to describe the processes of colloid release, transport, retention at pore constrictions, and subsequent permeability changes. Our experimental and modeling results indicated that only a small fraction of the in-situ colloids was released for any given change in the IS or flow velocity. Comparison of the fitted and experimentally measured effluent colloid concentrations and associated changes in the core permeability showed good agreement, indicating that the essential physics were accurately captured by the model. Copyright © 2015 Elsevier B.V. All rights reserved.

Physicochemical hydrodynamics of porous structures in vascular plants

NASA Astrophysics Data System (ADS)

Ryu, Jeongeun; Ahn, Sungsook; Kim, Seung-Gon; Kim, Taejoo; Lee, Sang Joon

2013-11-01

Transport of sap flow through xylem conduits of vascular plants has been considered as a passive process, because the xylem conduits are regarded as inert, dead wood. However, plants can actively regulate water transport using ion-mediated response for adapting to environmental changes. In order to understand the active regulation mechanism of physicochemical hydrodynamics of porous structures in vascular plants, the effects of specific ion types and their ionic ratios on the water transport were experimentally investigated under in vivocondition. Based on the experimental results, the principle of ionic effects will be explained through in-vitro comparative experiments and theoretical considerations. This work was supported by the National Research Foundation of Korea(NRF) grant funded by the Korea government (MSIP) (No. 2008-0061991).

Application of ionic liquids in liquid chromatography and electrodriven separation.

PubMed

Huang, Yi; Yao, Shun; Song, Hang

2013-08-01

Ionic liquids (ILs) are salts in the liquid state at ambient temperature, which are nonvolatile, nonflammable with high thermal stability and dissolve easily for a wide range of inorganic and organic materials. As a kind of potential green solvent, they show high efficiency and selectivity in the field of separation research, especially in instrumental analysis. Thus far, ILs have been successfully applied by many related researchers in high-performance liquid chromatography and capillary electrophoresis as chromatographic stationary phases, mobile phase additives or electroosmotic flow modifiers. This paper provides a detailed review of these applications in the study of natural products, foods, drugs and other fine chemicals. Furthermore, the prospects of ILs in liquid chromatographic and electrodriven techniques are discussed.

Nanoporous polysulfone membranes via a degradable block copolymer precursor for redox flow batteries

DOE PAGES

Gindt, Brandon P.; Abebe, Daniel G.; Tang, Zhijiang J.; ...

2016-02-16

In this study, nanoporous polysulfone (PSU) membranes were fabricated via post-hydrolysis of polylactide (PLA) from PLA–PSU–PLA triblock copolymer membranes. The PSU scaffold was thermally crosslinked before sacrificing PLA blocks. The resulting nanopore surface was chemically modified with sulfonic acid moieties. The membranes were analyzed and evaluated as separators for vanadium redox flow batteries. Nanoporous PSU membranes prepared by this new method and further chemically modified to a slight degree exhibited unique behavior with respect to their ionic conductivity when exposed to solutions of increasing acid concentration.

Metal-air flow batteries using oxygen enriched electrolyte

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

Zheng, Jian-ping; Andrei, Petru; Shellikeri, Annadanesh

A metal air flow battery includes an electrochemical reaction unit and an oxygen exchange unit. The electrochemical reaction unit includes an anode electrode, a cathode electrode, and an ionic conductive membrane between the anode and the cathode, an anode electrolyte, and a cathode electrolyte. The oxygen exchange unit contacts the cathode electrolyte with oxygen separate from the electrochemical reaction unit. At least one pump is provided for pumping cathode electrolyte between the electrochemical reaction unit and the oxygen exchange unit. A method for producing an electrical current is also disclosed.

Metal-air flow batteries using oxygen enriched electrolyte

DOEpatents

Zheng, Jian-ping; Andrei, Petru; Shellikeri, Annadanesh; Chen, Xujie

2017-08-01

A metal air flow battery includes an electrochemical reaction unit and an oxygen exchange unit. The electrochemical reaction unit includes an anode electrode, a cathode electrode, and an ionic conductive membrane between the anode and the cathode, an anode electrolyte, and a cathode electrolyte. The oxygen exchange unit contacts the cathode electrolyte with oxygen separate from the electrochemical reaction unit. At least one pump is provided for pumping cathode electrolyte between the electrochemical reaction unit and the oxygen exchange unit. A method for producing an electrical current is also disclosed.

