Size and Charge Dependence of Ion Transport in Human Nail Plate.

PubMed

Baswan, Sudhir M; Li, S Kevin; LaCount, Terri D; Kasting, Gerald B

2016-03-01

The electrical properties of human nail plate are poorly characterized yet are a key determinate of the potential to treat nail diseases, such as onychomycosis, using iontophoresis. To address this deficiency, molar conductivities of 17 electrolytes comprising 12 ionic species were determined in hydrated human nail plate in vitro. Cation transport numbers across the nail for 11 of these electrolytes were determined by the electromotive force method. Effective ionic mobilities and diffusivities at infinite dilution for all ionic species were determined by regression analysis. The ratios of diffusivities in nail to those in solution were found to correlate inversely with the hydrodynamic radii of the ions according to a power law relationship having an exponent of -1.75 ± 0.27, a substantially steeper size dependence than observed for similar experiments in skin. Effective diffusivities of cations in nail were 3-fold higher than those of comparably sized anions. These results reflect the strong size and charge selectivity of the nail plate for ionic conduction and diffusion. The analysis implies that efficient transungual iontophoretic delivery of ionized drugs having radii upward of 5 Å (molecular weight, ca. ≥ 340 Da) will require chemical or mechanical alteration of the nail plate. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Prediction of apatite lattice constants from their constituent elemental radii and artificial intelligence methods.

PubMed

Wu, P; Zeng, Y Z; Wang, C M

2004-03-01

Lattice constants (LCs) of all possible 96 apatite compounds, A(5)(BO(4))(3)C, constituted by A[double bond]Ba(2+), Ca(2+), Cd(2+), Pb(2+), Sr(2+), Mn(2+); B[double bond]As(5+), Cr(5+), P(5+), V(5+); and C[double bond]F(1-), Cl(1-), Br(1-), OH(1-), are predicted from their elemental ionic radii, using pattern recognition (PR) and artificial neural networks (ANN) techniques. In particular, by a PR study it is demonstrated that ionic radii predominantly govern the LCs of apatites. Furthermore, by using ANN techniques, prediction models of LCs a and c are developed, which reproduce well the measured LCs (R(2)=0.98). All the literature reported on 30 pure and 22 mixed apatite compounds are collected and used in the present work. LCs of all possible 66 new apatites (assuming they exist) are estimated by the developed ANN models. These proposed new apatites may be of interest to biomedical research especially in the design of new apatite biomaterials for bone remodeling. Similarly these techniques may also be applied in the study of interface growth behaviors involving other biomaterials.

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.

Curvature Effect on the Capacitance of Electric Double Layers at Ionic Liquid/Onion-Like Carbon Interfaces

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

Feng, Guang; Jiang, Deen; Cummings, Peter T

Recent experiments have revealed that onion-like carbons (OLCs) offer high energy density and charging/discharging rates when used as the electrodes in supercapacitors. To understand the physical origin of this phenomenon, molecular dynamics simulations were performed for a room-temperature ionic liquid near idealized spherical OLCs with radii ranging from 0.356 to 1.223 nm. We find that the surface charge density increases almost linearly with the potential applied on electric double layers (EDLs) near OLCs. This leads to a nearly flat shape of the differential capacitance versus the potential, unlike the bell or camel shape observed on planar electrodes. Moreover, our simulationsmore » reveal that the capacitance of EDLs on OLCs increases with the curvature or as the OLC size decreases, in agreement with experimental observations. The curvature effect is explained by dominance of charge overscreening over a wide potential range and increased ion density per unit area of electrode surface as the OLC becomes smaller.« less

Studies of ionic current rectification using polyethyleneimines coated glass nanopipettes.

PubMed

Liu, Shujuan; Dong, Yitong; Zhao, Wenbo; Xie, Xiang; Ji, Tianrong; Yin, Xiaohong; Liu, Yun; Liang, Zhongwei; Momotenko, Dmitry; Liang, Dehai; Girault, Hubert H; Shao, Yuanhua

2012-07-03

The modification of glass nanopipettes with polyethyleneimines (PEIs) has been successfully achieved by a relatively simple method, and the smallest tip opening is around 3 nm. Thus, in a much wider range of glass pipettes with radii from several nanometers to a few micrometers, the ion current rectification (ICR) phenomenon has been observed. The influences of different KCl concentrations, pH values, and tip radii on the ICR are investigated in detail. The sizes of PEIs have been determined by dynamic light scattering, and the effect of the sizes of PEIs for the modification, especially for a few nanometer-pipettes in radii, is also discussed. These findings systemically confirm and complement the theoretical model and provide a platform for possible selectively molecular detection and mimic biological ion channels.

Negative pressure driven phase transformation in Sr doped SmCoO₃.

PubMed

Arshad Farhan, M; Javed Akhtar, M

2010-02-24

Atomistic computer simulation techniques based on energy minimization procedures are utilized for the structural investigation of perovskite-type SmCoO(3). A reliable potential model is derived which reproduces both cubic as well as orthorhombic phases of SmCoO(3). We observe a negative chemical pressure induced structural phase transformation from distorted perovskite (orthorhombic) to perfect perovskite (cubic) due to the substitution of Sr(2 + ) at the Sm(3 + ) sites. However, external hydrostatic pressure shows isotropic compression and no pressure-induced structural transformation is observed up to 100 GPa. To maintain the electroneutrality of the system, charge compensation is through oxygen vacancies which results in the brownmillerite-type structure. A defect model is proposed, which is consistent with experimental results. The solution energies for divalent and trivalent cations are also calculated. These results show that the cations having ionic radii less than 0.75 Å will occupy the Co sites and those with ionic radii larger than 0.75 Å will substitute at the Sm sites.

Shell structures in aluminum nanocontacts at elevated temperatures

PubMed Central

2012-01-01

Aluminum nanocontact conductance histograms are studied experimentally from room temperature up to near the bulk melting point. The dominant stable configurations for this metal show a very early crossover from shell structures at low wire diameters to ionic subshell structures at larger diameters. At these larger radii, the favorable structures are temperature-independent and consistent with those expected for ionic subshell (faceted) formations in face-centered cubic geometries. When approaching the bulk melting temperature, these local stability structures become less pronounced as shown by the vanishing conductance histogram peak structure. PMID:22325572

Characterization of white poplar and eucalyptus after ionic liquid pretreatment as a function of biomass loading using X-ray diffraction and small angle neutron scattering

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

Yuan, Xueming; Duan, Yonghao; He, Lilin

A systematic study was done to understand interactions among biomass loading during ionic liquid (IL) pretreatment, biomass type and biomass structures. White poplar and eucalyptus samples were pretreated using 1-ethyl-3-methylimidazolium acetate (EmimOAc) at 110 °C for 3 h at biomass loadings of 5, 10, 15, 20 and 25 wt%. All of the samples were chemically characterized and tested for enzymatic hydrolysis. Physical structures including biomass crystallinity and porosity were measured by X-ray diffraction (XRD) and small angle neutron scattering (SANS), respectively. SANS detected pores of radii ranging from ~25 to 625 Å, enabling assessment of contributions of pores with different sizes to increased porositymore » after pretreatment. Contrasting dependences of sugar conversion on white poplar and eucalyptus as a function of biomass loading were observed and cellulose crystalline structure was found to play an important role.« less

Characterization of white poplar and eucalyptus after ionic liquid pretreatment as a function of biomass loading using X-ray diffraction and small angle neutron scattering.

PubMed

Yuan, Xueming; Duan, Yonghao; He, Lilin; Singh, Seema; Simmons, Blake; Cheng, Gang

2017-05-01

A systematic study was performed to understand interactions among biomass loading during ionic liquid (IL) pretreatment, biomass type and biomass structures. White poplar and eucalyptus samples were pretreated using 1-ethyl-3-methylimidazolium acetate (EmimOAc) at 110°C for 3h at biomass loadings of 5, 10, 15, 20 and 25wt%. All of the samples were chemically characterized and tested for enzymatic hydrolysis. Physical structures including biomass crystallinity and porosity were measured by X-ray diffraction (XRD) and small angle neutron scattering (SANS), respectively. SANS detected pores of radii ranging from ∼25 to 625Å, enabling assessment of contributions of pores with different sizes to increased porosity after pretreatment. Contrasting dependences of sugar conversion on white poplar and eucalyptus as a function of biomass loading were observed and cellulose crystalline structure was found to play an important role. Copyright © 2017 Elsevier Ltd. All rights reserved.

Long-living nanobubbles of dissolved gas in aqueous solutions of salts and erythrocyte suspensions.

PubMed

Bunkin, Nikolai F; Ninham, Barry W; Ignatiev, Pavel S; Kozlov, Valery A; Shkirin, Alexey V; Starosvetskij, Artem V

2011-03-01

Results of experiments combining laser modulation interference microscopy and Mueller matrix scatterometry show that macroscopic scatterers of light are present in liquids free of external solid impurities. Experimental data on distilled water and aqueous NaCl solutions of various concentrations as well as physiological saline solution are reported. The experimental data can be interpreted by using a model of micron-scale clusters composed of polydisperse air nanobubbles having effective radii of 70-100 nm. Their concentration increases with the growth of ionic content. We hypothesize that under certain conditions those clusters of nanobubbles can affect the erythrocyte structure. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Micro structural analysis and magnetic characteristics of rare earth substituted cobalt ferrite

NASA Astrophysics Data System (ADS)

Tapdiya, Swati; Singh, Sarika; Kulshrestha, Shobha; Shrivastava, A. K.

2018-05-01

A series of ultrafine nanoparticles of Gd3+ doped Co-ferrites CoGdxFe2-xO4 (x=0.0, 0.05 and 0.10) were prepared by wet chemical co-precipitation method using nitrates of respective metal ions. Structural and morphology studies were performed using XRD, SEM and EDAX. Indexed XRD patterns confirm the formation of cubic spinel phase. Average crystallite sizes found to be decreases with trivalent rare earth ion substitution. Lattice constant (a) and lattice strain increases with increase in Gd3+ concentration due to large ionic radii (0.94nm) of Gd3+ replacing Fe3+ (0.64nm). SEM images show the spherical morphology and uniform growth of nanoparticles. Magnetic studies show that magnetization (Ms), decreases with increase in Gd3+ concentration from 50.16 emu/gm to 31.26 emu/gm.

On the validity of Stokes-Einstein and Stokes-Einstein-Debye relations in ionic liquids and ionic-liquid mixtures.

PubMed

Köddermann, Thorsten; Ludwig, Ralf; Paschek, Dietmar

2008-09-15

Stokes-Einstein (SE) and Stokes-Einstein-Debye (SED) relations in the neat ionic liquid (IL) [C(2)mim][NTf(2)] and IL/chloroform mixtures are studied by means of molecular dynamics (MD) simulations. For this purpose, we simulate the translational diffusion coefficients of the cations and anions, the rotational correlation times of the C(2)--H bond in the cation C(2)mim(+), and the viscosities of the whole system. We find that the SE and SED relations are not valid for the pure ionic liquid, nor for IL/chloroform mixtures down to the miscibility gap (at 50 wt % IL). The deviations from both relations could be related to dynamical heterogeneities described by the non-Gaussian parameter alpha(t). If alpha(t) is close to zero, at a concentration of 1 wt % IL in chloroform, both relations become valid. Then, the effective radii and volumes calculated from the SE and SED equations can be related to the structures found in the MD simulations, such as aggregates of ion pairs. Overall, similarities are observed between the dynamical properties of supercooled water and those of ionic liquids.

Study of nanostructural organization of ionic liquids by electron paramagnetic resonance spectroscopy.

PubMed

Merunka, Dalibor; Peric, Mirna; Peric, Miroslav

2015-02-19

The X-band electron paramagnetic resonance spectroscopy (EPR) of a stable, spherical nitroxide spin probe, perdeuterated 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl (pDTO) has been used to study the nanostructural organization of a series of 1-alkyl-3-methylimidazolium tetrafluoroborate ionic liquids (ILs) with alkyl chain lengths from two to eight carbons. By employing nonlinear least-squares fitting of the EPR spectra, we have obtained values of the rotational correlation time and hyperfine coupling splitting of pDTO to high precision. The rotational correlation time of pDTO in ILs and squalane, a viscous alkane, can be fit very well to a power law functionality with a singular temperature, which often describes a number of physical quantities measured in supercooled liquids. The viscosity of the ILs and squalane, taken from the literature, can also be fit to the same power law expression, which means that the rotational correlation times and the ionic liquid viscosities have similar functional dependence on temperature. The apparent activation energy of both the rotational correlation time of pDTO and the viscous flow of ILs and squalane increases with decreasing temperature; in other words, they exhibit strong non-Arrhenius behavior. The rotational correlation time of pDTO as a function of η/T, where η is the shear viscosity and T is the temperature, is well described by the Stokes-Einstein-Debye (SED) law, while the hydrodynamic probe radii are solvent dependent and are smaller than the geometric radius of the probe. The temperature dependence of hyperfine coupling splitting is the same in all four ionic liquids. The value of the hyperfine coupling splitting starts decreasing with increasing alkyl chain length in the ionic liquids in which the number of carbons in the alkyl chain is greater than four. This decrease together with the decrease in the hydrodynamic radius of the probe indicates a possible existence of nonpolar nanodomains.

Understanding ethylammonium nitrate stabilized cytochrome c - Molecular dynamics and experimental approach

NASA Astrophysics Data System (ADS)

Jaganathan, Maheshkumar; Ramakrishnan, C.; Velmurugan, D.; Dhathathreyan, Aruna

2015-02-01

For a conceptual understanding of how an ionic liquid stabilizes a solvated protein, in this study, using new force field parameters, a molecular dynamics simulation (MDS) of the loop and helical regions of hydrated Cytochrome c (cyt c) and its interaction with the ionic liquid ethylammonium nitrate (EAN) have been studied. For a simulation trajectory of 100 ns, the changes in network of water around the protein due to EAN and subsequent reorganization of the protein have been analyzed. The radii of gyration of solvated cyt c (13.7 Å) and cyt c + EAN (13.4 Å) at the end of the trajectory are higher than the protein in its crystalline state (12.64 Å) suggesting enhanced stability of the protein due to tightly organized assembly of EAN near the solvated cyt c. This increase in stability of the protein has been verified experimentally using fluorescence, circular dichroic spectroscopy and differential scanning calorimetry. With increasing EAN in cyt c + EAN, protein conformation shows unusually high β strand population. To check whether the beta strand is an intermediate or a local minimum state, denaturation of cyt c with urea in the presence of EAN has been undertaken. Results show that EAN helps in renaturation of the protein by forming a tightly organized assembly around the protein with the beta strand state appearing as a local minimum energy state. Thus the feasibility of using ionic liquids to form networks around the protein and their possible applications in stabilization of the proteins has been demonstrated.

Role of Bi3+ substitution on structural, magnetic and optical properties of cobalt spinel ferrite

NASA Astrophysics Data System (ADS)

Anjum, Safia; Sehar, Fatima; Awan, M. S.; Zia, Rehana

2016-04-01

Bismuth-doped cobalt ferrite CoBi x Fe(2- x)O4 with x = 0, 0.1,0.2, 0.3, 0.4, 0.5 have been prepared using powder metallurgy route. The structural, morphological, elemental, magnetic and optical properties have been investigated using X-ray diffractometer, Fourier transform infrared spectroscopy, scanning electron microscope, energy dispersive X-rays, vibrating sample magnetometer and ultraviolet-visible spectrometer, respectively. X-ray diffractometer analysis confirms the formation of single-phase cubic spinel structure. As the substitution of larger ionic radii Bi3+ ions increases in cobalt ferrite which is responsible to increase the lattice parameters and decrease the crystallite size. SEM micrographs revealed the spherical shape of the particles with the nonuniform grain boundaries. The saturation magnetization decreases and bandgap energy increases as the concentration of non-magnetic Bi3+ ions increases.

High-pressure behavior of A 2 B 2 O 7 pyrochlore (A=Eu, Dy; B=Ti, Zr)

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

Rittman, Dylan R.; Turner, Katlyn M.; Park, Sulgiye

2017-01-24

In situ high-pressure X-ray diffraction and Raman spectroscopy were used to determine the influence of composition on the high-pressure behavior of A 2B 2O 7 pyrochlore (A = Eu, Dy; B = Ti, Zr) up to ~50 GPa. Based on X-ray diffraction results, all compositions transformed to the high-pressure cotunnite structure. The B-site cation species had a larger effect on the transition pressure than the A-site cation species, with the onset of the phase transformation occurring at ~41 GPa for B = Ti and ~16 GPa B = Zr. But, the A-site cation affected the kinetics of the phase transformation,more » with the transformation for compositions with the smaller ionic radii, i.e., A = Dy, proceeding faster than those with a larger ionic radii, i.e., A = Eu. Our results were consistent with previous work in which the radius-ratio of the A- and B-site cations determined the energetics of disordering, and compositions with more similarly sized A- and B-site cations had a lower defect formation energy. Raman spectra revealed differences in the degree of short-range order of the different compositions. Due to the large phase fraction of cotunnite at high pressure for B = Zr compositions, Raman modes for cotunnite could be observed, with more modes recorded for A = Eu than A = Dy. These additional modes are attributed to increased short-to-medium range ordering in the initially pyrochlore structured Eu 2Zr 2O 7 as compared with the initially defect-fluorite structured Dy 2Zr 2O 7.« less

VR-SCOSMO: A smooth conductor-like screening model with charge-dependent radii for modeling chemical reactions.

PubMed

Kuechler, Erich R; Giese, Timothy J; York, Darrin M

2016-04-28

To better represent the solvation effects observed along reaction pathways, and of ionic species in general, a charge-dependent variable-radii smooth conductor-like screening model (VR-SCOSMO) is developed. This model is implemented and parameterized with a third order density-functional tight binding quantum model, DFTB3/3OB-OPhyd, a quantum method which was developed for organic and biological compounds, utilizing a specific parameterization for phosphate hydrolysis reactions. Unlike most other applications with the DFTB3/3OB model, an auxiliary set of atomic multipoles is constructed from the underlying DFTB3 density matrix which is used to interact the solute with the solvent response surface. The resulting method is variational, produces smooth energies, and has analytic gradients. As a baseline, a conventional SCOSMO model with fixed radii is also parameterized. The SCOSMO and VR-SCOSMO models shown have comparable accuracy in reproducing neutral-molecule absolute solvation free energies; however, the VR-SCOSMO model is shown to reduce the mean unsigned errors (MUEs) of ionic compounds by half (about 2-3 kcal/mol). The VR-SCOSMO model presents similar accuracy as a charge-dependent Poisson-Boltzmann model introduced by Hou et al. [J. Chem. Theory Comput. 6, 2303 (2010)]. VR-SCOSMO is then used to examine the hydrolysis of trimethylphosphate and seven other phosphoryl transesterification reactions with different leaving groups. Two-dimensional energy landscapes are constructed for these reactions and calculated barriers are compared to those obtained from ab initio polarizable continuum calculations and experiment. Results of the VR-SCOSMO model are in good agreement in both cases, capturing the rate-limiting reaction barrier and the nature of the transition state.

The geometry of the ionic chànnel lumen formed by alpha-latroinsectotoxin from black widow spider venom in the bilayer lipid membranes.

PubMed

Shatursky, Oleg Ya; Volkova, Tatyana M; Himmelreich, Nina H; Grishin, Eugene V

2007-11-01

The dependence of single channel conductance formed by alpha-latroinsectotoxin (alpha-LIT) from black widow spider venom in the planar phospholipid membrane on the hydrodynamic radii of different nonelectrolytes allowed to determine the geometry of alpha-LIT water lumen. It was found that the cis- and trans-entrances of alpha-LIT channel had the same effective radii of 0.55-0.58 nm. Relatively small conductance of alpha-LIT channel (23.5+3.7 pS) in a symmetrical membrane bathing solution of 100 mM KCl (pH 7.4) may result from the constriction inside the channel with apparent radius of 0.37 nm located 32.5% of channel length away from the cis-entrance.

Modelos estereoquimicos na quimica de coordenacao e organometalica de lantanideos e actinideos: aplicacoes a complexos de torio (iv) com boratos de polipirazolilo (Stereochemical models in lanthanide and actinide coordination and organometallic chemistry: Applications to thorium (IV) complexes with polypyrazolylborates). Doctoral thesis

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

de Almeida, J.C.M.

1990-01-01

A detailed analysis is made of two stereochemical models commonly used in lanthanide and actinide coordination and organometallic chemistry. Li Xing-fu's Cone Packing Model and K. N. Raymond's Ionic Model. Corrections are introduced in the first model as a basis to discuss the stability and structure of known complexes. A Steric Coordination Number is defined for the second model, based on the solid angle to correlate metal-ligand distances in complexes with the ionic radii of the elements and to assign effective radii to the ligands, related to the donating power of the coordinating atoms. As an application of the models,more » the syntheses and characterizations of thorium(IV) complexes with polypyrazolylborates. (HBPz3) {sup -1} and (HB(3.5-Me2Pz)3) {sup -1}, and alkoxides, aryloxides, carboxylates, amides, thiolates, alkyls and cyclopentadienyl are described and their stabilities discussed. The geometries of the complexes in the solid and in solution are discussed and a mechanism is proposed to explain the fluxionality in solution of the complexes with (HBPz3) {sup -1}.« less

Mixing Halogens To Assemble an All-Inorganic Layered Perovskite with Warm White-Light Emission.