An Ionic Liquid Reaction and Separation Process for Production of Hydroxymethylfurfural from Sugars

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

Liu, Wei; Zheng, Feng; Li, Joanne

2014-01-01

There has been world-wide interest to making plastics out of renewable biomass feedstock for recent years. Hydroxymethylfurfural (HMF) is viewed as an attractive alternate to terephthalic acid (TPA) for production of polyesters (PET) and polyamides. Conversion of sugars into HMF has been studied in numerous publications. In this work, a complete ionic liquid reaction and separation process is presented for nearly stoichiometric conversion of fructose into HMF. Different adsorbent materials are evaluated and silicalite material is demonstrated effective for isolation of 99% pure HMF from actual ionic liquid reaction mixtures and for recovery of the un-converted sugars and reaction intermediatemore » along with the ionic liquid. Membrane-coated silicalite particles are prepared and studied for a practical adsorption process operated at low pressure drops but with separation performances comparable or better than the powder material. Complete conversion of fresh fructose feed into HMF in the recycled ionic liquid is shown under suitable reaction conditions. Stability of HMF product is characterized. A simplified process flow diagram is proposed based on these research results, and the key equipment such as reactor and adsorbent bed is sized for a plant of 200,000 ton/year of fructose processing capacity. The proposed HMF production process is much simpler than the current paraxylene (PX) manufacturing process from petroleum oil, which suggests substantial reduction to the capital cost and energy consumption be possible. At the equivalent value to PX on the molar basis, there can be a large gross margin for HMF production from fructose and/or sugars.« less

Determination of triazine herbicides in fresh vegetables by dynamic microwave-assisted extraction coupled with homogeneous ionic liquid microextraction high performance liquid chromatography.

PubMed

Wu, Lijie; Hu, Mingzhu; Li, Zhanchao; Song, Ying; Yu, Cui; Zhang, Yupu; Zhang, Hanqi; Yu, Aimin; Ma, Qiang; Wang, Ziming

2015-02-01

A novel extraction method, dynamic microwave-assisted extraction coupled with homogeneous ionic liquid microextraction, was developed for the determination of triazine herbicides, including desmetryn, terbumeton, propazine, terbuthylazine, dimethametryn, and dipropetryn in fresh vegetable samples by high performance liquid chromatography (HPLC). In the developed method, 120 μL of 1-butyl-3-methylimidazolium tetrafluoroborate ([C4MIM][BF4]) was added to 10 mL of aqueous solution containing 0.3 g of NaCl to obtained the extraction solvent. Six triazines could be extracted completely within 4 min by the present method. Then, [NH4][PF6] was added into the extract to form a water-insoluble ionic liquid [C4MIM][PF6] via a simple metathesis reaction, and the analytes were enriched into the ionic liquid phase. After centrifugation and dilution with acetonitrile, the resulting solution was analyzed directly by HPLC. The effects of some experimental parameters, including type and volume of ionic liquid, volume of extraction solvent, amount of ion-pairing agent [NH4][PF6], salt concentration, microwave power, and flow rate of extraction solvent on the extraction efficiency were investigated and optimized. Under the optimum experimental conditions, the linearity for determining the analytes was in the range of 2.50-250.00 μg kg(-1), with the correlation coefficients ranging from 0.9989 to 0.9999. When the present method was applied to the analysis of vegetable samples, satisfactory recoveries were obtained in the range of 76.8%-106.9%, and relative standard deviations were lower than 9.8%.

Aramid Nanofiber Composites for Energy Storage Applications

NASA Astrophysics Data System (ADS)

Tung, Siu on

Lithium ion batteries and non-aqueous redox flow batteries represent two of the most important energy storage technologies to efficient electric vehicles and power grid, which are essential to decreasing U.S. dependence on fossil fuels and sustainable economic growth. Many of the developmental roadblocks for these batteries are related to the separator, an electrically insulating layer between the cathode and anode. Lithium dendrite growth has limited the performance and threatened the safety of lithium ion batteries by piercing the separator and causing internal shorts. In non-aqueous redox flow batteries, active material crossover through microporous separators and the general lack of a suitable ion conducting membrane has led to low operating efficiencies and rapid capacity fade. Developing new separators for these batteries involve the combination of different and sometimes seemingly contradictory properties, such as high ionic conductivity, mechanical stability, thermal stability, chemical stability, and selective permeability. In this dissertation, I present work on composites made from Kevlar-drived aramid nanofibers (ANF) through rational design and fabrication techniques. For lithium ion batteries, a dendrite suppressing layer-by-layer composite of ANF and polyethylene oxide is present with goals of high ionic conductivity, improved safety and thermal stability. For non-aqueous redox flow batteries, a nanoporous ANF separator with surface polyelectrolyte modification is used to achieve high coulombic efficiencies and cycle life in practical flow cells. Finally, manufacturability of ANF based separators is addressed through a prototype machine for continuous ANF separator production and a novel separator coated on anode assembly. In combination, these studies serve as a foundation for addressing the challenges in separator engineering for lithium ion batteries and redox flow batteries.

Composition Pulse Time-Of-Flight Mass Flow Sensor

DOEpatents

Mosier, Bruce P.; Crocker, Robert W.; Harnett, Cindy K. l

2004-01-13

A device for measuring fluid flow rates over a wide range of flow rates (<1 nL/min to >10 .mu.L/min) and at pressures at least as great as 10,000 psi. The invention is particularly adapted for use in microfluidic systems. The device operates by producing compositional variations in the fluid, or pulses, that are subsequently detected downstream from the point of creation to derive a flow rate. Each pulse, comprising a small fluid volume, whose composition is different from the mean composition of the fluid, can be created by electrochemical means, such as by electrolysis of a solvent, electrolysis of a dissolved species, or electrodialysis of a dissolved ionic species. Measurements of the conductivity of the fluid can be used to detect the arrival time of the pulses, from which the fluid flow rate can be determined

Continuous-flow electrophoresis: Membrane-associated deviations of buffer pH and conductivity

NASA Technical Reports Server (NTRS)

Smolka, A. J. K.; Mcguire, J. K.

1978-01-01

The deviations in buffer pH and conductivity which occur near the electrode membranes in continuous-flow electrophoresis were studied in the Beckman charged particle electrophoresis system and the Hanning FF-5 preparative electrophoresis instrument. The nature of the membranes separating the electrode compartments from the electrophoresis chamber, the electric field strength, and the flow rate of electrophoresis buffer were all found to influence the formation of the pH and conductivity gradients. Variations in electrode buffer flow rate and the time of electrophoresis were less important. The results obtained supported the hypothesis that a combination of Donnan membrane effects and the differing ionic mobilities in the electrophoresis buffer was responsible for the formation of the gradients. The significance of the results for the design and stable operation of continuous-flow electrophoresis apparatus was discussed.

Self-Healing Natural Rubber with Tailorable Mechanical Properties Based on Ionic Supramolecular Hybrid Network.

PubMed

Xu, Chuanhui; Cao, Liming; Huang, Xunhui; Chen, Yukun; Lin, Baofeng; Fu, Lihua

2017-08-30

In most cases, the strength of self-healing supramolecular rubber based on noncovalent bonds is in the order of KPa, which is a challenge for their further applications. Incorporation of conventional fillers can effectively enhance the strength of rubbers, but usually accompanied by a sacrifice of self-healing capability due to that the filler system is independent of the reversible supramolecular network. In the present work, in situ reaction of methacrylic acid (MAA) and excess zinc oxide (ZnO) was realized in natural rubber (NR). Ionic cross-links in NR matrix were obtained by limiting the covalent cross-linking of NR molecules and allowing the in situ polymerization of MAA/ZnO. Because of the natural affinity between Zn 2+ ion-rich domains and ZnO, the residual nano ZnO participated in formation of a reversible ionic supramolecular hybrid network, thus having little obstructions on the reconstruction of ionic cross-links. Meanwhile, the well dispersed residual ZnO could tailor the mechanical properties of NR by changing the MAA/ZnO molar ratios. The present study thus provides a simple method to fabricate a new self-healing NR with tailorable mechanical properties that may have more potential applications.