PubMed

Li, Xianfeng; Wang, Sasa; Zhao, Sangen; Li, Lina; Li, Yanqiang; Zhao, Bingqing; Shen, Yaoguo; Wu, Zhenyue; Shan, Pai; Luo, Junhua

2018-05-01

Most of single-component white-light-emitting materials focus on organic-inorganic hybrid perovskites, metal-organic frameworks, as well as all-inorganic semiconductors. In this work, we successfully assembled an all-inorganic layered perovskite by mixing two halogens of distinct ionic radii, namely, Rb 2 CdCl 2 I 2 , which emits "warm" white light with a high color rendering index of 88. To date, Rb 2 CdCl 2 I 2 is the first single-component white-light-emitting material with an all-inorganic layered perovskite structure. Furthermore, Rb 2 CdCl 2 I 2 is thermally highly stable up to 575 K. A series of luminescence measurements show that the white-light emission arises from the lattice deformation, which are closely related to the [CdCl 4 I 2 ] 2- octahedra with high distortion from the distinct ionic radii of Cl and I. The first-principles calculations reveal that both the Cl and I components make significant contributions to the electronic band structures of Rb 2 CdCl 2 I 2 . These findings indicate that mixing halogens is an effective route to design and synthesize new single-component white-light-emitting materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Single-Walled Carbon Nanotubes: Mimics of Biological Ion Channels.

PubMed

Amiri, Hasti; Shepard, Kenneth L; Nuckolls, Colin; Hernández Sánchez, Raúl

2017-02-08

Here we report on the ion conductance through individual, small diameter single-walled carbon nanotubes. We find that they are mimics of ion channels found in natural systems. We explore the factors governing the ion selectivity and permeation through single-walled carbon nanotubes by considering an electrostatic mechanism built around a simplified version of the Gouy-Chapman theory. We find that the single-walled carbon nanotubes preferentially transported cations and that the cation permeability is size-dependent. The ionic conductance increases as the absolute hydration enthalpy decreases for monovalent cations with similar solid-state radii, hydrated radii, and bulk mobility. Charge screening experiments using either the addition of cationic or anionic polymers, divalent metal cations, or changes in pH reveal the enormous impact of the negatively charged carboxylates at the entrance of the single-walled carbon nanotubes. These observations were modeled in the low-to-medium concentration range (0.1-2.0 M) by an electrostatic mechanism that mimics the behavior observed in many biological ion channel-forming proteins. Moreover, multi-ion conduction in the high concentration range (>2.0 M) further reinforces the similarity between single-walled carbon nanotubes and protein ion channels.

Electrochemical sensing of modified ABO3 perovskite: LaFe0.8 R0.2O3(R= Cr, Co, Al)

NASA Astrophysics Data System (ADS)

Vidya Rajan, N.; Alexander, L. K.

2017-06-01

Perovskite LaFeO3 with orthorhombic structure has been synthesized by citric acid mediated solution method. The effectiveness of ionic radii and Oxidation state of the doping material on ionic conductivity of the host matrix was evaluated by B-site (Fe) doping on LaFeO3 with Cr, Co and Al, resulting LaFe0.8 R0.2O3 (R = Cr, Co, Al). XRD with Rietveld refinement and Raman spectroscopic analysis demonstrate successful synthesis. The effect of the 20% B site doping on electrochemical activity is reported. The doped materials exhibit a decrease in sensing activity towards the non enzymatic detection of H2O2.

Distribution coefficients of rare earth ions in cubic zirconium dioxide

NASA Astrophysics Data System (ADS)

Romer, H.; Luther, K.-D.; Assmus, W.

1994-08-01

Cubic zirconium dioxide crystals are grown with the skull melting technique. The effective distribution coefficients for Nd(exp 3+), Sm(exp 3+) and Er(sup 3+) as dopants are determined experimentally as a function of the crystal growth velocity. With the Burton-Prim-Slichter theory, the equilibrium distribution coefficients can be calculated. The distribution coefficients of all other trivalent rare earth ions can be estimated by applying the correlation towards the ionic radii.

Multi-charge-state molecular dynamics and self-diffusion coefficient in the warm dense matter regime

NASA Astrophysics Data System (ADS)

Fu, Yongsheng; Hou, Yong; Kang, Dongdong; Gao, Cheng; Jin, Fengtao; Yuan, Jianmin

2018-01-01

We present a multi-ion molecular dynamics (MIMD) simulation and apply it to calculating the self-diffusion coefficients of ions with different charge-states in the warm dense matter (WDM) regime. First, the method is used for the self-consistent calculation of electron structures of different charge-state ions in the ion sphere, with the ion-sphere radii being determined by the plasma density and the ion charges. The ionic fraction is then obtained by solving the Saha equation, taking account of interactions among different charge-state ions in the system, and ion-ion pair potentials are computed using the modified Gordon-Kim method in the framework of temperature-dependent density functional theory on the basis of the electron structures. Finally, MIMD is used to calculate ionic self-diffusion coefficients from the velocity correlation function according to the Green-Kubo relation. A comparison with the results of the average-atom model shows that different statistical processes will influence the ionic diffusion coefficient in the WDM regime.

Surface structure in simple liquid metals: An orbital-free first-principles study

NASA Astrophysics Data System (ADS)

González, D. J.; González, L. E.; Stott, M. J.

2006-07-01

Molecular dynamics simulations of the liquid-vapor interfaces in simple sp-bonded liquid metals have been performed using first-principles methods. Results are presented for liquid Li, Na, K, Rb, Cs, Mg, Ba, Al, Tl, and Si at thermodynamic conditions near their respective triple points, for samples of 2000 particles in a slab geometry. The longitudinal ionic density profiles exhibit a pronounced stratification extending several atomic diameters into the bulk, which is a feature already experimentally observed in liquid K, Ga, In, Sn, and Hg. The wavelength of the ionic oscillations shows a good scaling with the radii of the associated Wigner-Seitz spheres. The structural rearrangements at the interface are analyzed in terms of the transverse pair correlation function, the coordination number, and the bond-angle distribution between nearest neighbors. The valence electronic density profile also shows (weaker) oscillations whose phase, with respect to those of the ionic profile, changes from opposite phase in the alkalis to almost in-phase for Si.

Effects of feed solution chemistry on low pressure reverse osmosis filtration of cesium and strontium.

PubMed

Ding, Shiyuan; Yang, Yu; Huang, Haiou; Liu, Hengchen; Hou, Li-an

2015-08-30

The objective of this study was to identify the removal mechanisms of radionuclides by reverse osmosis (RO) membranes under conditions relevant to full-scale water treatment. For this purpose, the effects of feed solution chemistry on the removal of Cs and Sr by a low pressure RO system was investigated by systematically varying membrane surface charge, ionic composition, and organic matter concentrations. The results showed that the effects of solution chemistry on the filtration of Cs and Sr were related to their hydrated ionic radius, resulting in the predominance of the Donnan's effect and electrostatic interactions, respectively. Consequently, the rejection of Cs increased more pronouncedly than Sr with the increases of feed concentration. Due to the Donnan's effect, different anions decreased the rejection of Cs to different extents in accordance to the order of anions' radii as SO4(2-)>Cl(-)>NO3(-)>F(-). The variations in Sr rejection were influenced by the electrostatic interactions between Sr(2+) and the membrane. In addition, humic acid (HA) lowered the rejection of Cs and caused significant membrane flux decline, but did not change the rejection of Sr. Sr also aggravated HA fouling of the membrane. Copyright © 2015 Elsevier B.V. All rights reserved.

155Gd Mössbauer Spectroscopic Study of GdM(CN)6 · 4H2O (M = CrIII, FeIII and CoIII) and KGdM(CN)6 · 3H2O (M = FeII and RuII)

NASA Astrophysics Data System (ADS)

Wang, Junhu; Abe, Junko; Kitazawa, Takafumi; Takahashi, Masashi; Takeda, Masuo

2002-07-01

155Gd Mössbauer spectroscopic studies of the title complexes have been performed. Although the 155Gd isomer shifts (d) varied scarcely, the quadrupole coupling constants (e2qQ) changed in the range 4.07-4.81 mm s-1. The e2qQ values of KGdM(CN)6 · 3H2O (M = FeII and RuII) are larger than those of GdM(CN)6 · 4H2O (M = CrIII, FeIII, and CoIII), these values increasing with increasing orthorhombic distortion of the crystal structures. A relationship between the e2qQ values and the ionic radii of the transition metal ions has also been recognized

The distribution of Sr and REE between diopside and silicate liquid. [Rare Earth Elements

NASA Technical Reports Server (NTRS)

Grutzeck, M.; Kridelbaugh, S.; Weill, D.

1974-01-01

Experimental determination of the distribution coefficients in diopside-liquid pairs for strontium and nine rare-earth elements in the system CaMgSi2O6-NaAlSi3O8-CaAl2Si2O8. In experiments in air at 1265 C it is found that most of the Sr(2+), Eu(2+), and RE(3+) ions substitute for Ca(2+) and, in addition, a coupled substitution of Al(3+) for Si(4+) occurs. All of the trace ions considered are found to be excluded from the diopside lattice relative to the liquid. In the case of the trivalent ions the exclusion is much more pronounced for La and Ce, which have ionic radii larger than that of Ca(2+) in 8-fold oxygen coordination. Divalent Sr and Eu with even larger radii are also strongly excluded.

Cation-Inhibited Transport of Graphene Oxide Nanomaterials in Saturated Porous Media: The Hofmeister Effects.

PubMed

Xia, Tianjiao; Qi, Yu; Liu, Jing; Qi, Zhichong; Chen, Wei; Wiesner, Mark R

2017-01-17

Transport of negatively charged nanoparticles in porous media is largely affected by cations. To date, little is known about how cations of the same valence may affect nanoparticle transport differently. We observed that the effects of cations on the transport of graphene oxide (GO) and sulfide-reduced GO (RGO) in saturated quartz sand obeyed the Hofmeister series; that is, transport-inhibition effects of alkali metal ions followed the order of Na + < K + < Cs + , and those of alkaline earth metal ions followed the order of Mg 2+ < Ca 2+ < Ba 2+ . With batch adsorption experiments and microscopic data, we verified that cations having large ionic radii (and thus being weakly hydrated) interacted with quartz sand and GO and RGO more strongly than did cations of small ionic radii. In particular, the monovalent Cs + and divalent Ca 2+ and Ba 2+ , which can form inner-sphere complexes, resulted in very significant deposition of GO and RGO via cation bridging between quartz sand and GO and RGO, and possibly via enhanced straining, due to the enhanced aggregation of GO and RGO from cation bridging. The existence of the Hofmeister effects was further corroborated with the interesting observation that cation bridging was more significant for RGO, which contained greater amounts of carboxyl and phenolic groups (i.e., metal-complexing moieties) than did GO. The findings further demonstrate that transport of nanoparticles is controlled by the complex interplay between nanoparticle surface functionalities and solution chemistry constituents.

Video imaging analysis of the plasma membrane permeabilizing effects of Bacillus thuringiensis insecticidal toxins in Sf9 cells.

PubMed

Villalon, M; Vachon, V; Brousseau, R; Schwartz, J L; Laprade, R

1998-01-05

The size and ionic selectivity of the pores formed by the insecticidal crystal protein Cry1C from Bacillus thuringiensis in the plasma membrane of Sf9 cells, an established cell line derived from the fall armyworm Spodoptera frugiperda, were analyzed with a video imaging technique. Changes in the permeability of the membrane were estimated from the rate of osmotic swelling of the cells. In the presence of Cry1C, which is toxic to Sf9 cells, the permeability of the cell membrane to KCl and glucose increased in a dose-dependent manner. In contrast, Cry1Aa, Cry1Ab and Cry1Ac, toxins to which Sf9 cells are not susceptible, had no detectable effect. Pores formed by Cry1C allowed the diffusion of sucrose, but were impermeable to the trisaccharide raffinose. On the basis of the hydrodynamic radii of these substances, the diameter of the pores was estimated to be 1.0-1.2 nm. In the presence of salts, the rate of swelling of cells exposed to Cry1C was about equally influenced by the size of the anion as by that of the cation, indicating that the ionic selectivity of the pores is low.

Effect of Ionic Correlations on the Surface Forces in Thin Liquid Films: Influence of Multivalent Coions and Extended Theory

PubMed Central

Danov, Krassimir D.; Basheva, Elka S.; Kralchevsky, Peter A.

2016-01-01

Experimental data for the disjoining pressure of foam films stabilized by anionic surfactant in the presence of 1:1, 1:2, 1:3, and 2:2 electrolytes: NaCl, Na2SO4, Na3Citrate, and MgSO4 are reported. The disjoining pressure predicted by the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory coincides with the experimental data in the case of a 1:1 electrolyte, but it is considerably greater than the measured pressure in all other cases. The theory is extended to account for the effects of ionic correlations and finite ionic radii. Original analytical expressions are derived for the local activity coefficient, electrostatic disjoining pressure, and asymptotic screening parameter. With the same parameter of counterion binding as for a 1:1 electrolyte, the curves predicted by the extended theory are in perfect agreement with the experimental data for 1:2 and 1:3 electrolytes. In comparison with the DLVO theory, the effect of ionic correlations leads to more effective screening of electrostatic interactions, and lower electric potential and counterion concentrations in the film’s midplane, resulting in lower disjoining pressure, as experimentally observed. The developed theory is applicable to both multivalent coions and multivalent counterions. Its application could remove some discrepancies between theory and experiment observed in studies with liquid films from electrolyte solutions. PMID:28773269

[Relation between location of elements in periodic table and affinity for the malignant tumor (author's transl)].

PubMed

Ando, A; Hisada, K; Ando, I

1977-10-01

Affinity of many inorganic compounds for the malignant tumor was examined, using the rats which were subcutaneously transplanted with Yoshida sarcoma. And the relations between the uptake rate into the malignant tumor and in vitro binding power to the protein were investigated in these compounds. In these experiments, the bipositive ions and anions had not affinity for the tumor tissue with a few exceptions. On the other hand, Hg, Au and Bi, which have strong binding power to the protein, showed high uptake rate into the malignant tumor. As Hg++, Au+ and Bi+++ are soft acids according to classification of Lewis acids, it was thought that these elements would bind strongly to soft base (R-SH, R-S-) present in the tumor tissue. In many hard acids (according to classification of Lewis acids), the uptake rate into the tumor was shown as a function of ionic potentials (valency/ionic radii) of the metal ions. It is presumed that the chemical bond of these hard acids in the tumor tissue is ionic bond to hard base (R-COO-, R-PO3(2-), R-SO3-, R-NH2).

Relation between the location of elements in the periodic table and tumor-uptake rate.

PubMed

Ando, A; Ando, I; Hiraki, T; Hisada, K

1985-01-01

The bipositive ions and anions, with few exceptions, indicated a low tumor uptake rate. On the other hand, compounds of Hg, Au and Bi, which have a strong binding power to protein, showed a high tumor uptake rate. As Hg2+, Au+ and Bi3+ are soft acids according to the classification of Lewis acids, it was thought that these ions would bind strongly to soft bases (R-SH, R-S-) present in tumor tissue. For many hard acids such as 85Sr2+, 67Ga3+, 181Hf4+, and 95Nb5+, tumor uptake rates are shown as a function of ionic potentials (valency/ionic radii) of the metal ions. Considering the present data and previously reported results, it was presumed that hard acids of trivalence, quadrivalence and pentavalence would replace calcium in the calcium salts of hard bases (calcium salts of acid mucopolysaccharides, etc.). Ionic potentials of alkaline metals and Tl were small, but the tumor-uptake rate of these elements indicated various values. As Ge and Sb are bound by covalent bonds to chloride, GeCl4 and SbCl3 behaved differently from many metallic compounds in tumor tissue.

The effect of concentration- and temperature-dependent dielectric constant on the activity coefficient of NaCl electrolyte solutions

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

Valiskó, Mónika; Boda, Dezső, E-mail: boda@almos.vein.hu

2014-06-21

Our implicit-solvent model for the estimation of the excess chemical potential (or, equivalently, the activity coefficient) of electrolytes is based on using a dielectric constant that depends on the thermodynamic state, namely, the temperature and concentration of the electrolyte, ε(c, T). As a consequence, the excess chemical potential is split into two terms corresponding to ion-ion (II) and ion-water (IW) interactions. The II term is obtained from computer simulation using the Primitive Model of electrolytes, while the IW term is estimated from the Born treatment. In our previous work [J. Vincze, M. Valiskó, and D. Boda, “The nonmonotonic concentration dependencemore » of the mean activity coefficient of electrolytes is a result of a balance between solvation and ion-ion correlations,” J. Chem. Phys. 133, 154507 (2010)], we showed that the nonmonotonic concentration dependence of the activity coefficient can be reproduced qualitatively with this II+IW model without using any adjustable parameter. The Pauling radii were used in the calculation of the II term, while experimental solvation free energies were used in the calculation of the IW term. In this work, we analyze the effect of the parameters (dielectric constant, ionic radii, solvation free energy) on the concentration and temperature dependence of the mean activity coefficient of NaCl. We conclude that the II+IW model can explain the experimental behavior using a concentration-dependent dielectric constant and that we do not need the artificial concept of “solvated ionic radius” assumed by earlier studies.« less

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

Kuechler, Erich R.; Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455-0431; Giese, Timothy J.

To better represent the solvation effects observed along reaction pathways, and of ionic species in general, a charge-dependent variable-radii smooth conductor-like screening model (VR-SCOSMO) is developed. This model is implemented and parameterized with a third order density-functional tight binding quantum model, DFTB3/3OB-OPhyd, a quantum method which was developed for organic and biological compounds, utilizing a specific parameterization for phosphate hydrolysis reactions. Unlike most other applications with the DFTB3/3OB model, an auxiliary set of atomic multipoles is constructed from the underlying DFTB3 density matrix which is used to interact the solute with the solvent response surface. The resulting method is variational,more » produces smooth energies, and has analytic gradients. As a baseline, a conventional SCOSMO model with fixed radii is also parameterized. The SCOSMO and VR-SCOSMO models shown have comparable accuracy in reproducing neutral-molecule absolute solvation free energies; however, the VR-SCOSMO model is shown to reduce the mean unsigned errors (MUEs) of ionic compounds by half (about 2-3 kcal/mol). The VR-SCOSMO model presents similar accuracy as a charge-dependent Poisson-Boltzmann model introduced by Hou et al. [J. Chem. Theory Comput. 6, 2303 (2010)]. VR-SCOSMO is then used to examine the hydrolysis of trimethylphosphate and seven other phosphoryl transesterification reactions with different leaving groups. Two-dimensional energy landscapes are constructed for these reactions and calculated barriers are compared to those obtained from ab initio polarizable continuum calculations and experiment. Results of the VR-SCOSMO model are in good agreement in both cases, capturing the rate-limiting reaction barrier and the nature of the transition state.« less

Experimental observation of charge-shift bond in fluorite CaF2.

PubMed

Stachowicz, Marcin; Malinska, Maura; Parafiniuk, Jan; Woźniak, Krzysztof

2017-08-01

On the basis of a multipole refinement of single-crystal X-ray diffraction data collected using an Ag source at 90 K to a resolution of 1.63 Å -1 , a quantitative experimental charge density distribution has been obtained for fluorite (CaF 2 ). The atoms-in-molecules integrated experimental charges for Ca 2+ and F - ions are +1.40 e and -0.70 e, respectively. The derived electron-density distribution, maximum electron-density paths, interaction lines and bond critical points along Ca 2+ ...F - and F - ...F - contacts revealed the character of these interactions. The Ca 2+ ...F - interaction is clearly a closed shell and ionic in character. However, the F - ...F - interaction has properties associated with the recently recognized type of interaction referred to as `charge-shift' bonding. This conclusion is supported by the topology of the electron localization function and analysis of the quantum theory of atoms in molecules and crystals topological parameters. The Ca 2+ ...F - bonded radii - measured as distances from the centre of the ion to the critical point - are 1.21 Å for the Ca 2+ cation and 1.15 Å for the F - anion. These values are in a good agreement with the corresponding Shannon ionic radii. The F - ...F - bond path and bond critical point is also found in the CaF 2 crystal structure. According to the quantum theory of atoms in molecules and crystals, this interaction is attractive in character. This is additionally supported by the topology of non-covalent interactions based on the reduced density gradient.

Mechanisms of combustion synthesis and magnetic response of high-surface-area hexaboride compounds.

PubMed

Kanakala, Raghunath; Escudero, Roberto; Rojas-George, Gabriel; Ramisetty, Mohan; Graeve, Olivia A

2011-04-01

We present an analysis of the combustion synthesis mechanisms for the preparation of hexaboride materials using three compounds as model systems: EuB(6), YbB(6), and YB(6). These three hexaborides were chosen because of the differences in ionic radii between Eu(3+), Yb(3+), and Y(3+), which is a factor in their stability. The powders were prepared using metal nitrates, carbohydrazide, and two different boron precursor powders. The resulting materials were analyzed by X-ray diffraction, which showed that combustion synthesis is effective for the synthesis of EuB(6), since the Eu(3+) ion has an ionic radius greater than ∼1 Å. The synthesis of YbB(6) and YB(6) is not as effective because of the small size of the Yb(3+) and Y(3+) ions, making the hexaborides of these metals less stable and resulting in the synthesis of borates due to the presence of oxygen during the combustion process. Scanning electron microscopy and dynamic light scattering of the EuB(6) powders shows that the particle size of the hexaboride product is dependent on the particle size of the boron precursor. The magnetic susceptibility of our EuB(6) powders manifests irreversible behavior at low applied fields, which disappears at higher fields. This behavior can be attributed to the increase in size and number of magnetic polarons with increasing magnetic field. © 2011 American Chemical Society

Influence of Sn4+ on Structural and DC Electrical Resistivity of Ni-Zn Ferrite Thick Films

NASA Astrophysics Data System (ADS)

Dalawai, S. P.; Shinde, T. J.; Gadkari, A. B.; Tarwal, N. L.; Jang, J. H.; Vasambekar, P. N.

2017-03-01

Among the soft ferrites, Ni-Zn ferrite is one of the most versatile ceramic materials because of their important electrical and magnetic properties. These properties were improved by substituting Sn4+ in Ni-Zn ferrites with chemical composition of Ni x Zn1+ y- x Fe2-2 y Sn y O4 ( x = 0, 0.2, 0.4, 0.6, 0.8, 1.0; y = 0.1, 0.2). To achieve homogenous ferrite powder at lower sintering temperature and smaller duration in nano-size form, the oxalate co-precipitation method was preferred as compared to other physical and chemical methods. Using this powder, ferrite thick films (FTFs) were prepared by the screen printing technique because of its low cost and easy use. To study structural behavior, the FTFs were characterized by different techniques. The x-ray diffraction and thermo-gravimetric and differential thermal analysis studies show the formation of cubic spinel structure and ferrite phase formation, respectively. There is no remarkable trend observed in lattice constants for the Sn4+ ( y = 0.1)- and Sn4+ ( y = 0.2)-substituted Ni-Zn ferrites. The bond lengths as well as ionic radii on the A-site of Ni-Zn-Sn ferrites were found to decrease with increasing nickel content. The bond length and ionic radii on the B-sites remained almost constant for Sn4+ ( y = 0.1, 0.2)-substituted Ni-Zn ferrites. The energy dispersive x-ray analysis confirms the elemental analysis of FTFs. The Fourier transform infrared spectra show two major absorption bands near 400 cm-1 and 600 cm-1 corresponding to octahedral and tetrahedral sites, respectively, which also confirms the formation of the ferrites. The field emission scanning electron microscopy images shows that the particles are highly porous in nature and located in loosely packed agglomerates. The average particle size of the FTFs lies in the range 20-60 nm. Direct current (DC) resistivity of Ni-Zn-Sn FTFs shows the semiconductor nature. The DC resistivity of Ni-Zn-Sn0.2FTFs is lower than Ni-Zn-Sn0.1 FTFs. The DC resistivity is found to decrease with the increase in Ni2+ content up to x = 0.6. It increases thereafter for a further increase in Ni2+ content up to x = 1.0, and a similar trend is observed for the variations of activation energy with Ni2+ content.

Prediction of Osmotic Pressure of Ionic Liquids Inside a Nanoslit by MD Simulation and Continuum Approach

NASA Astrophysics Data System (ADS)

Moon, Gi Jong; Yang, Yu Dong; Oh, Jung Min; Kang, In Seok

2017-11-01

Osmotic pressure plays an important role in the processes of charging and discharging of lithium batteries. In this work, osmotic pressure of the ionic liquids confined inside a nanoslit is calculated by using both MD simulation and continuum approach. In the case of MD simulation, an ionic liquid is modeled as singly charged spheres with a short-ranged repulsive Lennard-Jones potential. The radii of the spheres are 0.5nm, reflecting the symmetry of ion sizes for simplicity. The simulation box size is 11nm×11nm×7.5nm with 1050 ion pairs. The concentration of ionic liquid is about 1.922mol/L, and the total charge on an individual wall varies from +/-60e(7.944 μm/cm2) to +/-600e(79.44 μm/cm2) . In the case of continuum approach, we classify the problems according to the correlation length and steric factor, and considered the four separate cases: 1) zero correlation length and zero steric factor, 2) zero correlation length and non-zero steric factor, 3) non-zero correlation length and zero steric factor, and 4) non-zero correlation and non-zero steric factor. Better understanding of the osmotic pressure of ionic liquids confined inside a nanoslit can be achieved by comparing the results of MD simulation and continuum approach. This research was supported by the National Research Foundation of Korea (NRF) Grant funded by the Korea government (MSIP: Ministry of Science, ICT & Future Planning) (No. 2017R1D1A1B05035211).

Crystal Chemical Substitutions of YBa2Cu3O7-d to Enhance Flux Pinning (Postprint)

DTIC Science & Technology

2012-02-01

ionic radii (1.42 A for 8-fold coordination), specifically including larger RE ions La, Pr, and Nd and Ca 2+ and Sr +2. Note also that Pm is normal1y...ng is especially critical for the larger RE ions or mixtures with these ions , which pre vents partial substitution of these RE io ns for Ba ...similar 123 phase can be formed with th e composition ThSr2Cu2•7Meo 30?. This 123 p hase can be formed by substituting Sr for Ba an d a small amount of

Characterization of gold nanoparticles with different hydrophilic coatings via capillary electrophoresis and Taylor dispersion analysis. Part I: determination of the zeta potential employing a modified analytic approximation.

PubMed

Pyell, Ute; Jalil, Alaa H; Pfeiffer, Christian; Pelaz, Beatriz; Parak, Wolfgang J

2015-07-15

Taking gold nanoparticles with different hydrophilic coatings as an example, it is investigated whether capillary electrophoresis in combination with Taylor dispersion analysis allows for the precise determination of mean electrophoretic mobilities, electrophoretic mobility distributions, and zeta potentials in a matrix of exactly known composition and the calibration-free determination of number-weighted mean hydrodynamic radii. Our experimental data confirm that the calculation of the zeta potential for colloidal nanoparticles with ζ>25 mV requires to take the relaxation effect into account. Because of the requirement to avoid particle-wall interactions, a solution of disodiumtetraborate decahydrate (borax) in deionized water had been selected as suitable electrolyte. Measurements of the electrophoretic mobility at different ionic strength and application of the analytic approximation developed by Ohshima show that in the present case of a buffered solution with a weak electrolyte co-ion and a strong electrolyte counterion, the effective ionic drag coefficient should be approximated with the ionic drag coefficient of the counterion. The obtained results are in good agreement with theoretical expectations regarding the dependence of the zeta potential and the electrokinetic surface charge density on the ionic strength. We also show that Taylor dispersion analysis (besides estimation of the number-weighted mean hydrodynamic radius) provides additional information on the type and width of the number-weighted particle distribution. Copyright © 2015 Elsevier Inc. All rights reserved.

Minor elements incorporation control by ionic radius and growth rate on a stalagmite from the Chauvet Cave (SE-France)

NASA Astrophysics Data System (ADS)

Bourdin, C.; Douville, E.; Genty, D.

2009-12-01

A multi-elemental study focusing on earth-alkalis (Mg, Ca, Sr and Ba), uranium and rare-earth elements (REE) in the calcite of a stalagmite from the Chauvet Cave (SE of France) has been achieved by ICP-MS. The Chau-stm6 stalagmite which grew from 33 to 11.5 ky had already been dated and the published d13C and d18O profile is used as a paleoclimatic benchmark. Ba and Sr profiles show an abrupt concentration increase at the beginning of the last deglaciation whereas U and Mg feature a decreasing trend. REY (REE+yttrium) concentrations decrease markedly during early deglaciation (between 15 and 14.5 ky). The transition corresponds to a change from a slow to a fast growth rate. These variations can be explained by the crystallographic control of ionic radii of the minor elements: incorporation of small ions compared to Ca such as U, Mg, heavy REE are favoured during slow growth period (i.e. glacial) whereas large ions such as Ba, Sr and light REE are preferentially precipitated during fast growth period (i.e. Bolling-Allerod). This crystallographic effect seems to be dominant here because the soil above the cave is sparse. And may not have played a major role on the opposite to the water-limestone interaction.

Structure and ionic diffusion of alkaline-earth ions in mixed cation glasses A 2O–2MO–4SiO 2 with molecular dynamics simulations

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

Konstantinou, Konstantinos; Sushko, Petr; Duffy, Dorothy M.

2015-05-15

A series of mixed cation silicate glasses of the composition A2O – 2MO – 4SiO2, with A=Li,Na,K and M=Ca,Sr,Ba has been investigated by means of molecular dynamics simulations in order to understand the effect of the nature of the cations on the mobility of the alkaline-earth ions within the glass network. The size of the alkaline-earth cation was found to affect the inter-atomic distances, the coordination number distributions and the bond angle distributions , whereas the medium-range order was almost unaffected by the type of the cation. All the alkaline-earth cations contribute to lower vibrational frequencies but it is observedmore » that that there is a shift to smaller frequencies and the vibrational density of states distribution gets narrower as the size of the alkaline-earth increases. The results from our modeling for the ionic diffusion of the alkaline-earth cations are in a qualitative agreement with the experimental observations in that there is a distinct correlation between the activation energy for diffusion of alkaline earth-ions and the cation radii ratio. An asymmetrical linear behavior in the diffusion activation energy with increasing size difference is observed. The results can be described on the basis of a theoretical model that relates the diffusion activation energy to the electrostatic interactions of the cations with the oxygens and the elastic deformation of the silicate network.« less

Structure and Magnetic Properties of Rare Earth Doped Transparent Alumina

NASA Astrophysics Data System (ADS)

Limmer, Krista; Neupane, Mahesh; Chantawansri, Tanya

Recent experimental studies of rare earth (RE) doped alumina suggest that the RE induced novel phase-dependent structural and magnetic properties. Motivated by these efforts, the effects of RE doping of alpha and theta alumina on the local structure, magnetic properties, and phase stability have been examined in this first principles study. Although a direct correlation between the magnetic field dependent materials properties observed experimentally and calculated from first principles is not feasible because of the applied field and the scale, the internal magnetic properties and other properties of the doped materials are evaluated. The RE dopants are shown to increase the substitutional site volume as well as increasingly distort the site structure as a function of ionic radii. Doping both the alpha (stable) and theta (metastable) phases enhanced the relative stability of the theta phase. The energetic doping cost and internal magnetic moment were shown to be a function of the electronic configuration of the RE-dopant, with magnetic moment directly proportional to the number of unpaired electrons and doping cost being inversely related.

Al3+ ions dependent structural and magnetic properties of Co-Ni nano-alloys.

PubMed

Kadam, R H; Alone, Suresh T; Gaikwad, Anil S; Birajdar, A P; Shirsath, Sagar E

2014-06-01

Ferrite samples with a chemical formula Co0.5Ni0.5Al(x)Fe(2-x)O4 (where x = 0.0, 0.25, 0.5, 0.75 and 1.0) were synthesized by sol-gel auto-combustion method. The synthesized samples were annealed at 600 degrees C for 4 h. An analysis of X-ray diffraction (XRD) patterns reveals the formation of single phase cubic spinel structure. The lattice parameter decreased linearly with the increasing Al content x. Nano size of the powders were confirmed by the transmission electron micrographs (TEM). Particle size, bulk density decreased whereas specific surface area and porosity of the samples increased with the Al substitution. Cation distribution of constituent ions shows linear dependence of Al substitution. Based on the cation distribution obtained from XRD data, structural parameters such as lattice parameters, ionic radii of available sites and the oxygen parameter 'u' is calculated. Saturation magnetization (M(s)), magneton number (n(B)) and coercivity (H(c)) decreased with the Al substitution. Possible explanation for the observed structural and magnetic behavior with various Al content are discussed.

Separation of both fibrous and globular proteins on the basis of molecular weight using high-performance size exclusion chromatography.

PubMed

Barden, J A

1983-11-01

A high-performance size exclusion liquid chromatographic system has been used to separate proteins with different shapes solely on the basis of their molecular weights. After the effects of ionic and hydrophobic interactions with the stationary phase have been overcome, protein elution is normally governed by their effective size in solution. Conditions are described under which proteins, with isoelectric points within the normal operating pH range of the columns, are eluted independent of their Stokes' radii. Even fibrous proteins with axial ratios of 50 elute according to their known molecular weights over the range 2000-2,000,000.

Doping effect in layer structured SrBi2Nb2O9 ferroelectrics

NASA Astrophysics Data System (ADS)

Wu, Yun; Forbess, Mike J.; Seraji, Seana; Limmer, Steven J.; Chou, Tammy P.; Nguyen, Carolyn; Cao, Guozhong

2001-11-01

This article reports a systematic study of doping effects on the crystal structure, microstructure, dielectric, and electrical properties of layer-structured strontium bismuth niobate, SrBi2Nb2O9 (SBN), ferroelectrics. Substitution in both the A site (Sr2+ by Ca2+ and Ba2+) and B site (Nb5+ by V5+) up to 30 at % were studied. It was found that crystal lattice constant, dielectric, and electrical properties of SBN ferroelectrics varied appreciably with the type and amount of dopants. The relationships among the ionic radii, structural constraint imposed by [Bi2O2]2+ interlayers, and properties were discussed.

Lanthanide contraction effect on crystal structures, magnetic, and dielectric properties in ordered double perovskites LnPbCoSbO{sub 6} (Ln = La, Pr, Nd)

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

Han, L.; Yao, C. G.; Meng, J. L.

The crystal structures, magnetic, and dielectric properties for the ordered double perovskites LnPbCoSbO{sub 6} (Ln = La, Pr, Nd) have been investigated. The crystal structure has been solved by Rietveld refinements of X-ray diffraction data in the monoclinic space group P2{sub 1}/n (No. 14). The Co{sup 2+} and Sb{sup 5+} ions are almost fully ordered over the B-site, and the octahedral framework displays significant tilting distortion according to the Glazer's tilt system a{sup –}a{sup –}c{sup +}. As the result of lanthanide contraction from La{sup 3+} to Nd{sup 3+}, the B-site sublattice distortions become stronger accompanying with the reduction of themore » tolerance factor and coordination number. The magnetization measurements show an antiferromagnetic ordering with large effective magnetic moments (μ{sub eff}) suggesting that the orbital component is significant. The maximum values of isothermal magnetization increase with the decrease in radii of rare earth ions, which is attributed to the weakening of antiferromagnetic interaction via Co{sup 2+}–O–Sb{sup 5+}–O–Co{sup 2+} paths. The dielectric constants present frequency dependence and monotonically decrease with the ionic radii reduction from La{sup 3+} to Nd{sup 3+} due to the suppression of electron transfer. These results indicate that the magnetic and dielectric properties can be tuned by controlling the degree of lattice distortion, which is realized by introducing different Ln{sup 3+} ions at the A-site.« less

[Characteristics of the aggregative state of the substrate in the reaction of 5-lipoxygenase oxidation of linoleic acid].

PubMed

Butovich, I A; Kharchenko, O V; Paboka, Iu N; Kazachkov, M G

2001-01-01

5-lipoxygenase (EC 1.13.11.12) oxidizes polyunsaturated fatty acids by molecular oxygen. The enzyme acts in close contact with the cell membranes, which main components are ionic and non-ionic lipids. In order to investigate the kinetic parameters of 5-lipoxygenase reaction in vitro, extremely hydrophobic fatty acid substrate (linoleic acid) should be solubilized in the reaction mixture. We used Lubrol PX ("Sigma" Chem. Co), as a non-ionic detergent consisted of oligoethylene glycol and fatty alcohol. Linoleic acid and Lubrol PX formed mixed micelles thus solubilizing the fatty acid substrate in a buffer with appropriate pH. We have studied the sizes and shapes of mixed micelles Lubrol PX/linoleic acid (aggregates type 1) and Lubrol PX/linoleic acid/SDS (aggregates type 2; SDS was an effective activator of potato tuber 5-lipoxygenase) by means of gel-filtration and laser light scattering techniques. The parameters under investigation were molecular weights, Stocks radii and shapes of the mixed micelles. The average molecular weights and Stocks radii of the mixed micelles type 1 determined by mean of gel-filtration on Sephadex G-200 were 95,142 +/- 5184 Da and 3.45 +/- 0.11 nm, respectively. The same parameters for the mixed micelles type 2 were 73,694 +/- 893 Da and 3.02 +/- 0.02 nm, respectively. The strong similarity in physicochemical parameters for both types of mixed micelles indicated that SDS did not influence the size and shape of mixed micelles of Lubrol PX and linoleic acid. The activatory action of SDS on potato tuber lipoxygenase may be a result of electrostatic effect or direct participation of SDS in enzymatic catalysis. The laser light scattering technique allowed to determine two main fraction of particles in type 1 system with hydrodynamic diameters 2.6 and 5.7 nm and relative contribution to light scattering 13 and 87%, respectively. The particles with d = 5.7 nm were interpreted as the mixed micelles. The particles with d = 2.6 nm were interpreted as isolated molecules of Lubrol PX, linoleic acid and (or) their premicellar aggregates. The data obtained are to be used in creation of reliable physical and mathematical models of 5-lipoxygenase.

Structural analysis of emerging ferrite: Doped nickel zinc ferrite

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

Kumar, Rajinder; Kumar, Hitanshu; Singh, Ragini Raj

2015-08-28

Ni{sub 0.6-x}Zn{sub 0.4}Co{sub x}Fe{sub 2}O{sub 4} (x = 0, 0.033, 0.264) nanoparticles were synthesized by sol-gel method and annealed at 900°C. Structural properties of all prepared samples were examined with X-ray diffraction (XRD). The partial formation of hematite (α-Fe{sub 2}O{sub 3}) secondary phase with spinel phase cubic structure of undoped and cobalt doped nickel zinc ferrite was found by XRD peaks. The variation in crystallite size and other structural parameters with cobalt doping has been calculated for most prominent peak (113) of XRD and has been explained on the basis of cations ionic radii difference.

Rietveld refinement and FTIR analysis of bulk ceramic Co3-xMnxO4 compositions

NASA Astrophysics Data System (ADS)

Meena, P. L.; Kumar, Ravi; Sreenivas, K.

2013-02-01

Co3-xMnxO4 (x = 0.0, 0.6, 1.2) prepared by solid state reaction method and characterized by powder X-ray diffraction (XRD) and Fourier transform infrared (FTIR). Lattice parameters (a), oxygen parameter (u), and ionic radii of cations have been determined through Rietveld analysis. Both a and u parameters are related to expansion of octahedral site as Mn content in Co3O4. Analysis of XRD data show that Mn (x ≤ 1.2) is accommodated at the octahedral site, while retaining the cubic spinel structure. FTIR results also confirm the same and signify strong interactions due to overlapping of Co and Mn octahedra.

Boson peak of alkali and alkaline earth silicate glasses: influence of the nature and size of the network-modifying cation.

PubMed

Richet, Nicolas F

2012-01-21

The influence of the size of the alkaline earth cation on the boson peak of binary metasilicate glasses, MSiO(3) (M = Mg, Ca, Sr, Ba), has been investigated from vibrational densities of states determined by inversion of low-temperature heat capacities. As given both by C(p)/T(3) and g(ω)/ω(2), the intensity of the boson peak undergoes a 7-fold increase from Mg to Ba, whereas its temperature and frequency correlatively decrease from 18 to 10 K and from 100 to 20 cm(-1), respectively. The boson peak results from a combination of librations of SiO(4) tetrahedra and localized vibrations of network-modifying cations with non-bridging oxygens whose contribution increases markedly with the ionic radius of the alkaline earth. As a function of ionic radii, the intensity for Sr and Ba varies in the same way as previously found for alkali metasilicate glasses. The localized vibrations involving alkali and heavy alkaline earth cations appear to be insensitive to the overall glass structure. Although the new data are coherent with an almost linear relationship between the temperature of the boson peak and transverse sound velocity, pure SiO(2) and SiO(2)-rich glasses make marked exceptions to this trend because of the weak transverse character of SiO(4) librations. Finally, the universality of the calorimetric boson peak is again borne out because all data for silicate glasses collapse on the same master curve when plotted in a reduced form (C(P)∕/T(3))/(C(P)/T(3))(b) vs. T/T(b). © 2012 American Institute of Physics

Systematic study of charged-pion and kaon femtoscopy in Au + Au collisions at √{sNN}=200 GeV

NASA Astrophysics Data System (ADS)