Instrumentation for low noise nanopore-based ionic current recording under laser illumination

NASA Astrophysics Data System (ADS)

Roelen, Zachary; Bustamante, José A.; Carlsen, Autumn; Baker-Murray, Aidan; Tabard-Cossa, Vincent

2018-01-01

We describe a nanopore-based optofluidic instrument capable of performing low-noise ionic current recordings of individual biomolecules under laser illumination. In such systems, simultaneous optical measurements generally introduce significant parasitic noise in the electrical signal, which can severely reduce the instrument sensitivity, critically hindering the monitoring of single-molecule events in the ionic current traces. Here, we present design rules and describe simple adjustments to the experimental setup to mitigate the different noise sources encountered when integrating optical components to an electrical nanopore system. In particular, we address the contributions to the electrical noise spectra from illuminating the nanopore during ionic current recording and mitigate those effects through control of the illumination source and the use of a PDMS layer on the SiNx membrane. We demonstrate the effectiveness of our noise minimization strategies by showing the detection of DNA translocation events during membrane illumination with a signal-to-noise ratio of ˜10 at 10 kHz bandwidth. The instrumental guidelines for noise minimization that we report are applicable to a wide range of nanopore-based optofluidic systems and offer the possibility of enhancing the quality of synchronous optical and electrical signals obtained during single-molecule nanopore-based analysis.

Molecular dynamics study of nano-porous materials—Enhancement of mobility of Li ions in lithium disilicate

NASA Astrophysics Data System (ADS)

Habasaki, Junko

2016-11-01

In several nano-porous materials and their composites, enhancement of ionic conductivity has been reported and several mechanisms having different origins have been proposed so far. In the present work, ionic motion of Li ions in porous lithium disilicates is examined by molecular dynamics simulation in the constant volume conditions and the enhancement of the dynamics is predicted. Structures and dynamics of ions in a nano-porous system were characterized and visualized to clarify the mechanism of the enhancement. The diffusion coefficient of Li ions has shown the maximum in the medium density (and porosity) region, and near the maximum, shortening of the nearly constant loss region in the mean squared displacement of ions as well as changes of the structures of the coordination polyhedra, LiOx is found. It suggests that the loosening of the cage, which increases the jump rate of ions, is an origin of the enhancement. When larger (but still in a nano-scale) voids are formed with a further decrease of density, more tight cages are reconstructed and the diffusion coefficient decreases again. These behaviors are closely related to the residual stress in the system. It is noteworthy that the explanation is not based on the percolation of the path only or formation of boundaries, although the former also affects the dynamics.

In Situ Local Contact Angle Measurement in a CO2-Brine-Sand System Using Microfocused X-ray CT.

PubMed

Lv, Pengfei; Liu, Yu; Wang, Zhe; Liu, Shuyang; Jiang, Lanlan; Chen, Junlin; Song, Yongchen

2017-04-11

The wettability of porous media is of major interest in a broad range of natural and engineering applications. The wettability of a fluid on a solid surface is usually evaluated by the contact angle between them. While in situ local contact angle measurements are complicated by the topology of porous media, which can make it difficult to use traditional methods, recent advances in microfocused X-ray computed tomography (micro-CT) and image processing techniques have made it possible to measure contact angles on the scale of the pore sizes in such media. However, the effects of ionic strength, CO 2 phase, and flow pattern (drainage or imbibition) on pore-scale contact angle distribution are still not clear and have not been reported in detail in previous studies. In this study, we employed a micro-CT scanner for in situ investigation of local contact angles in a CO 2 -brine-sand system under various conditions. The effects of ionic strength, CO 2 phase, and flow pattern on the local contact-angle distribution were examined in detail. The results showed that the local contact angles vary over a wide range as a result of the interaction of surface contaminants, roughness, pore topology, and capillarity. The wettability of a porous surface could thus slowly weaken with increasing ionic strength, and the average contact angle could significantly increase when gaseous CO 2 (gCO 2 ) turns into supercritical CO 2 (scCO 2 ). Contact angle hysteresis also occurred between drainage and imbibition procedures, and the hysteresis was more significant under gCO 2 condition.

Alternating current (AC) iontophoretic transport across human epidermal membrane: effects of AC frequency and amplitude.

PubMed

Yan, Guang; Xu, Qingfang; Anissimov, Yuri G; Hao, Jinsong; Higuchi, William I; Li, S Kevin

2008-03-01

As a continuing effort to understand the mechanisms of alternating current (AC) transdermal iontophoresis and the iontophoretic transport pathways in the stratum corneum (SC), the objectives of the present study were to determine the interplay of AC frequency, AC voltage, and iontophoretic transport of ionic and neutral permeants across human epidermal membrane (HEM) and use AC as a means to characterize the transport pathways. Constant AC voltage iontophoresis experiments were conducted with HEM in 0.10 M tetraethyl ammonium pivalate (TEAP). AC frequencies ranging from 0.0001 to 25 Hz and AC applied voltages of 0.5 and 2.5 V were investigated. Tetraethyl ammonium (TEA) and arabinose (ARA) were the ionic and neutral model permeants, respectively. In data analysis, the logarithm of the permeability coefficients of HEM for the model permeants was plotted against the logarithm of the HEM electrical resistance for each AC condition. As expected, linear correlations between the logarithms of permeability coefficients and the logarithms of resistances of HEM were observed, and the permeability data were first normalized and then compared at the same HEM electrical resistance using these correlations. Transport enhancement of the ionic permeant was significantly larger than that of the neutral permeant during AC iontophoresis. The fluxes of the ionic permeant during AC iontophoresis of 2.5 V in the frequency range from 5 to 1,000 Hz were relatively constant and were approximately 4 times over those of passive transport. When the AC frequency decreased from 5 to 0.001 Hz at 2.5 V, flux enhancement increased to around 50 times over passive transport. While the AC frequency for achieving the full effect of iontophoretic enhancement at low AC frequency was lower than anticipated, the frequency for approaching passive diffusion transport at high frequency was higher than expected from the HEM morphology. These observations are consistent with a transport model of multiple barriers in series and the previous hypothesis that the iontophoresis pathways across HEM under AC behave like a series of reservoirs interconnected by short pore pathways.

Electromechanically generating electricity with a gapped-graphene electric generator

NASA Astrophysics Data System (ADS)

Dressen, Donald; Golovchenko, Jene

2015-03-01

We demonstrate the fabrication and operation of a gapped-graphene electric generator (G-GEG) device. The G-GEG generates electricity from the mechanical oscillation of droplets of electrolytes and ionic liquids. The spontaneous adsorption of ionic species on graphene charges opposing electric double-layer capacitors (EDLCs) on each half of the device. Modulating the area of contact between the droplet and graphene leads to adsorption/desorption of ions, effectively charging/discharging each EDLC and generating a current. The flow of current supports a potential difference across the G-GEG due to the device's internal impedance. Both the magnitude and polarity of the induced current and voltage show a strong dependence on the type of ionic species used, suggesting that certain ions interact more strongly with graphene than others. We find that a simple model circuit consisting of an AC current source in series with a resistor and a time-varying capacitor accurately predicts the device's dynamic behavior. Additionally, we discuss the effect of graphene's intrinsic quantum capacitance on the G-GEG's performance and speculate on the utility of the device in the context of energy harvesting.

Purification of inulinases by changing the ionic strength of the medium and precipitation with alcohols.

PubMed

Golunski, Simone; Silva, Marceli F; Marques, Camila T; Rosseto, Vanusa; Kaizer, Rosilene R; Mossi, Altemir J; Rigo, Diane; Dallago, Rogério M; DI Luccio, Marco; Treichel, Helen

2017-01-01

The present study evaluated the purification of inulinase by changing the ionic strength of the medium by addition of NaCl and CaCl2 followed by precipitation with n-propyl alcohol or iso-propyl alcohol. The effects of the concentration of alcohols and the rate of addition of alcohols in the crude extract on the purification yield and purification factor were evaluated. Precipitation caused an activation of enzyme and allowed purification factors up to 2.4-fold for both alcohols. The purification factor was affected positively by the modification of the ionic strength of the medium to 0.5 mol.L-1 NaCl before precipitation with the alcohol (n-propyl or iso-propyl). A purification factor of 4.8-fold and an enzyme yield of 78.1 % could be achieved by the addition of 0.5 mol.L-1 of NaCl to the crude extract, followed by the precipitation with 50 % (v/v) of n-propyl alcohol, added at a flow rate of 19.9 mL/min.

Method for eliminating gas blocking in electrokinetic pumping systems

DOEpatents

Arnold, Don W.; Paul, Phillip H.; Schoeniger, Joseph S.