Adare, A.; Afanasiev, S.; Aidala, C.; Ajitanand, N. N.; Akiba, Y.; Al-Bataineh, H.; Alexander, J.; Alfred, M.; Aoki, K.; Apadula, N.; Aramaki, Y.; Asano, H.; Atomssa, E. T.; Averbeck, R.; Awes, T. C.; Azmoun, B.; Babintsev, V.; Bai, M.; Baksay, G.; Baksay, L.; Bandara, N. S.; Bannier, B.; Barish, K. N.; Bassalleck, B.; Basye, A. T.; Bathe, S.; Baublis, V.; Baumann, C.; Bazilevsky, A.; Beaumier, M.; Beckman, S.; Belikov, S.; Belmont, R.; Bennett, R.; Berdnikov, A.; Berdnikov, Y.; Bickley, A. A.; Blau, D. S.; Bok, J. S.; Boyle, K.; Brooks, M. L.; Bryslawskyj, J.; Buesching, H.; Bumazhnov, V.; Bunce, G.; Butsyk, S.; Camacho, C. M.; Campbell, S.; Chen, C.-H.; Chi, C. Y.; Chiu, M.; Choi, I. J.; Choi, J. B.; Choudhury, R. K.; Christiansen, P.; Chujo, T.; Chung, P.; Chvala, O.; Cianciolo, V.; Citron, Z.; Cole, B. A.; Connors, M.; Constantin, P.; Csanád, M.; Csörgő, T.; Dahms, T.; Dairaku, S.; Danchev, I.; Danley, D.; Das, K.; Datta, A.; Daugherity, M. S.; David, G.; Deblasio, K.; Dehmelt, K.; Denisov, A.; Deshpande, A.; Desmond, E. J.; Dietzsch, O.; Dion, A.; Diss, P. B.; Do, J. H.; Donadelli, M.; Drapier, O.; Drees, A.; Drees, K. A.; Durham, J. M.; Durum, A.; Dutta, D.; Edwards, S.; Efremenko, Y. V.; Ellinghaus, F.; Engelmore, T.; Enokizono, A.; En'yo, H.; Esumi, S.; Fadem, B.; Feege, N.; Fields, D. E.; Finger, M.; Finger, M.; Fleuret, F.; Fokin, S. L.; Fraenkel, Z.; Frantz, J. E.; Franz, A.; Frawley, A. D.; Fujiwara, K.; Fukao, Y.; Fusayasu, T.; Gal, C.; Gallus, P.; Garg, P.; Garishvili, I.; Ge, H.; Giordano, F.; Glenn, A.; Gong, H.; Gonin, M.; Goto, Y.; Granier de Cassagnac, R.; Grau, N.; Greene, S. V.; Grosse Perdekamp, M.; Gunji, T.; Gustafsson, H.-Å.; Hachiya, T.; Haggerty, J. S.; Hahn, K. I.; Hamagaki, H.; Hamblen, J.; Hamilton, H. F.; Han, R.; Han, S. Y.; Hanks, J.; Hartouni, E. P.; Hasegawa, S.; Haseler, T. O. S.; Hashimoto, K.; Haslum, E.; Hayano, R.; He, X.; Heffner, M.; Hemmick, T. K.; Hester, T.; Hill, J. C.; Hohlmann, M.; Hollis, R. S.; Holzmann, W.; Homma, K.; Hong, B.; Horaguchi, T.; Hornback, D.; Hoshino, T.; Hotvedt, N.; Huang, J.; Huang, S.; Ichihara, T.; Ichimiya, R.; Ide, J.; Ikeda, Y.; Imai, K.; Inaba, M.; Iordanova, A.; Isenhower, D.; Ishihara, M.; Isobe, T.; Issah, M.; Isupov, A.; Ivanishchev, D.; Jacak, B. V.; Jezghani, M.; Jia, J.; Jiang, X.; Jin, J.; Johnson, B. M.; Joo, K. S.; Jouan, D.; Jumper, D. S.; Kajihara, F.; Kametani, S.; Kamihara, N.; Kamin, J.; Kanda, S.; Kang, J. H.; Kapustinsky, J.; Karatsu, K.; Kawall, D.; Kawashima, M.; Kazantsev, A. V.; Kempel, T.; Key, J. A.; Khachatryan, V.; Khanzadeev, A.; Kijima, K. M.; Kim, B. I.; Kim, C.; Kim, D. H.; Kim, D. J.; Kim, E.; Kim, E.-J.; Kim, G. W.; Kim, M.; Kim, S. H.; Kim, Y.-J.; Kimelman, B.; Kinney, E.; Kiriluk, K.; Kiss, Á.; Kistenev, E.; Kitamura, R.; Klatsky, J.; Kleinjan, D.; Kline, P.; Koblesky, T.; Kochenda, L.; Komkov, B.; Konno, M.; Koster, J.; Kotchetkov, D.; Kotov, D.; Kozlov, A.; Král, A.; Kravitz, A.; Kunde, G. J.; Kurita, K.; Kurosawa, M.; Kwon, Y.; Kyle, G. S.; Lacey, R.; Lai, Y. S.; Lajoie, J. G.; Lebedev, A.; Lee, D. M.; Lee, J.; Lee, K.; Lee, K. B.; Lee, K. S.; Lee, S.; Lee, S. H.; Leitch, M. J.; Leite, M. A. L.; Leitner, E.; Lenzi, B.; Li, X.; Liebing, P.; Lim, S. H.; Linden Levy, L. A.; Liška, T.; Litvinenko, A.; Liu, H.; Liu, M. X.; Love, B.; Luechtenborg, R.; Lynch, D.; Maguire, C. F.; Makdisi, Y. I.; Makek, M.; Malakhov, A.; Malik, M. D.; Manion, A.; Manko, V. I.; Mannel, E.; Mao, Y.; Masui, H.; Matathias, F.; McCumber, M.; McGaughey, P. L.; McGlinchey, D.; McKinney, C.; Means, N.; Meles, A.; Mendoza, M.; Meredith, B.; Miake, Y.; Mignerey, A. C.; Mikeš, P.; Miki, K.; Milov, A.; Mishra, D. K.; Mishra, M.; Mitchell, J. T.; Miyasaka, S.; Mizuno, S.; Mohanty, A. K.; Montuenga, P.; Moon, T.; Morino, Y.; Morreale, A.; Morrison, D. P.; Moukhanova, T. V.; Murakami, T.; Murata, J.; Mwai, A.; Nagamiya, S.; Nagashima, K.; Nagle, J. L.; Naglis, M.; Nagy, M. I.; Nakagawa, I.; Nakagomi, H.; Nakamiya, Y.; Nakamura, T.; Nakano, K.; Nattrass, C.; Netrakanti, P. K.; Newby, J.; Nguyen, M.; Niida, T.; Nishimura, S.; Nouicer, R.; Novak, T.; Novitzky, N.; Nyanin, A. S.; O'Brien, E.; Oda, S. X.; Ogilvie, C. A.; Oka, M.; Okada, K.; Onuki, Y.; Orjuela Koop, J. D.; Osborn, J. D.; Oskarsson, A.; Ouchida, M.; Ozawa, K.; Pak, R.; Pantuev, V.; Papavassiliou, V.; Park, I. H.; Park, J.; Park, J. S.; Park, S.; Park, S. K.; Park, W. J.; Pate, S. F.; Patel, M.; Pei, H.; Peng, J.-C.; Pereira, H.; Perepelitsa, D. V.; Perera, G. D. N.; Peresedov, V.; Peressounko, D. Yu.; Perry, J.; Petti, R.; Pinkenburg, C.; Pinson, R.; Pisani, R. P.; Proissl, M.; Purschke, M. L.; Purwar, A. K.; Qu, H.; Rak, J.; Rakotozafindrabe, A.; Ramson, B. J.; Ravinovich, I.; Read, K. F.; Reygers, K.; Reynolds, D.; Riabov, V.; Riabov, Y.; Richardson, E.; Rinn, T.; Roach, D.; Roche, G.; Rolnick, S. D.; Rosati, M.; Rosen, C. A.; Rosendahl, S. S. E.; Rosnet, P.; Rowan, Z.; Rubin, J. G.; Rukoyatkin, P.; Ružička, P.; Sahlmueller, B.; Saito, N.; Sakaguchi, T.; Sakashita, K.; Sako, H.; Samsonov, V.; Sano, S.; Sarsour, M.; Sato, S.; Sato, T.; Sawada, S.; Schaefer, B.; Schmoll, B. K.; Sedgwick, K.; Seele, J.; Seidl, R.; Semenov, A. Yu.; Sen, A.; Seto, R.; Sett, P.; Sexton, A.; Sharma, D.; Shein, I.; Shibata, T.-A.; Shigaki, K.; Shimomura, M.; Shoji, K.; Shukla, P.; Sickles, A.; Silva, C. L.; Silvermyr, D.; Silvestre, C.; Sim, K. S.; Singh, B. K.; Singh, C. P.; Singh, V.; Slunečka, M.; Snowball, M.; Soltz, R. A.; Sondheim, W. E.; Sorensen, S. P.; Sourikova, I. V.; Sparks, N. A.; Stankus, P. W.; Stenlund, E.; Stepanov, M.; Stoll, S. P.; Sugitate, T.; Sukhanov, A.; Sumita, T.; Sun, J.; Sziklai, J.; Takagui, E. M.; Taketani, A.; Tanabe, R.; Tanaka, Y.; Tanida, K.; Tannenbaum, M. J.; Tarafdar, S.; Taranenko, A.; Tarján, P.; Themann, H.; Thomas, T. L.; Tieulent, R.; Timilsina, A.; Todoroki, T.; Togawa, M.; Toia, A.; Tomášek, L.; Tomášek, M.; Torii, H.; Towell, C. L.; Towell, R.; Towell, R. S.; Tserruya, I.; Tsuchimoto, Y.; Vale, C.; Valle, H.; van Hecke, H. W.; Vazquez-Zambrano, E.; Veicht, A.; Velkovska, J.; Vértesi, R.; Vinogradov, A. A.; Virius, M.; Vrba, V.; Vznuzdaev, E.; Wang, X. R.; Watanabe, D.; Watanabe, K.; Watanabe, Y.; Watanabe, Y. S.; Wei, F.; Wei, R.; Wessels, J.; White, A. S.; White, S. N.; Winter, D.; Wood, J. P.; Woody, C. L.; Wright, R. M.; Wysocki, M.; Xia, B.; Xie, W.; Xue, L.; Yalcin, S.; Yamaguchi, Y. L.; Yamaura, K.; Yang, R.; Yanovich, A.; Ying, J.; Yokkaichi, S.; Yoo, J. H.; Yoon, I.; You, Z.; Young, G. R.; Younus, I.; Yu, H.; Yushmanov, I. E.; Zajc, W. A.; Zelenski, A.; Zhang, C.; Zhou, S.; Zolin, L.; Zou, L.; Phenix Collaboration

2015-09-01

We present a systematic study of charged-pion and kaon interferometry in Au +Au collisions at √{s NN}=200 GeV. The kaon mean source radii are found to be larger than pion radii in the outward and longitudinal directions for the same transverse mass; this difference increases for more central collisions. The azimuthal-angle dependence of the radii was measured with respect to the second-order event plane and similar oscillations of the source radii were found for pions and kaons. Hydrodynamic models qualitatively describe the similar oscillations of the mean source radii for pions and kaons, but they do not fully describe the transverse-mass dependence of the oscillations.

Sorption of metals on humic acid

NASA Astrophysics Data System (ADS)

Kerndorff, H.; Schnitzer, M.

1980-11-01

The sorption on humic acid (HA) of metals from an aqueous solution containing Hg(II). Fe(III), Pb, Cu, Al, Ni, Cr(III), Cd, Zn, Co and Mn, was investigated with special emphasis on effects of pH, metal concentration and HA concentration. The sorption efficiency tended to increase with rise in pH, decrease in metal concentration and increase in HA concentration of the equilibrating solution. At pH 2.4. the order of sorption was: Hg≫ Fe≫ Pb≫ CuAl ≫ Ni ≫ CrZnCdCoMn. At pH 3.7. the order was: Hg and Fe were always most readily removed, while Co and Mn were sorbed least readily. There were indications of competition for active sites (CO 2H and phenolic OH groups) on the HA between the different metals. We were unable to find correlations between the affinities of the eleven metals to sorb on HA and their atomic weights, atomic numbers, valencies, and crystal and hydrated ionic radii. The sorption of the eleven metals on the HA could be described by the equation Y = 100/[1 + exp - (A + BX)], where Y = % metal removed by HA; X = mgHA; and A and B are empirical constants.

Investigations on structural, vibrational and dielectric properties of nanosized Cu doped Mg-Zn ferrites

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

Yadav, Anand; Department of Physics, MEDICAPS Institute of Science and Technology, Pithampur 453331; Rajpoot, Rambabu

2016-05-23

Transition metal Cu{sup 2+} doped Mg-Zn ferrite [Mg{sub 0.5}Zn{sub 0.5-x}Cu{sub x}Fe{sub 2}O{sub 4} (0.0 ≤ x ≤ 0.5)] were prepared by sol gel auto combustion (SGAC) method to probe the structural, vibrational and electrical properties. X-ray diffraction (XRD) pattern reveals a single-phase cubic spinel structure without the presence of any secondary phase corresponding to other structure. The average particle size of the parent Mg{sub 0.5}Zn{sub 0.5}Fe{sub 2}O{sub 4} is found to be ~29.8 nm and is found to increase with Cu{sup 2+} doping. Progressive reduction in lattice parameter of Mg{sub 0.5}Zn{sub 0.5}Fe{sub 2}O{sub 4} has been observed due to difference inmore » ionic radii of cations with improved Cu doping. Spinel cubic structure is further confirmed by Raman spectroscopy. Small shift in Raman modes towards higher wave number has been observed in doped Mg-Zn ferrites. The permittivity and dielectric loss decreases at lower doping and increases at higher order doping of Cu{sup 2+}.« less

Tungsten doped titanium dioxide nanowires for high efficiency dye-sensitized solar cells.

PubMed

Archana, P S; Gupta, Arunava; Yusoff, Mashitah M; Jose, Rajan

2014-04-28

Metal oxide semiconductors offering simultaneously high specific surface area and high electron mobility are actively sought for fabricating high performance nanoelectronic devices. The present study deals with synthesis of tungsten doped TiO2 (W:TiO2) nanowires (diameter ∼50 nm) by electrospinning and evaluation of their performance in dye-sensitized solar cells (DSCs). Similarity in the ionic radii between W(6+) and Ti(4+) and availability of two free electrons per dopant are the rationale for the present study. Materials were characterized by X-ray diffraction, scanning and transmission electron microscopy, X-ray fluorescence measurements, and absorption spectroscopy. Nanowires containing 2 at% W:TiO2 gave 90% higher short circuit current density (JSC) (∼15.39 mA cm(-2)) in DSCs with a nominal increase in the open circuit voltage compared with that of the undoped analogue (JSC ∼8.1 mA cm(-2)). The results are validated by multiple techniques employing absorption spectroscopy, electrochemical impedance spectroscopy and open circuit voltage decay. The above studies show that the observed increments resulted from increased dye-loading, electron density, and electron lifetime in tungsten doped samples.

Single-crystal diffraction at megabar conditions by synchrotron radiation

NASA Astrophysics Data System (ADS)

Merlini, Marco; Hanfland, Michael

2013-08-01

Crystal structure determination at extreme pressures is currently possible at synchrotron beamlines optimized for such a purpose. We report the description of the experimental setup available at European Synchrotron Radiation Facility ID09 beamline (Grenoble, France) and, with two examples, we illustrate the state-of-the-art experiments currently performed at third-generation synchrotrons. The first example concerns the determination of the equation of state and the structural behavior of low-spin Fe-bearing siderite in the megabar pressure range. Siderite, in fact, undergoes a first-order isosymmetric transition at 45 GPa, and, above this pressure, it features Fe2+ in electronic low-spin configuration. The local configuration of Fe coordination polyhedra, determined by structural refinements, significantly deviates from a regular octahedron. Nevertheless, no further structural transition is detected up to the maximum pressure reached in our experiments, 135 GPa. The analysis of the Fe-O bond length extrapolated to ambient pressure, which indicates that the difference in ionic radii between the high- and the low-spin state of Fe2+ is 0.172 Å, in excellent agreement with the tabulated data by Shannon and Prewitt [Effective ionic radii in oxides and fluorides. Acta Crystallogr. 1969;B25:925-946]. The second example concerns the determination and refinement of the oP8 structure adopted by sodium in the pressure interval 118-125 GPa, using an experimental dataset collected at 118 GPa. The orthorhombic [a=4.7687(15) Å, b=3.0150(6) Å, c=5.2423(7) Å, V=75.4(3) Å3] oP8 structure is topologically related to the MnP structure, with two non-equivalent atoms in the unit cell. Despite the weak scattering factor of Na atoms, the quality of the data also allows meaningful displacement parameters refinements (R1=4.6%, 14 parameters, 190 diffractions, and 105 unique) demonstrating that the current accuracy of diffraction data at extreme pressures can be comparable with ambient condition measurements.

Synchrotron X-ray diffraction and Raman spectroscopy of Ln{sub 3}NbO{sub 7} (Ln=La, Pr, Nd, Sm-Lu) ceramics obtained by molten-salt synthesis

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

Siqueira, K.P.F.; Soares, J.C.; Granado, E.

2014-01-15

Ln{sub 3}NbO{sub 7} (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) ceramics were obtained by molten-salt synthesis and their structures were systematically investigated by synchrotron X-ray diffraction (SXRD), second harmonic generation (SHG) and Raman spectroscopy. It was observed that ceramics with the largest ionic radii (La, Pr, Nd) crystallized into the Pmcn space group, while the ceramics with intermediate ionic radii (Sm-Gd) exhibited a different crystal structure belonging to the Ccmm space group. For this last group of ceramics, this result was corroborated by SHG and Raman scattering and ruled out any possibility formore » the non-centrosymmetric C 222{sub 1} space group, solving a recent controversy in the literature. Finally, according to SXRD, Tb-Lu containing samples exhibited an average defect fluorite structure (Fm3{sup ¯}m space group). Nonetheless, broad scattering at forbidden Bragg reflections indicates the presence of short-range domains with lower symmetry. Vibrational spectroscopy showed the presence of six Raman-active modes, inconsistent with the average cubic fluorite structure, and in line with the existence of lower-symmetry nano-domains immersed in the average fluorite structure of these ceramics. - Graphical abstract: Raman spectrum for Sm{sub 3}NbO{sub 7} ceramics showing their 27 phonon modes adjusted through Lorentzian lines. According to synchrotron X-ray diffraction and Raman scattering, this material belongs to the space group Cmcm. Display Omitted - Highlights: • Ln{sub 3}NbO{sub 7} ceramics were obtained by molten-salt synthesis. • SXRD, SHG and Raman scattering confirmed orthorhombic and cubic structures. • Ccmm instead of C222{sub 1} is the correct structure for Sm–Gd ceramics. • Pmcn space group was confirmed for La-, Pr- and Nd-based ceramics. • For Tb–Lu ceramics, ordered domains of a pyrochlore structure were observed.« less

Systematic study of charged-pion and kaon femtoscopy in Au+Au collisions at √s NN = 200 GeV

DOE PAGES

Adare, A.

2015-09-23

We present a systematic study of charged pion and kaon interferometry in Au+Au collisions at √s NN=200 GeV. The kaon mean source radii are found to be larger than pion radii in the outward and longitudinal directions for the same transverse mass; this difference increases for more central collisions. The azimuthal-angle dependence of the radii was measured with respect to the second-order event plane and similar oscillations of the source radii were found for pions and kaons. Hydrodynamic models qualitatively describe the similar oscillations of the mean source radii for pions and kaons, but they do not fully describe themore » transverse-mass dependence of the oscillations.« less

Small angle x-ray scattering of chromatin. Radius and mass per unit length depend on linker length.

PubMed Central

Williams, S P; Langmore, J P

1991-01-01

Analyses of low angle x-ray scattering from chromatin, isolated by identical procedures but from different species, indicate that fiber diameter and number of nucleosomes per unit length increase with the amount of nucleosome linker DNA. Experiments were conducted at physiological ionic strength to obtain parameters reflecting the structure most likely present in living cells. Guinier analyses were performed on scattering from solutions of soluble chromatin from Necturus maculosus erythrocytes (linker length 48 bp), chicken erythrocytes (linker length 64 bp), and Thyone briareus sperm (linker length 87 bp). The results were extrapolated to infinite dilution to eliminate interparticle contributions to the scattering. Cross-sectional radii of gyration were found to be 10.9 +/- 0.5, 12.1 +/- 0.4, and 15.9 +/- 0.5 nm for Necturus, chicken, and Thyone chromatin, respectively, which are consistent with fiber diameters of 30.8, 34.2, and 45.0 nm. Mass per unit lengths were found to be 6.9 +/- 0.5, 8.3 +/- 0.6, and 11.8 +/- 1.4 nucleosomes per 10 nm for Necturus, chicken, and Thyone chromatin, respectively. The geometrical consequences of the experimental mass per unit lengths and radii of gyration are consistent with a conserved interaction among nucleosomes. Cross-linking agents were found to have little effect on fiber external geometry, but significant effect on internal structure. The absolute values of fiber diameter and mass per unit length, and their dependencies upon linker length agree with the predictions of the double-helical crossed-linker model. A compilation of all published x-ray scattering data from the last decade indicates that the relationship between chromatin structure and linker length is consistent with data obtained by other investigators. Images FIGURE 1 PMID:2049522

High-pressure behavior of A 2 B 2 O 7 pyrochlore (A=Eu, Dy; B=Ti, Zr)

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

Rittman, Dylan R.; Turner, Katlyn M.; Park, Sulgiye

2017-01-28

In situ high-pressure X-ray diffraction and Raman spectroscopy were used to determine the influence of composition on the high-pressure behavior of A 2B 2O 7 pyrochlore (A=Eu, Dy; B=Ti, Zr) up to ~50GPa. Based on X-ray diffraction results, all compositions transformed to the high-pressure cotunnite structure. The B-site cation species had a larger effect on the transition pressure than the A-site cation species, with the onset of the phase transformation occurring at ~41 GPa for B=Ti and ~16 GPa B=Zr. However, the A-site cation affected the kinetics of the phase transformation, with the transformation for compositions with the smaller ionicmore » radii, i.e., A=Dy, proceeding faster than those with a larger ionic radii, i.e., A=Eu. These results were consistent with previous work in which the radius-ratio of the A- and B-site cations determined the energetics of disordering, and compositions with more similarly sized A- and B-site cations had a lower defect formation energy. Raman spectra revealed differences in the degree of short-range order of the different compositions. Due to the large phase fraction of cotunnite at high pressure for B=Zr compositions, Raman modes for cotunnite could be observed, with more modes recorded for A=Eu than A=Dy. These additional modes are attributed to increased short-to-medium range ordering in the initially pyrochlore structured Eu 2Zr 2O 7 as compared with the initially defect-fluorite structured Dy 2Zr 2O 7.« less

Pauling Electronegativity On/Off Effects Assessed by 13 C and 29 Si NMR Spectroscopic Analysis.

PubMed

Benedetti, Michele; De Castro, Federica; Fanizzi, Francesco P

2017-11-27

In carbon and silicon tetrahalide compounds, the experimental 13 C and 29 Si NMR chemical-shift values are known to increase or decrease on increasing the overall sum of the ionic radii of the bonded halides Σ(r h ) (normal and inverse halogen dependence (NHD and IHD, respectively)). Herein, we extrapolate the main factors responsible for such NMR chemical shifts. Intriguingly, we found a characteristic value for the overall sum of the Pauling electronegativities of the bonded halides Σ(χ h ), which works as a triggering factor to determine the transition from the NHD to IHD. Below this Σ(χ h ) value, the chemical shift of the central atom was strictly related to only the Σ(r h ) value, thus producing a NHD trend. Conversely, above this value, the chemical shift of the central atom was dependent on both the Σ(r h ) and Σ(χ h ) values, thus producing a IHD trend. A simple model, in which the effect of the Σ(χ h ) value on 13 C and 29 Si NMR chemical shifts is related to an apparent increase in the Σ(r h ) value, is deduced. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Variation of Nb-Ta, Zr-Hf, Th-U and K-Cs in two diabase-granophyre suites

USGS Publications Warehouse

Gottfried, D.; Greenland, L.P.; Campbell, E.Y.