2001-09-11

A method for eliminating gas bubble blockage of current flow during operation of an electrokinetic pump. By making use of the ability to modify the surface charge on the porous dielectric medium used in electrokinetic pumps, it becomes possible to place electrodes away from the pressurized region of the electrokinetic pump. While gas is still generated at the electrodes they are situated such that the generated gas can escape into a larger buffer reservoir and not into the high pressure region of the pump where the gas bubbles can interrupt current flow. Various combinations of porous dielectric materials and ionic conductors can be used to create pumps that have desirable electrical, material handling, and flow attributes.

Composite gel polymer electrolyte for lithium ion batteries

NASA Astrophysics Data System (ADS)

Naderi, Roya

Composite gel polymer electrolyte (CGPE) films, consisting of poly (vinylidene fluoride-hexafluoropropylene) (PVdF-HFP) as the membrane, DMF and PC as solvent and plasticizing agent, mixture of charge modified TiO2 and SiO 2 nano particles as ionic conductors, and LiClO4+LiPF 6 as lithium salts were fabricated. Following the work done by Li et al., CGPE was coated on an O2-plasma treated trilayer polypropylene-polyethylene-polypropylene membrane separator using solution casting technique in order to improve the adhesive properties of gel polymer electrolyte to the separator membrane and its respective ionic conductivity due to decreasing the bulk resistance. In acidic CGPE with, the mixture of acid treated TiO2 and neutral SiO2 nano particles played the role of the charge modified nano fillers with enhanced hydroxyl groups. Likely, the mixture of neutral TiO 2 nano particles with basic SiO2 prepared through the hydrolization of tetraethyl orthosilicate (TEOS) provided a more basic environment due to the residues of NH4OH (Ammonium hydroxide) catalyst. The O2 plasma treated separator was coated with the solution of PVDF-HFP: modified nano fillers: Organic solvents with the mixture ratio of 0.1:0.01:1. After the evaporation of the organic solvents, the dried coated separator was soaked in PC-LiClO4+LiPF6 in EC: DMC:DEC (4:2:4 in volume) solution (300% wt. of PVDF-HFP) to form the final CGPE. Lim et al. has reported the enhanced ionic conductivity of 9.78*10-5 Scm-1 in an acidic composite polystyrene-Al2O3 solid electrolyte system with compared to that of basic and neutral in which the ionic conductivity undergoes an ion hopping process in solid interface rather than a segmental movement of ions through the plasticized polymer chain . Half-cells with graphite anode and Li metal as reference electrode were then assembled and the electrochemical measurements and morphology examinations were successfully carried out. Half cells demonstrated a considerable change in their electrochemical performance upon the enhancement of acidic properties of the CGPE, gaining the reversible specific capacity of 314 mAh.g-1 in acidic CGPE vs. 247 mAh.g-1 in basic CGPE C/20 after 33 cycles. The CGPE exhibited submicron pore size while the ionic conductivities were in order of 10-3 and 10-5 Scm-1 with and without modified nano-fillers respectively.

Materials genomics screens for adaptive ion transport behavior by redox-switchable microporous polymer membranes in lithium–sulfur batteries

DOE PAGES

Ward, Ashleigh L.; Doris, Sean E.; Li, Longjun; ...

2017-04-27

Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance an analogous strategy for achieving adaptivemore » ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device’s active materials when they enter the membrane’s pore. This transformation has little influence on the membrane’s ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium-sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. Furthermore, the origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development« less

Materials genomics screens for adaptive ion transport behavior by redox-switchable microporous polymer membranes in lithium–sulfur batteries

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

Ward, Ashleigh L.; Doris, Sean E.; Li, Longjun

Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance an analogous strategy for achieving adaptivemore » ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device’s active materials when they enter the membrane’s pore. This transformation has little influence on the membrane’s ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium-sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. Furthermore, the origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development« less

Enhanced ionic conductivity in LAGP/LATP composite electrolyte

NASA Astrophysics Data System (ADS)

Ling, Shi-Gang; Peng, Jia-Yue; Yang, Qi; Qiu, Ji-Liang; Lu, Jia-Ze; Li, Hong

2018-03-01

Not Available Project supported by the National Key Research and Development Program of China (Grant No. 2016YFB0100100), the National Natural Science Foundation of China (Grant Nos. 52315206 and 51502334), Fund from Beijing Municipal Science & Technology Commission, China (Grant No. D171100005517001).