1968-01-01

Concentrations of Nb, Ta, Zr, Hf, Th, U and Cs have been determined in samples of igneous rocks representing the diabase-granophyre suites from Dillsburg, Pennsylvania, and Great Lake, Tasmania. Niobium and tantalum have a three to fourfold increase with differentiation in each of the suites. The chilled margin of the Great Lake intrusion contains half the niobium and tantalum content (5.3 ppm and 0.4 ppm, respectively) of the chilled basalt from Dillsburg (10 ppm and 0.9 ppm, respectively). The twofold difference between the suites is correlated with differences in their titanium content. The average Nb Ta ratios for each suite are similar: 13.5 for the Great Lake suite, and 14.4 for the Dillsburg suite. The zirconium content of the two suites is essentially the same and increases from 50 to 60 ppm in the chilled margins to 240-300 ppm in the granophyres. Hafnium is low in the early formed rocks (0.5 -1.5 ppm and achieves a maximum in the granophyres (5-8 ppm). The Zr Hfratio decreases from 68 to 33 with progressive differentiation. In the Dillsburg suite thorium and uranium increase from 2.6 ppm and 0.6 ppm, respectively, in the chilled samples to 11.8 ppm and 3.1 ppm in the granophyres. The chilled margin of the Great Lake suite contains 3.2 ppm thorium and 9.8 ppm uranium; the granophyre contains 11.2 ppm thorium and 2.8 ppm uranium. The average Th U ratios of the Dillsburg and Great Lake suites are nearly the same-4.1 and 4.4, respectively. Within each suite the Th U ratio remains quite constant. Cesium and the K Cs ratio do not vary systematically in the Dillsburg suite possibly because of redistribution or loss of cesium by complex geologic processes. Except for the chilled margin of the Great Lake suite, the variation of Cs and the K Cs ratio are in accord with theoretical considerations. Cesium increases from about 0.6 ppm in the lower zone to 3.5 ppm in the granophyre; the K Cs ratio varies from 10 ?? 103 in the lower zone to 6 ?? 103 in the granophyre. A comparison of the abundance of some of these elements is made with those reported on oceanic tholeiites from the Atlantic and Pacific oceans. Trace elements with large ionic radii (Th, U, Cs) are present in significantly greater concentrations in the two continental tholeiitic series than in the oceanic tholeiites. However, this does not seem to be true for lithophilic elements of smaller ionic radii (Zr and Nb). These trace element distribution patterns, when considered with other minor element and isotopic studies, indicate that 1. (1) crustal contamination does not entirely account for differences between continental and oceanic tholeiites, and 2. (2) the oceanic tholeiites do not necessarily delimit the geochemical characteristics of the mantle. ?? 1968.

Sticky ions in biological systems.

PubMed Central

Collins, K D

1995-01-01

Aqueous gel sieving chromatography on Sephadex G-10 of the Group IA cations (Li+, Na+, K+, Rb+, Cs+) plus NH4+ as the Cl- salts, in combination with previous results for the halide anions (F-, Cl-, Br-, I-) as the Na+ salts [Washabaugh, M.W. & Collins, K.D. (1986) J. Biol. Chem. 261, 12477-12485], leads to the following conclusions. (i) The small monovalent ions (Li+, Na+, F-) flow through the gel with water molecules attached, whereas the large monovalent ions (K+, Rb+, Cs+, Cl-, Br-, I-) adsorb to the nonpolar surface of the gel, a process requiring partial dehydration of the ion and implying that these ions bind the immediately adjacent water molecules weakly. (ii) The transition from strong to weak hydration occurs at a radius of about 1.78 A for the monovalent anions, compared with a radius of about 1.06 A for the monovalent cations (using ionic radii), indicating that the anions are more strongly hydrated than the cations for a given charge density. (iii) The anions show larger deviations from ideal behavior (an elution position corresponding to the anhydrous molecular weight) than do the cations and dominate the chromatographic behavior of the neutral salts. These results are interpreted to mean that weakly hydrated ions (chaotropes) are "pushed" onto weakly hydrated surfaces by strong water-water interactions and that the transition from strong ionic hydration to weak ionic hydration occurs where the strength of ion-water interactions approximately equals the strength of water-water interactions in bulk solution. PMID:7539920

A controllable molecular sieve for Na+ and K+ ions.

PubMed

Gong, Xiaojing; Li, Jichen; Xu, Ke; Wang, Jianfeng; Yang, Hui

2010-02-17

The selective rate of specific ion transport across nanoporous material is critical to biological and nanofluidic systems. Molecular sieves for ions can be achieved by steric and electrical effects. However, the radii of Na(+) and K(+) are quite similar; they both carry a positive charge, making them difficult to separate. Biological ionic channels contain precisely arranged arrays of amino acids that can efficiently recognize and guide the passage of K(+) or Na(+) across the cell membrane. However, the design of inorganic channels with novel recognition mechanisms that control the ionic selectivity remains a challenge. We present here a design for a controllable ion-selective nanopore (molecular sieve) based on a single-walled carbon nanotube with specially arranged carbonyl oxygen atoms modified inside the nanopore, which was inspired by the structure of potassium channels in membrane spanning proteins (e.g., KcsA). Our molecular dynamics simulations show that the remarkable selectivity is attributed to the hydration structure of Na(+) or K(+) confined in the nanochannels, which can be precisely tuned by different patterns of the carbonyl oxygen atoms. The results also suggest that a confined environment plays a dominant role in the selectivity process. These studies provide a better understanding of the mechanism of ionic selectivity in the KcsA channel and possible technical applications in nanotechnology and biotechnology, including serving as a laboratory-in-nanotube for special chemical interactions and as a high-efficiency nanodevice for purification or desalination of sea and brackish water.

Crystal chemistry and the role of ionic radius in rare earth tetrasilicates: Ba2RE2Si4O12F2 (RE = Er3+-Lu3+) and Ba2RE2Si4O13 (RE = La3+-Ho3+).

PubMed

Fulle, Kyle; Sanjeewa, Liurukara D; McMillen, Colin D; Kolis, Joseph W

2017-10-01

Structural variations across a series of barium rare earth (RE) tetrasilicates are studied. Two different formulas are observed, namely those of a new cyclo-silicate fluoride, BaRE 2 Si 4 O 12 F 2 (RE = Er 3+ -Lu 3+ ) and new compounds in the Ba 2 RE 2 Si 4 O 13 (RE = La 3+ -Ho 3+ ) family, covering the whole range of ionic radii for the rare earth ions. The Ba 2 RE 2 Si 4 O 13 series is further subdivided into two polymorphs, also showing a dependence on rare earth ionic radius (space group P{\\overline 1} for La 3+ -Nd 3+ , and space group C2/c for Sm 3+ -Ho 3+ ). Two of the structure types identified are based on dinuclear rare earth units that differ in their crystal chemistries, particularly with respect to the role of fluorine as a structural director. The broad study of rare earth ions provides greater insight into understanding structural variations within silicate frameworks and the nature of f-block incorporation in oxyanion frameworks. The single crystals are grown from high-temperature (ca 953 K) hydrothermal fluids, demonstrating the versatility of the technique to access new phases containing recalcitrant rare earth oxides, enabling the study of structural trends.

Recovery of gold from electronic waste using chemical assisted microbial biosorption (hybrid) technique.

PubMed

Sheel, Anvita; Pant, Deepak

2018-01-01

The aim of present study was to develop a modified method of gold recovery from e-waste. Selective biosorption of gold from contact point of printed circuit board was achieved by using the combination of ammonium thiosulfate (AT) and Lactobacillus acidophilus (LA).Improvement in biosorption was due to the π-π interaction and resultant change in amide absorption bond between AT and LA, as evidenced by infrared spectroscopy. Selection was justified by some basic postulates of ionic radii and confirmed by inductively coupled plasma atomic emission spectroscopy. This methodology provides a unique leaching-sorption method for gold recovery and 85% of gold was recovered (from AT leachant) by the proposed combination. Copyright © 2017 Elsevier Ltd. All rights reserved.

Asymmetric epoxidation of unsaturated ketones catalyzed by heterobimetallic rare earth-lithium complexes bearing phenoxy-functionalized chiral diphenylprolinolate ligand.

PubMed

Qian, Qinqin; Tan, Yufang; Zhao, Bei; Feng, Tao; Shen, Qi; Yao, Yingming

2014-09-05

Four novel heterobimetallic complexes [REL2]{[(THF)3Li]2(μ-Cl)} stabilized by chiral phenoxy-functionalized prolinolate (RE = Yb (1), Y (2), Sm (3), Nd (4), H2L = (S)-2,4-di-tert-butyl-6-[[2-(hydroxydiphenylmethyl)pyrrolidin-1-yl]methyl]phenol have been synthesized and characterized. These readily available complexes are highly active in catalyzing the epoxidation of α,β-unsaturated ketones, while the enantioselectivity varies according to the ionic radii of the rare earth center. A series of chalcone derivatives were converted to chiral epoxides in 80 → 99% ee at 0 °C using TBHP as the oxidant in the presence of 10 mol % of 1.

Local structure and polarization resistance of Ce doped SrMnO{sub 3} using extended x-ray fine structure analysis

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

Ryu, Jiseung; Lee, Heesoo, E-mail: heesoo@pusan.ac.kr

2014-09-15

Changes to the local structure of Sr and Mn atoms in Sr{sub 1−x}Ce{sub x}MnO{sub 3} (SCM) according to increasing Ce content and the effect of the structural change on the polarization resistance of SCM were investigated. The reduction of manganese was confirmed by the absorption edge shift of the Mn K-edge toward lower energies. The noise of oscillation in extended X-ray absorption fine structure k{sup 3}χ data at Mn K-edge reveals the distortion of the local structure of Mn atoms, and the peak that indicates the bonding length of Mn-O, Sr/Ce, and -Mn decreased with the addition of Ce contentmore » in Fourier transformations of the Mn K-edge. The distortion of the local structure at Mn atoms was affected by the reduced manganese ions having larger ionic radii than Mn{sup 4+}. Meanwhile, few distortions of local atomic structures of Sr atoms occurred, and the average nearest neighboring distances of Sr-O and Sr-Mn are ∼2.13 Å and ∼2.95 Å, respectively. The average bonding lengths of the Ce-O and Ce-Mn increased because the ionic radius of substituted Ce ion with 12 coordination number is smaller than that of Sr ion, which leads the reduction of Mn ions and the distortion of local structure at the substituted A-site. Therefore, we reasoned that the distortion of the local atomic structure at Mn atoms in MnO{sub 6} and Ce atoms in A-site is one of the causes for interrupting oxygen ion transfers as a geometric factor, which results in an increase in the polarization resistance of SCM within the Ce composition range from 10 mol. % to 30 mol. %.« less

The Observational and Theoretical Tidal Radii of Globular Clusters in M87

NASA Astrophysics Data System (ADS)

Webb, Jeremy J.; Sills, Alison; Harris, William E.

2012-02-01

Globular clusters have linear sizes (tidal radii) which theory tells us are determined by their masses and by the gravitational potential of their host galaxy. To explore the relationship between observed and expected radii, we utilize the globular cluster population of the Virgo giant M87. Unusually deep, high signal-to-noise images of M87 are used to measure the effective and limiting radii of approximately 2000 globular clusters. To compare with these observations, we simulate a globular cluster population that has the same characteristics as the observed M87 cluster population. Placing these simulated clusters in the well-studied tidal field of M87, the orbit of each cluster is solved and the theoretical tidal radius of each cluster is determined. We compare the predicted relationship between cluster size and projected galactocentric distance to observations. We find that for an isotropic distribution of cluster velocities, theoretical tidal radii are approximately equal to observed limiting radii for R gc < 10 kpc. However, the isotropic simulation predicts a steep increase in cluster size at larger radii, which is not observed in large galaxies beyond the Milky Way. To minimize the discrepancy between theory and observations, we explore the effects of orbital anisotropy on cluster sizes, and suggest a possible orbital anisotropy profile for M87 which yields a better match between theory and observations. Finally, we suggest future studies which will establish a stronger link between theoretical tidal radii and observed radii.

UNDERSTANDING THE STRUCTURE OF THE HOT INTERSTELLAR MEDIUM IN NORMAL EARLY-TYPE GALAXIES.

NASA Astrophysics Data System (ADS)

Traynor, Liam; Kim, Dong-Woo; Chandra Galaxy Atlas

2018-01-01

The hot interstellar medium (ISM) of early-type galaxies (ETG's) provides crucial insight into the understanding of their formation and evolution. Mechanisms such as type Ia supernovae heating, AGN feedback, deepening potential depth through dark matter assembly and ramp-pressure stripping are known to affect the structure of the ISM. By using temperature maps and radial temperature profiles of the hot ISM from ~70 ETG's with archival Chandra data, it is possible to classify the galaxy's ISM into common structural types. This is extended by using 3D fitting of the radial temperature profile in order to provide models that further constrain the structural types. Five structural types are present, negative (temperature decreases with radii), positive (temperature increases with radii), hybrid-dip (temperature decreases at small radii and increases at large radii), hybrid-bump (inverse of hybrid-dip) and quasi-isothermal (temperature is constant at all radii). This work will be continued by 1) determining which mechanisms are present in which galaxies and 2) analysing the model parameters between galaxies within each structural type to determine whether each type can be described by a single set of model parameters, indicating that the same physical processes are responsible for creating that structural type.

Anomalous magnetic and spin glass behavior in Nb-substituted LaCo1 -xNbxO3

NASA Astrophysics Data System (ADS)

Shukla, Rishabh; Dhaka, R. S.

2018-01-01

We report the structural, magnetic, transport, and electronic properties of Nb-substituted LaCo1 -xNbxO3 (x =0 -0.2 ). The Rietveld refinement of x-ray diffraction data demonstrate structural phase transitions from rhombohedral to orthorhombic and further to monoclinic with increasing the Nb concentration up to x ≥0.2 . Interestingly, we observed dramatic changes in the magnetization (M ) with increasing the Nb concentration, as the M sharply increases below 10 K even at 2.5% substitution. Furthermore, ac susceptibility data show the spin glass behavior in x =0.1 sample. We find that the density of states near the Fermi level decreases and the activation energy increases, which results in the decreasing conductivity with higher Nb concentration. A significant shift in the peak position of A2 g phonon mode has been observed using Raman spectroscopy, which indicates the change in the coupling due to the structural distortion with Nb substitution. The core-level photoemission study confirms that the Nb is present in 5 + valence state. Our study reveals that the nonmagnetic Nb5 + (d0) substitution converts Co3 + ions to Co2 + and stabilizes both in the high-spin state. Our results suggest that structural and spin-state transitions as well as the difference in the ionic radii between Nb5 + and Co3 + are playing an important role in tuning the physical properties.

Comprehensive analysis of structure and temperature, frequency and concentration-dependent dielectric properties of lithium-substituted cobalt ferrites (Li x Co1- x Fe2O4)

NASA Astrophysics Data System (ADS)

Anjum, Safia; Nisa, Mehru; Sabah, Aneeqa; Rafique, M. S.; Zia, Rehana

2017-08-01

This paper has been dedicated to the synthesis and characterization of a series of lithium-substituted cobalt ferrites Li x Co1- x Fe2O4 ( x = 0, 0.2, 0.4, 0.6, 0.8, 1). These samples have been prepared using simple ball milling machine through powder metallurgy route. The structural analysis is carried out using X-ray diffractometer and their 3D vitalization is simulated using diamond software. The frequency and temperature-dependent dielectric properties of prepared samples have been measured using inductor capacitor resistor (LCR) meter. The structural analysis confirms that all the prepared samples have inverse cubic spinel structure. It is also revealed that the crystallite size and lattice parameter decrease with the increasing concentration of lithium (Li+1) ions, it is due to the smaller ionic radii of lithium ions. The comprehensive analysis of frequency, concentration and temperature-dependent dielectric properties of prepared samples is described in this paper. It is observed that the dielectric constant and tangent loss have decreased and conductivity increased as the frequency increases. It is also revealed that the dielectric constant, tangent loss and AC conductivity increase as the concentration of lithium increases due to its lower electronegativity value. Temperature plays a vital role in enhancing the dielectric constant, tangent loss and AC conductivity because the mobility of ions increases as the temperature increases.

Average configuration of the distant (less than 220-earth-radii) magnetotail - Initial ISEE-3 magnetic field results

NASA Technical Reports Server (NTRS)

Slavin, J. A.; Tsurutani, B. T.; Smith, E. J.; Jones, D. E.; Sibeck, D. G.

1983-01-01

Magnetic field measurements from the first two passes of the ISEE-3 GEOTAIL Mission have been used to study the structure of the trans-lunar tail. Good agreement was found between the ISEE-3 magnetopause crossings and the Explorer 33, 35 model of Howe and Binsack (1972). Neutral sheet location was well ordered by the hinged current sheet models based upon near earth measurements. Between X = -20 and -120 earth radii the radius of the tail increases by about 30 percent while the lobe field strength decreases by approximately 60 percent. Beyond X = -100 to -1200 earth radii the tail diameter and lobe field magnitude become nearly constant at terminal values of approximately 60 earth radii and 9 nT, respectively. The distance at which the tail was observed to cease flaring, 100-120 earth radii, is in close agreement with the predictions of the analytic tail model of Coroniti and Kennel (1972). Overall, the findings of this study suggest that the magnetotail retains much of its near earth structure out to X = -220 earth radii.

Characteristic analysis and comparison of two kinds of hybrid plasmonic annular resonators

NASA Astrophysics Data System (ADS)

Zhou, Jie; Shi, Feifei; Zhou, Taojie; He, Kebo; Qiu, Bocang; Zhang, Zhaoyu

2017-04-01

We designed two kinds of hybrid plasmonic annular resonators with different cross-sectional shapes, i.e., a square and circle called "square ring" and "circle ring" resonators, respectively. Both resonators feature an ultracompact mode volume of ˜10-4 μm3 and a relatively high-quality factor of ˜102 at a submicron footprint within our studied wavelength range from 400 to 900 nm. Their performance as defined by the Q/V ratio (quality factor over mode volume) is enhanced considerably with a reduction in their physical dimensions. There exists critical annular radii, which increase from 400 to 600 nm with an increase in the azimuthal numbers from m=7 to m=10, if the two types of rings are compared with the same mode numbers and same ring thickness of 120 nm. Below the critical radii, the circle ring resonator outperforms the square ring resonator in terms of the Q/V ratio, and the difference in Q/V of the two types of rings increases rapidly with the decrease of the radii. On the other hand, they have critical annular radii of ˜250 nm, below which the square ring resonator outperforms the circle ring resonator at the wavelengths of 490 and 595 nm however, the difference in Q/V of the two types of rings remains small within the radii range we consider. It is suggested that, in practice, with the consideration of the wavelength of green emission for these two ring structures with radii from 100 to 500 nm and ring thickness ˜120 nm, they have a negligible difference in Q/V performance.

Faraday rotation fluctutation spectra observed during solar occultation of the Helios spacecraft

NASA Technical Reports Server (NTRS)

Andreev, V.; Efimov, A. I.; Samoznaev, L.; Bird, M. K.

1995-01-01

Faraday rotation (FR) measurements using linearly polarized radio signals from the two Helios spacecraft were carried out during the period from 1975 to 1984. This paper presents the results of a spectral analysis of the Helios S-band FR fluctuations observed at heliocentric distances from 2.6 to 15 solar radii during the superior conjunctions 1975-1983. The mean intensity of the FR fluctuations does not exceed the noise level for solar offsets greater than ca. 15 solar radii. The rms FR fluctuation amplitude increases rapidly as the radio ray path approaches the Sun, varying according to a power law (exponent: 2.85 +/- 0.15) at solar distances 4-12 solar radii. At distances inside 4 solar radii the increase is even steeper (exponent: 5.6 +/- 0.2). The equivalent two-dimensional FR fluctuation spectrum is well modeled by a single power-law over the frequency range from 5 to 50 mHz. For heliocentric distances larger than 4 solar radii the spectral index varies between 1.1 and 1.6 with a mean value of 1.4 +/- 0.2, corresponding to a 3-D spectral index p = 2.4. FR fluctuations thus display a somwhat lower spectral index compared with phase and amplitude fluctuations. Surprisingly high values of the spectral index were found for measurements inside 4 solar radii (p = 2.9 +/- 0.2). This may arise from the increasingly dominant effect of the magnetic field on radio wave propagation at small solar offsets. Finally, a quasiperiodic component, believed to be associated with Alfven waves, was discovered in some (but not all!) fluctuation spectra observed simultaneously at two ground stations. Characteristic periods and bulk velocities of this component were 240 +/- 30 sec and 300 +/- 60 km/s, respectively.

Role of phonon scattering by elastic strain field in thermoelectric Sr1-xYxTiO3-δ

NASA Astrophysics Data System (ADS)

Bhattacharya, S.; Mehdizadeh Dehkordi, A.; Tennakoon, S.; Adebisi, R.; Gladden, J. R.; Darroudi, T.; Alshareef, H. N.; Tritt, T. M.