[Optimized isolation and purification of non-typeable Haemophilus influenzae Haps protein].

PubMed

Li, Wan-yi; Kuang, Yu; Li, Ming-yuan; Yang, Yuan; Jiang, Zhong-hua; Yao, Feng; Chen, Chang-chun

2007-12-01

To optimize the isolation and purification conditions for Hap(s) protein of non-typeable Haemophilus influenzae. Hap(s) protein was purified by ammonium sulfate precipitation, dialysis desalting and Hitrap weak cation exchange columns of CM Sepharose Fast Flow. The condition of the elution was optimized for pH and ionic strength, the absorbance at 280 nm of the elution samples were detected, and the targeted protein band in the collected samples was observed by SDS-PAGE electrophoresis. The Hitrap ion exchange column was eluted with buffer 1, which resulted in a baseline distribution of absorbance at 280 nm. Buffer 2 elution of the column resulted in the presence of peak absorbance with trails, which was identified to be constituted by some low molecular weight bands by subsequent SDS-PAGE. In serial column elution with buffer 3 with different ionic strength, a peak absorbance was observed with the ionic strength of 100 mmol/L NaCl, and SDS-PAGE confirmed that the peak was generated by the target protein. No obvious peaks or bands in SDS-PAGE occurred with the other ionic strengths. The pH of the buffer only affect the elution of the irrelevant proteins rather than the Hap(s) protein, and elution with the buffer containing 100 mmol/L NaCl can be optimal for eluting the Hap(s) protein.

Signal and Noise in FET-Nanopore Devices.

PubMed

Parkin, William M; Drndić, Marija

2018-02-23

The combination of a nanopore with a local field-effect transistor (FET-nanopore), like a nanoribbon, nanotube, or nanowire, in order to sense single molecules translocating through the pore is promising for DNA sequencing at megahertz bandwidths. Previously, it was experimentally determined that the detection mechanism was due to local potential fluctuations that arise when an analyte enters a nanopore and constricts ion flow through it, rather than the theoretically proposed mechanism of direct charge coupling between the DNA and nanowire. However, there has been little discussion on the experimentally observed detection mechanism and its relation to the operation of real devices. We model the intrinsic signal and noise in such an FET-nanopore device and compare the results to the ionic current signal. The physical dimensions of DNA molecules limit the change in gate voltage on the FET to below 40 mV. We discuss the low-frequency flicker noise (<10 kHz), medium-frequency thermal noise (<100 kHz), and high-frequency capacitive noise (>100 kHz) in FET-nanopore devices. At bandwidths dominated by thermal noise, the signal-to-noise ratio in FET-nanopore devices is lower than in the ionic current signal. At high frequencies, where noise due to parasitic capacitances in the amplifier and chip is the dominant source of noise in ionic current measurements, high-transconductance FET-nanopore devices can outperform ionic current measurements.

Simultaneous extraction and HPLC determination of 3-indole butyric acid and 3-indole acetic acid in pea plant by using ionic liquid-modified silica as sorbent.

PubMed

Sheikhian, Leila; Bina, Sedigheh

2016-01-15

In this study, ionic liquid-modified silica was used as sorbent for simultaneous extraction and preconcentration of 3-indole butyric acid and 3-indole acetic acid in pea plants. The effect of some parameters such as pH and ionic strength of sample solution, amount of sorbent, flow rate of aqueous sample solution and eluent solution, concentration of eluent solution, and temperature were studied for each hormone solution. Percent extraction of 3-indole butyric acid and 3-indole acetic acid was strongly affected by pH of aqueous sample solution. Ionic strength of aqueous phase and temperature showed no serious effects on extraction efficiency of studied plant hormones. Obtained breakthrough volume was 200mL for each of studied hormones. Preconcentration factor for spectroscopic and chromatographic determination of studied hormones was 100 and 4.0×10(3) respectively. Each solid sorbent phase was reusable for almost 10 times of extraction/stripping procedure. Relative standard deviations of extraction/stripping processes of 3-indole butyric acid and 3-indole acetic acid were 2.79% and 3.66% respectively. The calculated limit of detections for IBA and IAA were 9.1×10(-2)mgL(-1) and 1.6×10(-1)mgL(-1) respectively. Copyright © 2015 Elsevier B.V. All rights reserved.