2014-06-01

Perovskite-type SrTiO3-δ ceramics are multifunctional materials with significant potential as n-type thermoelectric (TE) materials. The electronic and thermal transport properties of spark plasma sintered polycrystalline Sr1-xYxTiO3-δ (x = 0.05, 0.075, 0.1) ceramics are systematically investigated from (15-800) K. The Sr0.9Y0.1TiO3-δ simultaneously exhibits a large Seebeck coefficient, α > -80 μV/K and moderately high electrical resistivity, ρ ˜ 0.8 mΩ-cm at a carrier concentration of ˜1021 cm-3 at 300 K resulting in a high TE power factor defined herein as (α2σT) ˜ 0.84 W/m-K at 760 K. Despite the similar atomic masses of Sr (87.6 g/mol) and Y (88.9 g/mol), the lattice thermal conductivity (κL) of Sr1-xYxTiO3-δ is significantly reduced with increased Y-doping, owing to the smaller ionic radii of Y3+ (˜1.23 Å, coordination number 12) compared to Sr2+ (˜1.44 Å, coordination number 12) ions. In order to understand the thermal conductivity reduction mechanism, the κL in the Sr1-xYxTiO3-δ series are phenomenologically modeled with a modified Callaway's equation from 30-600 K. Phonon scattering by elastic strain field due to ionic radii mismatch is found to be the prominent scattering mechanism in reducing κL of these materials. In addition, the effect of Y-doping on the elastic moduli of Sr1-xYxTiO3-δ (x = 0, 0.1) is investigated using resonant ultrasound spectroscopy, which exhibits an anomaly in x = 0.1 in the temperature range 300-600 K. As a result, the phonon mean free path is found to be further reduced in the Sr0.9Y0.1TiO3-δ compared to that of SrTiO3-δ, resulting in a considerably low thermal conductivity κ ˜ 2.7 W/m-K at 760 K. Finally, we report a thermoelectric figure of merit (ZT) ˜ 0.3 at 760 K in the Sr0.9Y0.1TiO3-δ, the highest ZT value reported in the Y-doped SrTiO3 ceramics thus far.

Partition coefficients for REE between garnets and liquids - Implications of non-Henry's Law behaviour for models of basalt origin and evolution

NASA Technical Reports Server (NTRS)

Harrison, W. J.

1981-01-01

An experimental investigation of Ce, Sm and Tm rare earth element (REE) partition coefficients between coexisting garnets (both natural and synthetic) and hydrous liquids shows that Henry's Law may not be obeyed over a range of REE concentrations of geological relevance. Systematic differences between the three REE and the two garnet compositions may be explained in terms of the differences between REE ionic radii and those of the dodecahedral site into which they substitute, substantiating the Harrison and Wood (1980) model of altervalent substitution. Model calculations demonstrate that significant variation can occur in the rare earth contents of melts produced from a garnet lherzolite, if Henry's Law partition coefficients do not apply for the garnet phase.

Lanthanum(III) and Lutetium(III) in Nitrate-Based Ionic Liquids: A Theoretical Study of Their Coordination Shell.

PubMed

Bodo, Enrico

2015-09-03

By using ab initio molecular dynamics, we investigate the solvent shell structure of La(3+) and Lu(3+) ions immersed in two ionic liquids, ethylammonium nitrate (EAN) and its hydroxy derivative (2-ethanolammonium nitrate, HOEAN). We provide the first study of the coordination properties of these heavy metal ions in such a highly charged nonacqueous environment. We find, as expected, that the coordination in the liquid is mainly due to nitrate anions and that, due to the bidentate nature of the ligand, the complexation shell of the central ion has a nontrivial geometry and a coordination number in terms of nitrate molecules that apparently violates the decrease of ionic radii along the lanthanides series, since the smaller Lu(3+) ion seems to coordinate six nitrate molecules and the La(3+) ion only five. A closer inspection of the structural features obtained from our calculations shows, instead, that the first shell of oxygen atoms is more compact for Lu(3+) than for La(3+) and that the former coordinates 8 oxygen atoms while the latter 10 in accord with the typical lanthanide's trend along the series and that their first solvation shells have a slight irregular and complex geometrical pattern. When moving to the HOEAN solutions, we have found that the solvation of the central ion is possibly also due to the cation itself through the oxygen atom on the side chain. Also, in this liquid, the coordination numbers in terms of oxygen atoms in both solvents is 10 for La(3+) and 8 for Lu(3+).

Structural characterization combined with the first principles simulations of barium/strontium cobaltite/ferrite as promising material for solid oxide fuel cells cathodes and high-temperature oxygen permeation membranes.

PubMed

Gangopadhayay, Shruba; Inerbaev, Talgat; Masunov, Artëm E; Altilio, Deanna; Orlovskaya, Nina

2009-07-01

Mixed ionic-electronic conducting perovskite type oxides with a general formula ABO(3) (where A = Ba, Sr, Ca and B = Co, Fe, Mn) often have high mobility of the oxygen vacancies and exhibit strong ionic conductivity. They are key materials that find use in several energy related applications, including solid oxide fuel cell (SOFC), sensors, oxygen separation membranes, and catalysts. Barium/strontium cobaltite/ferrite (BSCF) Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-delta) was recently identified as a promising candidate for cathode material in intermediate temperature SOFCs. In this work, we perform experimental and theoretical study of the local atomic structure of BSFC. Micro-Raman spectroscopy was performed to characterize the vibrational properties of BSCF. The Jahn-Teller distortion of octahedral coordination around Co(4+) cations was observed experimentally and explained theoretically. Different cations and oxygen vacancies ordering are examined using plane wave pseudopotential density functional theory. We find that cations are completely disordered, whereas oxygen vacancies exhibit a strong trend for aggregation in L-shaped trimer and square tetramer structure. On the basis of our results, we suggest a new explanation for BSCF phase stability. Instead of linear vacancy ordering, which must take place before the phase transition into brownmillerite structure, the oxygen vacancies in BSCF prefer to form the finite clusters and preserve the disordered cubic structure. This structural feature could be found only in the first-principles simulations and can not be explained by the effect of the ionic radii alone.

Cation radius effects on the helix-coil transition of DNA. Cryptates and other large cations.

PubMed Central

Trend, B L; Knoll, D A; Ueno, M; Evans, D F; Bloomfield, V A

1990-01-01

Most polyelectrolyte theories of the effect of ions on the thermal melting of DNA assume that the predominant influence of the cations comes through their charge. Ion size and structure are treated, for analytic convenience, as negligible variables. We have examined the validity of this assumption by measuring the melting temperature of calf thymus DNA as a function of salt concentration with four univalent cations of different hydrated radii. These are K+ (3.3 A), (n-Pr)4N+ (4.5 A), (EtOH)4N+ (4.5 A), and C222-K+ (5 A). C222-K+ is a complex of cryptand C222 with K+. With K+ as the sole cation, Tm varies linearly with the log of ionic strength over the range 0.001-0.1 M. With all the K+ sequestered by an equimolar amount of C222, Tm is depressed by 10-20 degrees C and the slope of Tm vs. ionic strength is lower. At low ionic strength, an even greater reduction in Tm is achieved with (n-Pr)4N+; but the similar-sized (EtOH)4N+ gives a curve more similar to K+. Theoretical modeling, taking into account cation size through the Poisson-Boltzmann equation for cylindrical polyelectrolytes, predicts that larger cations should be less effective in stabilizing the double helix; but the calculated effect is less than observed experimentally. These results show that valence, cation size, and specific solvation effects are all important in determining the stability of the double-helical form of DNA. PMID:2344467

Measurement of UO2 surface oxidation using grazing-incidence x-ray diffraction: Implications for nuclear forensics

NASA Astrophysics Data System (ADS)

Tracy, Cameron L.; Chen, Chien-Hung; Park, Sulgiye; Davisson, M. Lee; Ewing, Rodney C.

2018-04-01

Nuclear forensics involves determination of the origin and history of interdicted nuclear materials based on the detection of signatures associated with their production and trafficking. The surface oxidation undergone by UO2 when exposed to air is a potential signature of its atmospheric exposure during handling and transport. To assess the sensitivity of this oxidation to atmospheric parameters, surface sensitive grazing-incidence x-ray diffraction (GIXRD) measurements were performed on UO2 samples exposed to air of varying relative humidity (34%, 56%, and 95% RH) and temperature (room temperature, 50 °C, and 100 °C). Near-surface unit cell contraction was observed following exposure, indicating oxidation of the surface and accompanying reduction of the uranium cation ionic radii. The extent of unit cell contraction provides a measure of the extent of oxidation, allowing for comparison of the effects of various exposure conditions. No clear influence of relative humidity on the extent of oxidation was observed, with samples exhibiting similar degrees of unit cell contraction at all relative humidities investigated. In contrast, the thickness of the oxidized layers increased substantially with increasing temperature, such that differences on the order of 10 °C yielded readily observable crystallographic signatures of the exposure conditions.

New reversed phase-high performance liquid chromatographic method for selective separation of yttrium from all rare earth elements employing nitrilotriacetate complexes in anion exchange mode.

PubMed

Dybczyński, Rajmund S; Kulisa, Krzysztof; Pyszynska, Marta; Bojanowska-Czajka, Anna

2015-03-20

Separation of Y from other rare earth elements (REE) is difficult because of similarity of its ionic radius to ionic radii of Tb, Dy and Ho. In the new RP-HPLC system with C18 column, tetra-n-butyl ammonium hydroxide (TBAOH) as an ion interaction reagent (IIR), nitrilotriacetic acid (NTA) as a complexing agent at pH=2.8-3.5, and post column derivatization with Arsenazo III, yttrium is eluted in the region of light REE, between Nd and Sm and is base line separated from Nd and Sm and even from promethium. Simple model employing literature data on complex formation of REE with NTA and based on anion exchange mechanism was developed to foresee the order of elution of individual REE. The model correctly predicted that lanthanides up to Tb will be eluted in the order of increasing Atomic Number (At.No.) but all heavier REE will show smaller retention factors than Tb. Concurrent UV/VIS detection at 658nm and the use of radioactive tracers together with γ-ray spectrometric measurements made possible to establish an unique elution order of elution of REE: La, Ce, Pr, Nd, Pm, Y, Sm, Er, Ho, Tm, Yb, Eu, Lu, Dy+Gd, Tb, Sc. The real place of Y however, in this elution series differs from that predicted by the model (Y between Sm and Eu). The method described in this work enables selective separation of Y from La, Ce, Pr, Nd, Pm, Sm and all heavier REE treated as a group. Copyright © 2015 Elsevier B.V. All rights reserved.

Oxygen "getter" effects on microstructure and carrier transport in low temperature combustion-processed a-InXZnO (X = Ga, Sc, Y, La) transistors.

PubMed

Hennek, Jonathan W; Smith, Jeremy; Yan, Aiming; Kim, Myung-Gil; Zhao, Wei; Dravid, Vinayak P; Facchetti, Antonio; Marks, Tobin J

2013-07-24

In oxide semiconductors, such as those based on indium zinc oxide (IXZO), a strong oxygen binding metal ion ("oxygen getter"), X, functions to control O vacancies and enhance lattice formation, hence tune carrier concentration and transport properties. Here we systematically study, in the IXZO series, the role of X = Ga(3+) versus the progression X = Sc(3+) → Y(3+) → La(3+), having similar chemical characteristics but increasing ionic radii. IXZO films are prepared from solution over broad composition ranges for the first time via low-temperature combustion synthesis. The films are characterized via thermal analysis of the precursor solutions, grazing incidence angle X-ray diffraction (GIAXRD), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and scanning transmission electron microscopy (STEM) with high angle annular dark field (HAADF) imaging. Excellent thin-film transistor (TFT) performance is achieved for all X, with optimal compositions after 300 °C processing exhibiting electron mobilities of 5.4, 2.6, 2.4, and 1.8 cm(2) V(-1) s(-1) for Ga(3+), Sc(3+), Y(3+), and La(3+), respectively, and with I(on)/I(off) = 10(7)-10(8). Analysis of the IXZO TFT positive bias stress response shows X = Ga(3+) to be superior with mobilities (μ) retaining >95% of the prestress values and threshold voltage shifts (ΔV(T)) of <1.6 V, versus <85% μ retention and ΔV(T) ≈ 20 V for the other trivalent ions. Detailed microstructural analysis indicates that Ga(3+) most effectively promotes oxide lattice formation. We conclude that the metal oxide lattice formation enthalpy (ΔH(L)) and metal ionic radius are the best predictors of IXZO oxygen getter efficacy.

China's rare-earth industry

USGS Publications Warehouse

Tse, Pui-Kwan

2011-01-01

Introduction China's dominant position as the producer of over 95 percent of the world output of rare-earth minerals and rapid increases in the consumption of rare earths owing to the emergence of new clean-energy and defense-related technologies, combined with China's decisions to restrict exports of rare earths, have resulted in heightened concerns about the future availability of rare earths. As a result, industrial countries such as Japan, the United States, and countries of the European Union face tighter supplies and higher prices for rare earths. This paper briefly reviews China's rare-earth production, consumption, and reserves and the important policies and regulations regarding the production and trade of rare earths, including recently announced export quotas. The 15 lanthanide elements-lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium (atomic numbers 57-71)-were originally known as the rare earths from their occurrence in oxides mixtures. Recently, some researchers have included two other elements-scandium and yttrium-in their discussion of rare earths. Yttrium (atomic number 39), which lies above lanthanum in transition group III of the periodic table and has a similar 3+ ion with a noble gas core, has both atomic and ionic radii similar in size to those of terbium and dysprosium and is generally found in nature with lanthanides. Scandium (atomic number 21) has a smaller ionic radius than yttrium and the lanthanides, and its chemical behavior is intermediate between that of aluminum and the lanthanides. It is found in nature with the lanthanides and yttrium. Rare earths are used widely in high-technology and clean-energy products because they impart special properties of magnetism, luminescence, and strength. Rare earths are also used in weapon systems to obtain the same properties.

Dielectric studies of Co3-xMnxO4 (x=0.1-1.0) cubic spinel multiferroic

NASA Astrophysics Data System (ADS)

Meena, P. L.; Kumar, Ravi; Prajapat, C. L.; Sreenivas, K.; Gupta, Vinay

2009-07-01

A series of Co3-xMnxO4 (x =0.1-1.0) multiferroic cubic spinel ceramics were prepared to study the effect of Mn substitution at Co site on the crystal structures and dielectric properties. No significant change in the structural symmetry was observed with increasing x up to 1.0. A linear increase in lattice parameter with x is attributed to the substitution of Co3+ by Mn3+ (large ionic radii) at the octahedral sites. An antiferromagnetic-type ordering of Co3O4 changes to ferrimagnetic-type order after incorporation of Mn. The effect of Mn substitution on the dielectric constant and loss tangent was studied over a wide range of frequency (75 kHz-5 MHz) and temperature of 150-450 K. The measured value of room temperature ac conductivity at 1.0 MHz was found to increase from 2.0×10-6 to 4.4×10-4 Ω-1 cm-1 and follows power law (σac=Aωs) behavior. The dielectric constant ɛ'(ω) shows a weak frequency dispersion and small temperature dependence below 250 K for all ceramic samples. However, a strong temperature and frequency dependence on ɛ'(ω) was observed at higher temperature (>250 K). The temperature dependent ɛ'(ω) data show the existence of room temperature ferroelectricity in all prepared samples.

Effects of Temperature on Aggregation Kinetics of Graphene Oxide in Aqueous Solutions

NASA Astrophysics Data System (ADS)

Wang, M.; Gao, B.; Tang, D.; Sun, H.; Yin, X.; Yu, C.

2017-12-01

Temperature may play an important role in controlling graphene oxide (GO) stability in aqueous solutions, but it has been overlooked in the literature. In this work, laboratory experiments were conducted to determine the effects of temperature (6, 25, and 40 °C) on GO aggregation kinetics under different combinations of ionic strength, cation type, humic acid (HA) concentration by monitoring GO hydrodynamic radii and attachment efficiencies. The results showed that, without HA, temperature increase promoted GO aggregation in both monovalent (Na+ and K+) and divalent (Ca2+) solutions. This phenomenon might be caused by multiple processes including enhanced collision frequency, enhanced cation dehydration, and reduced electrostatic repulsion. The presence of HA introduced steric repulsion forces that enhanced GO stability and temperature showed different effects GO aggregation kinetics in monovalent and divalent electrolytes. In monovalent electrolytes, cold temperature diminished the steric repulsion of HA-coated GO. As a result, the fastest increasing rate of GO hydrodynamic radius and the smallest critical coagulation concentration value appeared at the lowest temperature (6 °C). Conversely, in divalent electrolyte solutions with HA, high temperate favored GO aggregation, probably because the interactions between Ca2+ and HA increased with temperature resulting in lower HA coating on GO. Findings of this work emphasized the importance of temperature as well as solution chemistry on the stability and fate of GO nanoparticles in aquatic environment.

Nuclear charge radii: density functional theory meets Bayesian neural networks

NASA Astrophysics Data System (ADS)

Utama, R.; Chen, Wei-Chia; Piekarewicz, J.

2016-11-01

The distribution of electric charge in atomic nuclei is fundamental to our understanding of the complex nuclear dynamics and a quintessential observable to validate nuclear structure models. The aim of this study is to explore a novel approach that combines sophisticated models of nuclear structure with Bayesian neural networks (BNN) to generate predictions for the charge radii of thousands of nuclei throughout the nuclear chart. A class of relativistic energy density functionals is used to provide robust predictions for nuclear charge radii. In turn, these predictions are refined through Bayesian learning for a neural network that is trained using residuals between theoretical predictions and the experimental data. Although predictions obtained with density functional theory provide a fairly good description of experiment, our results show significant improvement (better than 40%) after BNN refinement. Moreover, these improved results for nuclear charge radii are supplemented with theoretical error bars. We have successfully demonstrated the ability of the BNN approach to significantly increase the accuracy of nuclear models in the predictions of nuclear charge radii. However, as many before us, we failed to uncover the underlying physics behind the intriguing behavior of charge radii along the calcium isotopic chain.

Boric acid flux synthesis, structure and magnetic property of MB₁₂O₁₄(OH)₁₀ (M=Mn, Fe, Zn)

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

Yang, Dingfeng; Cong, Rihong; Gao, Wenliang, E-mail: gaowl@cqu.edu.cn

2013-05-01

Three new borates MB₁₂O₁₄(OH)₁₀ (M=Mn, Fe, Zn) have been synthesized by boric acid flux methods, which are isotypic to NiB₁₂O₁₄(OH)₁₀. Single-crystal XRD was performed to determine the crystal structures in detail. They all crystallize in the monoclinic space group P2₁/c. The size of MO{sub 6} (M=Mg, Mn, Fe, Co, Ni, Zn) octahedron shows a good agreement with the Shannon effective ionic radii of M²⁺. Magnetic measurements indicate MnB₁₂O₁₄(OH)₁₀ is antiferromagnetic without a long-range ordering down to 2 K. The values of its magnetic superexchange constants were evaluated by DFT calculations, which explain the observed magnetic behavior. The UV–vis diffuse reflectancemore » spectrum of ZnB₁₂O₁₄(OH)₁₀ suggests a band gap ~4.6 eV. DFT calculations indicate it has a direct band gap 4.9 eV. The optical band gap is contributed by charge transfers from the occupied O 2p to the unoccupied Zn 4s states. - Graphical abstract: Experimental and theoretical studies indicate MnB₁₂O₁₄(OH)₁₀ is antiferromagnetic without a long-range ordering. DFT calculations show ZnB₁₂O₁₄(OH)₁₀ has a direct band gap of 4.9 eV. Highlights: • MB₁₂O₁₄(OH)₁₀ (M=Mn, Fe, Zn) are synthesized by two-step boric acid flux method. • Single-crystal XRD was performed to determine the crystal structures in detail. • Size of MO₆ (M=Mg, Mn, Fe, Co, Ni, Zn) agrees with the effective ionic radii. • MnB₁₂O₁₄(OH)₁₀ is antiferromagnetic without a long-range ordering down to 2 K. • DFT calculations indicate ZnB₁₂O₁₄(OH)₁₀ has a direct band gap 4.9 eV.« less

The Production of Cold Gas Within Galaxy Outflows

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

Scannapieco, Evan

2017-03-01

I present a suite of three-dimensional simulations of the evolution of initially hot material ejected by starburst-driven galaxy outflows. The simulations are conducted in a comoving frame that moves with the material, tracking atomic/ionic cooling, Compton cooling, and dust cooling and destruction. Compton cooling is the most efficient of these processes, while the main role of atomic/ionic cooling is to enhance density inhomogeneities. Dust, on the other hand, has little effect on the outflow evolution, and is rapidly destroyed in all the simulations except for the case with the smallest mass flux. I use the results to construct a simplemore » steady-state model of the observed UV/optical emission from each outflow. The velocity profiles in this case are dominated by geometric effects, and the overall luminosities are extremely strong functions of the properties of the host system, as observed in ultra-luminous infrared galaxies (ULIRGs). Furthermore the luminosities and maximum velocities in several models are consistent with emission-line observations of ULIRGs, although the velocities are significantly greater than observed in absorption-line studies. It may be that absorption line observations of galaxy outflows probe entrained cold material at small radii, while emission-line observations probe cold material condensing from the initially hot medium at larger distances.« less

A new model to study the phase transition from microstructures to nanostructures in ionic/ionic surfactants mixture.

PubMed

Sohrabi, Beheshteh; Gharibi, Hussein; Javadian, Soheila; Hashemianzadeh, Majid

2007-08-30

The phase behavior and aggregate structures of mixtures of the oppositely charged surfactants cetyltrimethyl ammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) are explored at high dilution by pulsed field gradient stimulated echo (PFG-STE) NMR. The aggregation numbers and hydrodynamic radii of vesicles and mixed micelles were determined by a combination of viscosity and self-diffusion coefficient measurements. The average size of the mixed micelles was larger than that of micelles containing uniformly charged head groups. Analysis of the variations of the self-diffusion coefficient and viscosity with changing concentration of CTAB or SDS in the cationic-rich and anionic-rich regions revealed a phase transition from vesicles to mixed micelles. Differences in the lengths of the CTAB and SDS hydrophobic chains stabilize vesicles relative to other microstructures (e.g., liquid crystalline and precipitate phase), and vesicles form spontaneously over a wide range of compositions in both cationic-rich and anionic-rich solutions. The results obtained from conductometry measurements confirmed this transition. Finally, according to the capacitor model, a new model was developed for estimating the surface potentials and electrostatic free energy (g(elec)). Then we investigated the variations of electrostatic and transfer free energy in phase transition between mixed micelle and vesicle.