Comparison of diffusivity data derived from electrochemical and NMR investigations of the SeCN¯/(SeCN)2/(SeCN)3¯ system in ionic liquids.

PubMed

Solangi, Amber; Bond, Alan M; Burgar, Iko; Hollenkamp, Anthony F; Horne, Michael D; Rüther, Thomas; Zhao, Chuan

2011-06-02

Electrochemical studies in room temperature ionic liquids are often hampered by their relatively high viscosity. However, in some circumstances, fast exchange between participating electroactive species has provided beneficial enhancement of charge transport. The iodide (I¯)/iodine (I(2))/triiodide (I(3)¯) redox system that introduces exchange via the I¯ + I(2) ⇌ I(3)¯ process is a well documented example because it is used as a redox mediator in dye-sensitized solar cells. To provide enhanced understanding of ion movement in RTIL media, a combined electrochemical and NMR study of diffusion in the {SeCN¯-(SeCN)(2)-(SeCN)(3)¯} system has been undertaken in a selection of commonly used RTILs. In this system, each of the Se, C and N nuclei is NMR active. The electrochemical behavior of the pure ionic liquid, [C(4)mim][SeCN], which is synthesized and characterized here for the first time, also has been investigated. Voltammetric studies, which yield readily interpreted diffusion-limited responses under steady-state conditions by means of a Random Assembly of Microdisks (RAM) microelectrode array, have been used to measure electrochemically based diffusion coefficients, while self-diffusion coefficients were measured by pulsed field gradient NMR methods. The diffusivity data, derived from concentration and field gradients respectively, are in good agreement. The NMR data reveal that exchange processes occur between selenocyanate species, but the voltammetric data show the rates of exchange are too slow to enhance charge transfer. Thus, a comparison of the iodide and selenocyanate systems is somewhat paradoxical in that while the latter give RTILs of low viscosity, sluggish exchange kinetics prevent any significant enhancement of charge transfer through direct electron exchange. In contrast, faster exchange between iodide and its oxidation products leads to substantial electron exchange but this effect does not compensate sufficiently for mass transport limitations imposed by the higher viscosity of iodide RTILs.

Ionic liquid-impregnated activated carbon for biohydrogen purification in an adsorption unit

NASA Astrophysics Data System (ADS)

Yusuf, N. Y.; Masdar, M. S.; Isahak, W. N. R. W.; Nordin, D.; Husaini, T.; Majlan, E. H.; Rejab, S. A. M.; Chew, C. L.

2017-06-01

Biological methods for hydrogen production (biohydrogen) are known as energy intensive and can be operated at ambient temperature and pressure; however, consecutive productions such as purification and separation processes still remain challenging in the industry. Various techniques are used to purify and separate hydrogen. These techniques include the use of sorbents/solvents, membranes and cryogenic distillation. In this study, carbon dioxide (CO2) was purified and separated from biohydrogen to produce high purity hydrogen gas. CO2 capture was studied using the activated carbon (AC) modified with the ionic liquid (IL) choline chloride as adsorbent. The physical and chemical properties of the adsorbents were characterized through XRD, FTIR, SEM-EDX, TGA, and BET analyses. The effects of IL loading, flow rate, temperature, and gas mixture were also investigated based on the absorption and desorption of CO2. The CO2 level in the biohydrogen composition was analyzed using a CO2 gas analyzer. The SEM image indicated that the IL homogeneously covered the AC surface. High IL dispersion inlet enhanced the capability of the adsorbent to capture CO2 gas. The thermal stability and presence of the functionalized group of ILs on AC were analyzed by TGA and FTIR techniques, respectively. CO2 adsorption experiments were conducted using a 1 L adsorber unit. Hence, adsorption technologies exhibit potential for biohydrogen purification and mainly affected by adsorbent ability and operating parameters. This research presents an improved biohydrogen technique based on adsorption technology with novel adsorbents. Two different types of commercial CO2 adsorbents were used in the experiment. Results show that the IL/AC exhibited properties suitable for CO2 adsorption. The IL/AC sample presented a high CO2 uptake of 30 wt. % IL when treated at 30 °C for 6 h under a flow rate of 1 L/min. The presence of IL increased the selectivity of CO2 removal during the adsorption process. This IL/AC can be regenerated for several times without any significant loss in the performance.