Applied-field MPD thruster geometry effects

NASA Technical Reports Server (NTRS)

Myers, Roger M.

1991-01-01

Eight MPD thruster configurations were used to study the effects of applied field strength, propellant, and facility pressure on thruster performance. Vacuum facility background pressures higher than approx. 0.12 Pa were found to greatly influence thruster performance and electrode power deposition. Thrust efficiency and specific impulse increased monotonically with increasing applied field strength. Both cathode and anode radii fundamentally influenced the efficiency specific impulse relationship, while their lengths influence only the magnitude of the applied magnetic field required to reach a given performance level. At a given specific impulse, large electrode radii result in lower efficiencies for the operating conditions studied. For all test conditions, anode power deposition was the largest efficiency loss, and represented between 50 and 80 pct. of the input power. The fraction of the input power deposited into the anode decreased with increasing applied field and anode radii. The highest performance measured, 20 pct. efficiency at 3700 seconds specific impulse, was obtained using hydrogen propellant.

Effects of Mo-doping on microstructure and near-infrared shielding performance of hydrothermally prepared tungsten bronzes

NASA Astrophysics Data System (ADS)

Wang, Qingjuan; Li, Can; Xu, Wenai; Zhao, Xiaolin; Zhu, Jingxin; Jiang, Haiwei; Kang, Litao; Zhao, Zhe

2017-03-01

Both Mo and W belong to VIB-sub-group, and possess similar ionic radii, electronegativity and oxide lattice configuration. Herein, Mo-doped (0-80 at.%) tungsten bronzes, MxWO3, were hydrothermally prepared to systematically explore the influence of Mo-doping on their micro-structure and optical performance. The products adopted a hexagonal structure within 6 at.% Mo-doping, and transformed into a monoclinic phase with higher Mo-doping content. Further tests suggested that 1.5 at.% Mo-doping is beneficial for the formation of pure hexagonal phase and uniform nano-rod morphology. Optical measures showed that all samples exhibited high and comparable visible transmittance (70-80%), but a very different near infrared (NIR) shielding ability. The sample doped with 1.5 at.% Mo demonstrated the best NIR shielding ability with a transmittance minimum of 20% at 1300 nm. Further increase of Mo-doping dosage remarkably deteriorated NIR shielding ability by depressing the absorption of localized surface plasmon resonance (LSPR). However, the optical absorption from small-polaron was less influenced by the introduction of Mo. As a result, Mo-doping caused an evident blue shift of the infrared absorption peaks from 1350 to 750 nm.

Study of structural and magnetic properties of melt spun Nd2Fe13.6Zr0.4B ingot and ribbon

NASA Astrophysics Data System (ADS)

Amin, Muhammad; Siddiqi, Saadat A.; Ashfaq, Ahmad; Saleem, Murtaza; Ramay, Shahid M.; Mahmood, Asif; Al-Zaghayer, Yousef S.

2015-12-01

Nd2Fe13.6Zr0.4B hard magnetic material were prepared using arc-melting technique on a water-cooled copper hearth kept under argon gas atmosphere. The prepared samples, Nd2Fe13.6Zr0.4B ingot and ribbon are characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM) for crystal structure determination and morphological studies, respectively. The magnetic properties of the samples have been explored using vibrating sample magnetometer (VSM). The lattice constants slightly increased due to the difference in the ionic radii of Fe and that of Zr. The bulk density decreased due to smaller molar weight and low density of Zr as compared to that of Fe. Ingot sample shows almost single crystalline phase with larger crystallite sizes whereas ribbon sample shows a mixture of amorphous and crystalline phases with smaller crystallite sizes. The crystallinity of the material was highly affected with high thermal treatments. Magnetic measurements show noticeable variation in magnetic behavior with the change in crystallite size. The sample prepared in ingot type shows soft while ribbon shows hard magnetic behavior.

Ca$sup 45$ UPTAKE BY DOG ERYTHROCYTES SUSPENDED IN SODIUM AND POTASSIUM CHLORIDE SOLUTIONS

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

Omachi, A.; Markel, R.P.; Hegarty, H.

1961-04-01

The disappearance of Ca/sup 4//sup 5/ from the medium was greater when washed dog erythrocytes were suspended in isotonic KCl rather than in isotonic NaCl. Cells stored in a refrigerator for 24 hr or more took up even greater quantities of Ca/sup 4//sup 5/ when incubated in KCl but cells suspended in NaCl did not show any difference from fresh cells. This result is consistent with the view that competition takes place between Ca and Na ions for binding sites as a consequence of the similarity in ionic radii. Acid-citrate-dextrose and, to a certain extent, heparin appeared to delay themore » increased uptake by stored cells. Addition of glucose, adenosine, or Nembutal to stored blood had no effect. Fresh cells hemolyzed by saponin or by hypotonic media took up no more Ca than unhemolyzed fresh cells. Calcium uptake in KCl was -dependent upon pH, greater amounts being taken up at alkaline pH. In contrast to dog red cells, human and cat erythrocytes did not show differences in uptake in NaCl and in KCl, before or after storage. (auth)« less

Boundary layer charge dynamics in ionic liquid-ionic polymer transducers

NASA Astrophysics Data System (ADS)

Davidson, Jacob D.; Goulbourne, N. C.

2011-01-01

Ionic polymer transducers (IPTs), also known as ionic polymer-metal composites, are soft sensors and actuators which operate through a coupling of microscale chemical, electrical, and mechanical interactions. The use of an ionic liquid as solvent for an IPT has been shown to dramatically increase transducer lifetime in free-air use, while also allowing for higher applied voltages without electrolysis. In this work, we apply Nernst-Planck/Poisson theory to model charge transport in an ionic liquid IPT by considering a certain fraction of the ionic liquid ions as mobile charge carriers, a phenomenon which is unique to ionic liquid IPTs compared to their water-based counterparts. Numerical simulations are performed using the finite element method to examine how the introduction of another pair of mobile ions affects boundary layer charge dynamics, concentration, and charge density distributions in the electric double layer, and the overall charge transferred and current response of the IPT. Due to interactions with the Nafion ionomer, not all of the ionic liquid ions will function as mobile charge carriers; only a certain fraction will exist as "free" ions. The presence of mobile ionic liquid ions in the transducer will increase the overall charge transferred when a voltage is applied, and cause the current in the transducer to decay more slowly. The additional mobile ions also cause the ionic concentration profiles to exhibit a nonlinear dynamic response, characterized by nonmonotonic ionic concentration profiles in space and time. Although the presence of mobile ionic liquid ions increases the overall amount of charge transferred, this additional charge transfer occurs in a somewhat symmetric manner. Therefore, the additional charge transferred due to the ionic liquid ions does not greatly increase the net bending moment of the transducer; in fact, it is possible that ionic liquid ion movement actually decreases the observed bending response. This suggests that an optimal electromechanical conversion efficiency for bending actuation is achieved by using an ionic liquid where only a relatively small fraction of the ionic liquid ions exist as free ions. Conversely, if it is desired to increase the overall amount of charge transferred, an ionic liquid with a large fraction of free ions should be used. These theoretical considerations are found to be in good qualitative agreement with recent experimental results.

Optical study of Tm-doped solid solution (Sc0.5Y0.5)2SiO5 crystal

NASA Astrophysics Data System (ADS)

Shi, Jiaojiao; Liu, Bin; Zheng, Lihe; Wang, Qingguo; Tang, Huili; Liu, Junfang; Su, Liangbi; Wu, Feng; Zhao, Hengyu; He, Nuotian; Li, Na; Li, Qiu; Guo, Chao; Xu, Jun; Yang, Kejian; Xu, Xiaodong; Ryba-Romanowski, Witold; Lisiecki, Radosław; Solarz, Piotr

2018-04-01

Tm-doped (Sc0.5Y0.5)2SiO5 (SYSO) crystals were grown by Czochralski method. The UV-VIR-NIR absorption spectra and the near-infrared emission spectra were measured and analysed by the Judd-Ofelt approach. Temperature influence on both absorption and emission spectra has been determined from the data recorded at room temperature and 10 K. It has been found that the structural disorder resulting from dissimilar ionic radii of Sc3+ and Y3+ in the solid solution (Sc0.5Y0.5)2SiO5 crystal brings about a strong inhomogeneous broadening of Tm3+ ions spectra. However, it affects the excited state relaxation dynamics inherent to thulium-doped Y2SiO5 and Sc2SiO5 hosts weakly.

Preparation of Some Novel Copper(I) Complexes and their Molar Conductances in Organic Solvents

NASA Astrophysics Data System (ADS)

Gill, Dip Singh; Rana, Dilbag

2009-04-01

Attempts have been made to prepare some novel copper(I) nitrate, sulfate, and perchlorate complexes. Molar conductances of these complexes have been measured in organic solvents like acetonitrile (AN), acetone (AC), methanol (MeOH), N,N-dimethylformamide (DMF), N,Ndimethylacetamide (DMA), and dimethylsulfoxide (DMSO) at 298 K. The molar conductance data have been analyzed to obtain limiting molar conductances (λ0) and ion association constants (KA) of the electrolytes. The results showed that all these complexes are strong electrolytes in all organic solvents. The limiting ionic molar conductances (λo± ) for various ions have been calculated using Bu4NBPh4 as reference electrolyte. The actual radii for copper(I) complex ions are very large and different in different solvents and indicate some solvation effects in each solvent system

73Ge, 119Sn and 207Pb: general cooperative effects of single atom ligands on the NMR signals observed in tetrahedral [MXnY4-n] (M = Ge, Sn, Pb; 1 ≤ n ≤ 4; X, Y = Cl, Br, I) coordination compounds of heavier XIV group elements.

PubMed

Benedetti, M; De Castro, F; Fanizzi, F P

2017-02-28

An inverse linear relationship between 73 Ge, 119 Sn and 207 Pb NMR chemical shifts and the overall sum of ionic radii of coordinated halido ligands has been discovered in tetrahedral [MX n Y 4-n ] (M = Ge, Sn, Pb; 1 ≤ n ≤ 4; X, Y = Cl, Br, I) coordination compounds. This finding is consistent with a previously reported correlation found in octahedral, pentacoordinate and square planar platinum complexes. The effect of the coordinated halido ligands acting on the metal as shielding conducting rings is therefore confirmed also by 73 Ge, 119 Sn and 207 Pb NMR spectroscopy.

Impact of Lu/Gd ratio and activator concentration on structure and scintillation properties of LGSO:Ce crystals

NASA Astrophysics Data System (ADS)

Sidletskiy, O.; Bondar, V.; Grinyov, B.; Kurtsev, D.; Baumer, V.; Belikov, K.; Katrunov, K.; Starzhinsky, N.; Tarasenko, O.; Tarasov, V.; Zelenskaya, O.

2010-02-01

We have studied the dependence of structural and scintillation characteristics of Lu 2 xGd 2-2 xSiO 5:Ce (LGSO:Ce) crystals on cation composition. LGSO:Ce crystals at x=0-1 have been obtained by the Czochralski method. We report here a strong correlation between ionic radii of trivalent cations and their distribution between non-equivalent sites in lattice. By choosing the optimal Lu/Gd ratio and Ce concentration we were able to obtain the light output by˜70%, as compared to LSO:Ce crystals, and energy resolution ˜7 at% 662 KeV ( 137Cs); the afterglow level was decreased by 1-3 orders of magnitude as compared to LSO:Ce. We also discuss the possible mechanisms of control on scintillation characteristics of mixed orthosilicates.

Hypersonic boundary-layer transition measurements at Mach 10 on a large seven-degree cone at angle of attack

NASA Astrophysics Data System (ADS)

Moraru, Ciprian G.

The ability to predict the onset of boundary-layer transition is critical for hypersonic flight vehicles. The development of prediction methods depends on a thorough comprehension of the mechanisms that cause transition. In order to improve the understanding of hypersonic boundary-layer transition, tests were conducted on a large 7° half-angle cone at Mach 10 in the Arnold Engineering Development Complex Wind Tunnel 9. Twenty-four runs were performed at varying unit Reynolds numbers and angles of attack for sharp and blunt nosetip configurations. Heat-transfer measurements were used to determine the start of transition on the cone. Increasing the unit Reynolds number caused a forward movement of transition on the sharp cone at zero angle of attack. Increasing nosetip radius delayed transition up to a radius of 12.7 mm. Larger nose radii caused the start of transition to move forward. At angles of attack up to 10°, transition was leeside forward for nose radii up to 12.7 mm and windside forward for nose radii of 25.4 mm and 50.8 mm. Second-mode instability waves were measured on the sharp cone and cones with small nose radii. At zero angle of attack, waves at a particular streamwise location on the sharp cone were in earlier stages of development as the unit Reynolds number was decreased. The same trend was observed as the nosetip radius was increased. No second-mode waves were apparent for the cones with large nosetip radii. As the angle of attack was increased, waves at a particular streamwise location on the sharp cone moved to earlier stages of growth on the windward ray and later stages of growth on the leeward ray. RMS amplitudes of second-mode waves were computed. Comparison between maximum second-mode amplitudes and edge Mach numbers showed good correlation for various nosetip radii and unit Reynolds numbers. Using the e N method, initial amplitudes were estimated and compared to freestream noise in the second-mode frequency band. Correlations indicate that freestream noise likely has a significant influence on initial second-mode amplitudes.

Bayesian Analysis of Hot-Jupiter Radius Anomalies: Evidence for Ohmic Dissipation?

NASA Astrophysics Data System (ADS)

Thorngren, Daniel P.; Fortney, Jonathan J.

2018-05-01

The cause of hot-Jupiter radius inflation, where giant planets with {T}eq} > 1000 K are significantly larger than expected, is an open question and the subject of many proposed explanations. Many of these hypotheses postulate an additional anomalous power that heats planets’ convective interiors, leading to larger radii. Rather than examine these proposed models individually, we determine what anomalous powers are needed to explain the observed population’s radii, and consider which models are most consistent with this. We examine 281 giant planets with well-determined masses and radii and apply thermal evolution and Bayesian statistical models to infer the anomalous power as a fraction of (and varying with) incident flux ɛ(F) that best reproduces the observed radii. First, we observe that the inflation of planets below about M = 0.5 M J appears very different than their higher-mass counterparts, perhaps as the result of mass loss or an inefficient heating mechanism. As such, we exclude planets below this threshold. Next, we show with strong significance that ɛ(F) increases with {T}eq} toward a maximum of ∼2.5% at T eq ≈ 1500 K, and then decreases as temperatures increase further, falling to ∼0.2% at T eff = 2500 K. This high-flux decrease in inflation efficiency was predicted by the Ohmic dissipation model of giant planet inflation but not other models. We also show that the thermal tides model predicts far more variance in radii than is observed. Thus, our results provide evidence for the Ohmic dissipation model and a functional form for ɛ(F) that any future theories of hot-Jupiter radii can be tested against.

CdO as the archetypical transparent conducting oxide. Systematics of dopant ionic radius and electronic structure effects on charge transport and band structure.

PubMed

Yang, Yu; Jin, Shu; Medvedeva, Julia E; Ireland, John R; Metz, Andrew W; Ni, Jun; Hersam, Mark C; Freeman, Arthur J; Marks, Tobin J

2005-06-22

A series of yttrium-doped CdO (CYO) thin films have been grown on both amorphous glass and single-crystal MgO(100) substrates at 410 degrees C by metal-organic chemical vapor deposition (MOCVD), and their phase structure, microstructure, electrical, and optical properties have been investigated. XRD data reveal that all as-deposited CYO thin films are phase-pure and polycrystalline, with features assignable to a cubic CdO-type crystal structure. Epitaxial films grown on single-crystal MgO(100) exhibit biaxial, highly textured microstructures. These as-deposited CYO thin films exhibit excellent optical transparency, with an average transmittance of >80% in the visible range. Y doping widens the optical band gap from 2.86 to 3.27 eV via a Burstein-Moss shift. Room temperature thin film conductivities of 8,540 and 17,800 S/cm on glass and MgO(100), respectively, are obtained at an optimum Y doping level of 1.2-1.3%. Finally, electronic band structure calculations are carried out to systematically compare the structural, electronic, and optical properties of the In-, Sc-, and Y-doped CdO systems. Both experimental and theoretical results reveal that dopant ionic radius and electronic structure have a significant influence on the CdO-based TCO crystal and band structure: (1) lattice parameters contract as a function of dopant ionic radii in the order Y (1.09 A) < In (0.94 A) < Sc (0.89 A); (2) the carrier mobilities and doping efficiencies decrease in the order In > Y > Sc; (3) the dopant d state has substantial influence on the position and width of the s-based conduction band, which ultimately determines the intrinsic charge transport characteristics.

Roles of Bi, M and VO{sub 4} tetrahedron in photocatalytic properties of novel Bi{sub 0.5}M{sub 0.5}VO{sub 4} (M=La, Eu, Sm and Y) solid solutions for overall water splitting

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

Liu Hui; Research Center for Combustion and Environment Technology, Shanghai Jiao Tong University, shanghai 200240; Faculty of Engineering Sciences, Kyushu University, Fukuoka 816-8580

2012-02-15

Novel Bi{sub 0.5}M{sub 0.5}VO{sub 4} (BMV; M=La, Eu, Sm and Y) solid solutions were prepared and studied in this paper. All the samples were proved to produce H{sub 2} and O{sub 2} simultaneously from pure water under the irradiation of UV light. M-O bond lengths were proved to increase with M cations by refining cell parameters and atomic positions. Besides, band gaps, energy gaps and photocatalytic activities of BMV also changed with M cations. Both of M-O and V-O bond lengths were suggested to account for this phenomenon. Inactive A{sub 0.5}Y{sub 0.5}VO{sub 4} (A=La, Ce) for water splitting proved incorporationmore » of Bi rather than distortion of VO{sub 4} tetrahedron was a critical factor for improving efficiency of overall water splitting by facilitating the generation of electron and hole with lighter effective masses. Replacement of Bi by M cations not only gave indirect effect on band structure but also raised position of conduction band minimum to meet requirement of H{sub 2} production. - Graphical abstract: Novel Bi{sub 0.5}M{sub 0.5}VO{sub 4} (M=La, Eu, Sm and Y) solid solutions showed the high and stable photocatalytic activities for overall water splitting with their crystal radii of M elements. Highlights: Black-Right-Pointing-Pointer BMV solid solutions were novel highly efficient V-based photocatalysts for overall water splitting. Black-Right-Pointing-Pointer Photocatalytic activity of BMV solid solution related to the effective ionic radii of M cations. Black-Right-Pointing-Pointer Incorporation of Bi is one of key factors for the highly efficient activity of BMV solid solution. Black-Right-Pointing-Pointer Incorporation of Y is dispensable for H{sub 2} production.« less

Insights into the crystal chemistry of Earth materials rendered by electron density distributions: Pauling's rules revisited

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

Gibbs, Gerald V.; Ross, Nancy L.; Cox, David F.

2014-05-20

Pauling's first two rules are examined in terms of the accumulation of the electron density between bonded pairs of atoms for a relatively large number of oxide and silicate crystals and siloxane molecules. The distribution of the electron density shows that the radius of the oxygen atom is not fixed, but that it actually decreases systematically from ~1.40 Å to ~ 0.65 Å as the polarizing power and the electronegativity of the bonded metal atoms increase and the distribution of the O atom is progressively polarized and contracted along the bond vectors by the impact of the bonded interactions. Themore » contractions result in an aspherical oxygen atom that displays as many different bonded “radii” as it has bonded interactions. The bonded radii for the metal atoms match the Shannon and Prewitt ionic radii for the more electropositive atoms like potassium and sodium, but they are systematically larger for the more electronegative atoms like aluminum, silicon and phosphorous. Pauling's first rule is based on the assumption that the radius of the oxide anion is fixed and that the radii of the cations are such that radius sum of the spherical oxide anion and a cation necessarily equals the separation between the cation-anion bonded pair with the coordination number of the cation being determined by the ratio of the radii of the cation and anion. In the case of the bonded radii, the sum of the bonded radii for the metal atoms and the oxide anion necessarily equals the bond lengths by virtue of the way that the bonded radii were determined in the partitioning of the electron density along the bond path into metal and O atom parts. But, the radius ratio for the O and M atoms is an unsatisfactory rule for determining the coordination number of the metal atom inasmuch as a bonded O atom is not, in general, spherical, and its size varies substantially along its bonded directions. But by counting the number of bond paths that radiate from a bonded atom, the coordination number of the atom is determined uniquely independent of the asphericity and sizes of the atom. A power law connection established between the bond lengths and bond strengths for crystals and molecules is mirrored by a comparable power law connection between bond length and the accumulation of the electron density between bonded pairs of atoms, a connection that is consistent with Pauling's electroneutrality postulate that the charges of the atoms in an oxide are negligibly small. The connection indicates that a one-to-one correspondence exists between the accumulation between a pair of bonded atoms and the Pauling bond strength for M-O bonded interaction for all atoms of the periodic table. The connection provides a common basis for understanding the success of the manifold applications that have been made with the bond valence theory model together with the modeling of crystal structures, chemical zoning, leaching and cation transport in batteries and the like. We believe that the wide spread applications of the model in mineralogy and material science owes much of its success to the direct connection between bond strength and the quantum mechanical observable, the electron density distribution. Comparable power law expressions established for the bonded interactions for both crystals and molecules support Pauling's assertion that his second rule has significance for molecules as well as for crystals. A simple expression is found that provides a one to one connection between the accumulation of the electron density between bonded M and O atoms and the Pauling bond strength for all M atoms of the periodic table with ~ 95 % of the variation of the bond strength being explained in terms of a linear dependence on the accumulated electron density. Compelling evidence is presented that supports the argument that the Si-O bonded interactions for tiny siloxane molecules and silicate crystals are chemically equivalent.« less

Zn-Al layered double hydroxide prepared at different molar ratios: Preparation, characterization, optical and dielectric properties

NASA Astrophysics Data System (ADS)

Ahmed, Abdullah Ahmed Ali; Talib, Zainal Abidin; bin Hussein, Mohd Zobir; Zakaria, Azmi

2012-07-01

The co-precipitation method was used to prepare Zn-Al-NO3-LDH at different Zn2+/Al3+ molar ratios (2, 3, 4, 5 and 6) and pH value of 7.5. The structure, textural, composition and morphological properties were investigated using powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR) and scanning electron microscope (SEM), respectively. The crystallinity of LDH samples were found to improve as molar ratio decreased which is attributed to the distortion of the hydroxide layers networks of the LDH crystal by the larger difference in ionic radii of Zn2+ and Al3+. The optical band gap energy of LDH samples were evaluated using absorbance data from UV-Vis-NIR Diffuse reflectance spectroscopy. Band gaps were affected by the variation of the Zn2+/Al3+ molar ratio is due to the formation of the low crystalline phases (ZnO and ZnAl2O4). The water molecules and anionic NO3- in the LDH interlayer were responsible for the generation of the dielectric response. This response can be described by an anomalous low frequency dispersion using the second type of Universal Power Law. The dominance of ZnO dipoles and charge carriers (NO3- ions) in the dielectric relaxation increases with the increasing molar ratio.

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

Wu, Chunya; Skelton, Adam A.; Chen, Mingjun

Here the binding of a negatively charged residue, aspartic acid (Asp) in tripeptide arginine-glycine-aspartic acid, onto a negatively charged hydroxylated rutile (110) surface in aqueous solution, containing divalent (Mg 2+, Ca 2+, or Sr 2+) or monovalent (Na +, K +, or Rb +) cations, was studied by molecular dynamics (MD) simulations. The results indicate that ionic radii and charges will significantly affect the hydration, adsorption geometry, and distance of cations from the rutile surface, thereby regulating the Asp/rutile binding mode. The adsorption strength of monovalent cations on the rutile surface in the order Na + > K + >more » Rb + shows a “reverse” lyotropic trend, while the divalent cations on the same surface exhibit a “regular” lyotropic behavior with decreasing crystallographic radii (the adsorption strength of divalent cations: Sr 2+ > Ca 2+ > Mg 2+). The Asp side chain in NaCl, KCl, and RbCl solutions remains stably H-bonded to the surface hydroxyls and the inner-sphere adsorbed compensating monovalent cations act as a bridge between the COO – group and the rutile, helping to “trap” the negatively charged Asp side chain on the negatively charged surface. In contrast, the mediating divalent cations actively participate in linking the COO– group to the rutile surface; thus the Asp side chain can remain stably on the rutile (110) surface, even if it is not involved in any hydrogen bonds with the surface hydroxyls. Inner- and outer-sphere geometries are all possible mediation modes for divalent cations in bridging the peptide to the rutile surface.« less

First-principles studies of the local structure and relaxor behavior of Pb(Mg 1 /3Nb2 /3) O3-PbTiO3 -derived ferroelectric perovskite solid solutions

NASA Astrophysics Data System (ADS)

Tan, Hengxin; Takenaka, Hiroyuki; Xu, Changsong; Duan, Wenhui; Grinberg, Ilya; Rappe, Andrew M.

2018-05-01

We have investigated the effect of transition-metal dopants on the local structure of the prototypical 0.75 Pb (Mg1 /3Nb2 /3) O3-0.25 PbTiO3 relaxor ferroelectric. We find that these dopants give rise to very different local structure and other physical properties. For example, when Mg is partially substituted by Cu or Zn, the displacement of Cu or Zn is much larger than that of Mg and is even comparable to that of Nb. The polarization of these systems is also increased, especially for the Cu-doped solution, due to the large polarizability of Cu and Zn. As a result, the predicted maximum dielectric constant temperatures Tm are increased. On the other hand, the replacement of a Ti atom with a Mo or Tc atom dramatically decreases the displacements of the cations and the polarization, and thus, the Tm values are also substantially decreased. The higher Tm cannot be explained by the conventional argument based on the ionic radii of the cations. Furthermore, we find that Cu, Mo, or Tc doping increases the cation displacement disorder. The effect of the dopants on the temperature dispersion Δ Tm , which is the change in Tm for different frequencies, is also discussed. Our findings lay the foundation for further investigations of unexplored dopants.

The measurement of dynamic radii for passenger car tyre

NASA Astrophysics Data System (ADS)

Anghelache, G.; Moisescu, R.

2017-10-01

The tyre dynamic rolling radius is an extremely important parameter for vehicle dynamics, for operation of safety systems as ESP, ABS, TCS, etc., for road vehicle research and development, as well as for validation or as an input parameter of automotive simulations and models. The paper investigates the dynamic rolling radii of passenger car tyre and the influence of rolling speed and inflation pressure on their magnitude. The measurement of dynamic rolling radii has been performed on a chassis dynamometer test rig. The dynamic rolling radii have been measured indirectly, using longitudinal rolling speed and angular velocity of wheel. Due to the subtle effects that the parameters have on rolling radius magnitude, very accurate equipment has to be used. Two different methods have been chosen for measuring the wheel angular velocity: the stroboscopic lamp and the incremental rotary encoder. The paper shows that the stroboscopic lamp has an insufficient resolution, therefore it was no longer used for experimental investigation. The tyre dynamic rolling radii increase with rolling speed and with tyre inflation pressure, but the effect of pressure is more significant. The paper also makes considerations on the viability of simplified formulae from literature for calculating the tyre dynamic rolling radius.

Formation of hybrid ABX3 perovskite compounds for solar cell application: first-principles calculations of effective ionic radii and determination of tolerance factors.

PubMed

Becker, Markus; Klüner, Thorsten; Wark, Michael

2017-03-14

The development of hybrid organic-inorganic perovskite solar cells is one of the most rapidly growing fields in the photovoltaic community and is on its way to challenge polycrystalline silicon and thin film technologies. High power conversion efficiencies can be achieved by simple processing with low cost. However, due to the limited long-term stability and environmental toxicity of lead in the prototypic CH 3 NH 3 PbI 3 , there is a need to find alternative ABX 3 constitutional combinations in order to promote commercialization. The Goldschmidt tolerance factor and the octahedral factor were found to be necessary geometrical concepts to evaluate which perovskite compounds can be formed. It was figured out that the main challenge lies in estimating an effective ionic radius for the molecular cation. We calculated tolerance factors and octahedral factors for 486 ABX 3 monoammonium-metal-halide combinations, where the steric size of the molecular cation in the A-position was estimated concerning the total charge density. A thorough inquiry about existing mixed organic-inorganic perovskites was undertaken. Our results are in excellent agreement with the reported hybrid compounds and indicate the potential existence of 106 ABX 3 combinations hitherto not discussed in the literature, giving hints for more intense research on prospective individual candidates.

Structure-substitution limit correlation study on Cr{sup 3+} substituted polycrystalline yttrium iron garnet

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

Modi, K. B.; Saija, K. G.; Sharma, P. U.

2016-05-06

Polycrystalline samples of Cr{sup 3+} - substituted yttrium iron garnet (Y{sub 3}Fe{sub 5}O{sub 12}) system with general chemical formula, Y{sub 3}Fe{sub 5-x}Cr{sub x}O{sub 12}, x = 0.0, 0.2, 0.4 and 0.6 were synthesized by double sintering ceramic technique and characterized by X-ray powder diffractometry. The Rietveld fitted X-ray diffraction patterns analysis revealed mono phase formation for x = 0.0 - 0.4 compositions while x = 0.6 composition possesses mixed phase character. The observed substitution limit has been discussed in the light of ionic size of substituent, electrostatic energy, electronic configuration and synthesis parameters. These observations strongly suggest that the electronicmore » configuration of Cr{sup 3+}, which is favorable to the formation of d2sp3 (octahedral) type bonds, must be important. In the case of Cr{sup 3+}, the substitution does not appear to proceed well for x much greater than 0.5, this limitation probably is a consequence of the strong preference of a smaller ion Cr{sup 3+}, for a larger octahedral site which quickly leads to a condition not comparable with the requirement of the structure. The distribution of cations, mean ionic radii and theoretical lattice constant values have been determined.« less

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

Oliver, S. A.; Harris, V. G.; Hamdeh, H. H.

The cation site occupancy of a mechanically activated nanocrystalline zinc ferrite powder was determined as (Zn{sub 0.55}{sup 2+}Fe{sub 0.18}{sup 3+}){sub tet}[Zr{sub 0.45}{sup 2+}Fe{sub 1.82}{sup 3+}]{sub oct}O{sub 4} through analysis of extended x-ray absorption fine structure measurements, showing a large redistribution of cations between sites compared to normal zinc ferrite samples. The overpopulation of cations in the octahedral sites was attributed to the ascendance in importance of the ionic radii over the crystal energy and bonding coordination in determining which interstitial sites are occupied in this structurally disordered powder. Slight changes are observed in the local atomic environment about the zincmore » cations, but not the iron cations, with respect to the spinel structure. The presence of Fe{sup 3+} on both sites is consistent with the measured room temperature magnetic properties. (c) 2000 American Institute of Physics.« less

Minor elements in Keweenawan lavas, Michigan

USGS Publications Warehouse

Cornwall, H.R.; Rose, H.J.

1957-01-01

The distribution of minor elements in three basaltic flows of the Keweenawan series, of Michigan, is related to differentiation in the flows. Thus, nickel is most abundant in the early differentiates; nickel, chromium, and barium are generally deficient in the pegmatites, which formed late; whereas copper, vanadium, yttrium, and other minor elements are concentrated in the pegmatites. The minor-element content of individual minerals in the Greenstone flow varies markedly from one mineral to another and seems to depend primarily on the presence or absence in the minerals of major elements for which the minor elements can substitute. Minor elements have substituted most readily for those major elements with similar ionic radii. Valence and electronegativity also seem to influence the ease of substitution. The distribution of other minor elements in copper-bearing lodes of the Michigan copper district shows no apparent relation to copper mineralization. ?? 1957.

Multisite occupation of divalent dopants in barium and strontium titanates

NASA Astrophysics Data System (ADS)

Zulueta, Yohandys A.; Nguyen, Minh Tho

2018-10-01

Based on recent experimental and theoretical proofs of calcium multisite occupation in barium titanate, we investigated a mixed incorporation mechanism for divalent dopants in barium and strontium titanates (BaTiO3 and SrTiO3). Our present theoretical results demonstrated the multisite occupation of divalent dopants in both perovskite structures. We determined the dependences of the solution, binding energies, and final solution energies with respect to the ionic radii of the dopants. Calculated results obtained based on classical simulations showed that the divalent dopants can occupy both A- and Ti- cation sites in ATiO3 perovskite structures. Such a multisite occupation has direct implications for other experimental findings regarding BaTiO3, such as non-stabilization of the tetragonal phase, shifts in the Curie temperature, intensification of the diffuse phase transition, and shifts in the absorption of ultraviolet light to the visible range in photocatalytic applications related to solar cells for producing energy.

AME - Asteroseismology Made Easy. Estimating stellar properties by using scaled models

NASA Astrophysics Data System (ADS)

Lundkvist, Mia; Kjeldsen, Hans; Silva Aguirre, Victor

2014-06-01

Context. Stellar properties and, in particular stellar radii of exoplanet host stars, are essential for measuring the properties of exoplanets, therefore it is becoming increasingly important to be able to supply reliable stellar radii fast. Grid-modelling is an obvious choice for this, but that only offers a low degree of transparency to non-specialists. Aims: Here we present a new, easy, fast, and transparent method of obtaining stellar properties for stars exhibiting solar-like oscillations. The method, called Asteroseismology Made Easy (AME), can determine stellar masses, mean densities, radii, and surface gravities, as well as estimate ages. We present AME as a visual and powerful tool that could be useful, in particular, in light of the large number of exoplanets being found. Methods: AME consists of a set of figures from which the stellar parameters can be deduced. These figures are made from a grid of stellar evolutionary models that cover masses ranging from 0.7 M⊙ to 1.6 M⊙ in steps of 0.1 M⊙ and metallicities in the interval -0.3 dex ≤ [Fe/H] ≤ +0.3 dex in increments of 0.1 dex. The stellar evolutionary models are computed using the Modules for Experiments in Stellar Astrophysics (MESA) code with simple input physics. Results: We have compared the results from AME with results for three groups of stars: stars with radii determined from interferometry (and measured parallaxes), stars with radii determined from measurements of their parallaxes (and calculated angular diameters), and stars with results based on modelling their individual oscillation frequencies. We find that a comparison of the radii from interferometry to those from AME yields a weighted mean of the fractional differences of just 2%. This is also the level of deviation that we find when we compare the parallax-based radii to the radii determined from AME. Conclusions: The comparison between independently determined stellar parameters and those found using AME show that our method can provide reliable stellar masses, radii, and ages, with median uncertainties in the order of 4%, 2%, and 25%, respectively. http://sac.au.dk/scientific-data/ame

U(SMes*)n, (n = 3, 4) and Ln(SMes*)3 (Ln = La, Ce, Pr, Nd): lanthanide(III)/actinide(III) differentiation in agostic interactions and an unprecedented eta3 ligation mode of the arylthiolate ligand, from X-ray diffraction and DFT analysis.

PubMed

Roger, Mathieu; Barros, Noémi; Arliguie, Thérèse; Thuéry, Pierre; Maron, Laurent; Ephritikhine, Michel

2006-07-12

Reaction of U(NEt(2))(4) with HS-2,4,6-(t)Bu(3)C(6)H(2) (HSMes) gave U(SMes)(3)(NEt(2))(py) (1), whereas similar treatment of U[N(SiMe(3))SiMe(2)CH(2)][N(SiMe(3))(2)](2) afforded U(SMes)[N(SiMe(3))(2)](3) (2) and U(SMes)(3)[N(SiMe(3))(2)]. The first neutral homoleptic uranium(IV) thiolate to have been crystallographically characterized, U(SMes)(4) (4), was isolated from the reaction of U(BH(4))(4) and KSMes. The first homoleptic thiolate complex of uranium(III), U(SMes)(3) (5), was synthesized by protonolysis of U[N(SiMe(3))(2)](3) with HSMes in cyclohexane. The crystal structure of 5 exhibits the novel eta(3) ligation mode for the arylthiolate ligand. Comparison of the crystal structure of 5 with those of the isomorphous lanthanide congeners Ln(SMes)(3) (Ln = La, Ce, Pr, and Nd) indicates that the U-S, U-C(ipso)(), and U-C(ortho)() bond lengths are shorter than the corresponding ones in the 4f-element analogues, when taking into account the variation in the ionic radii of the metals. The distance between the uranium and the carbon atoms involved in the U...H-C epsilon agostic interaction of each thiolate ligand is shorter, by approximately 0.05 A, than that expected from a purely ionic bonding model. The lanthanide(III)/actinide(III) differentiation was analyzed by density functional theory (DFT). The nature of the M-S bond is shown to be ionic strongly polarized at the sulfur for M = U and iono-covalent (i.e. strongly ionic with low orbital interaction), for M = Ln. The strength of the U...H-C epsilon agostic interaction is proposed to be controlled by the maximization of the interaction between U(+) and S(-) under steric constraints. The eta(3) ligation mode of the arylthiolate ligand is also obtained from DFT.

Development and validation of a canine radius replica for mechanical testing of orthopedic implants.

PubMed

Little, Jeffrey P; Horn, Timothy J; Marcellin-Little, Denis J; Harrysson, Ola L A; West, Harvey A

2012-01-01

To design and fabricate fiberglass-reinforced composite (FRC) replicas of a canine radius and compare their mechanical properties with those of radii from dog cadavers. Replicas based on 3 FRC formulations with 33%, 50%, or 60% short-length discontinuous fiberglass by weight (7 replicas/group) and 5 radii from large (> 30-kg) dog cadavers. Bones and FRC replicas underwent nondestructive mechanical testing including 4-point bending, axial loading, and torsion and destructive testing to failure during 4-point bending. Axial, internal and external torsional, and bending stiffnesses were calculated. Axial pullout loads for bone screws placed in the replicas and cadaveric radii were also assessed. Axial, internal and external torsional, and 4-point bending stiffnesses of FRC replicas increased significantly with increasing fiberglass content. The 4-point bending stiffness of 33% and 50% FRC replicas and axial and internal torsional stiffnesses of 33% FRC replicas were equivalent to the cadaveric bone stiffnesses. Ultimate 4-point bending loads did not differ significantly between FRC replicas and bones. Ultimate screw pullout loads did not differ significantly between 33% or 50% FRC replicas and bones. Mechanical property variability (coefficient of variation) of cadaveric radii was approximately 2 to 19 times that of FRC replicas, depending on loading protocols. Within the range of properties tested, FRC replicas had mechanical properties equivalent to and mechanical property variability less than those of radii from dog cadavers. Results indicated that FRC replicas may be a useful alternative to cadaveric bones for biomechanical testing of canine bone constructs.

Research on the drag reduction performance induced by the counterflowing jet for waverider with variable blunt radii

NASA Astrophysics Data System (ADS)

Li, Shi-bin; Wang, Zhen-guo; Barakos, George N.; Huang, Wei; Steijl, Rene

2016-10-01

Waverider will endure the huge aero-heating in the hypersonic flow, thus, it need be blunt for the leading edge. However, the aerodynamic performance will decrease for the blunt waverider because of the drag hoik. How to improve the aerodynamic performance and reduce the drag and aero-heating is very important. The variable blunt radii method will improve the aerodynamic performance, however, the huge aero-heating and bow shock wave at the head is still serious. In the current study, opposing jet is used in the waverider with variable blunt radii to improve its performance. The three-dimensional coupled implicit Reynolds-averaged Navier-Stokes(RANS) equation and the two equation SST k-ω turbulence model have been utilized to obtain the flow field properties. The numerical method has been validated against the available experimental data in the open literature. The obtained results show that the L/D will drop 7-8% when R changes from 2 to 8. The lift coefficient will increase, and the drag coefficient almost keeps the same when the variable blunt radii method is adopted, and the L/D will increase. The variable blunt radii method is very useful to improve the whole characteristics of blunt waverider and the L/D can improve 3%. The combination of the variable blunt radii method and opposing jet is a novel way to improve the whole performance of blunt waverider, and L/D can improve 4-5%. The aperture as a novel way of opposing jet is suitable for blunt waverider and also useful to improve the aerodynamic and aerothermodynamic characteristics of waverider in the hypersonic flow. There is the optimal P0in/P0 that can make the detached shock wave reattach the lower surface again so that the blunt waverider can get the better aerodynamic performance.

The two radii of a charged particle.

PubMed

Michov, B M

1989-01-01

The existence of two radii of each charged particle-a geometric and electrokinetic radii, is supposed. The mathematical relationship between them in the four possible combinations of an ion and its counterion is analyzed: (i) at equal geometric radii and, in absolute values, equal valencies; (ii) at equal geometric radii and, in absolute values, different valencies; (iii) at different geometric radii and, in absolute values, equal valencies; (iv) at different geometric radii and, in absolute values, different valencies. One of the equations worked out can be used to define the relationship between the geometric and electrokinetic radii of a polyion. All the equations are used in working out precise calculations.

Correlation between ionic size and valence state of tetra, penta and hexavalent B-site substitution with solubility limit, phase transformation and multiferroic properties of Bi0.875Eu0.125FeO3

NASA Astrophysics Data System (ADS)

Mumtaz, Fiza; Jaffari, G. Hassnain; Hassan, Qadeer ul; Shah, S. Ismat

2018-06-01

We present detailed comparative study of effect of isovalent i.e. Eu+3 substitution at A-site and tetra (Ti+4, Zr+4), penta (V+5) and hexavalent (W+6) substitutions at B-site in BiFeO3. Eu+3 substitution led to phase transformation and exhibited mixed phases i.e. rhombohedral and orthorhombic, while tetravalent substituents (Ti+4 and Zr+4) led to stabilization of cubic phase. In higher valent (i.e. V+5 and W+6) cases solubility limit was significantly reduced where orthorhombic phase was observed as in the case of parent compound. Phase transformation as a consequence of increase in microstrain and chemical pressure induced by the substituent has been discussed. Solubility limit of different B-site dopants i.e. Zr, W and V was extracted to 5%, 2% and 2%, respectively. Extra phases in various cases were Bi2Fe4O9, Bi25FeO40, Bi14W2O27, and Bi23V4O44.5 and their fractional amount have been quantified. Ti was substituted up to 15% and has been observed to be completely soluble in the parent compound. Solubility limits depends on ionic radii mismatch and valance difference of Fe+3 and dopant, in which valance difference plays more dominant role. Solubility limit and phase transformation has been explained in terms of change in bond strength and tolerance factor induced by incorporation of dopant which depend on its size and valence state. Detail optical, dielectric, ferroelectric, magnetic and transport properties of Eu and Ti co-doped samples and selected low concentration B-site doped compositions (i.e. 2%) have presented and discussed. Two d-d transitions and three charge transfer transitions were observed within UV-VIS range. Both change in cell volume for the same phase and transformation in crystal structure affects the band gap. Increase in room temperature dielectric constant and saturation polarization was also found to increase in case of Eu-Ti co-doped samples with increasing concentration of Ti. Substitution of Eu at A-site and Ti at B-site led to observation of weak ferromagnetism. Effect of extra phases on ferroelectricity and transport properties have also been discussed.

Morphological and electromechanical characterization of ionic liquid/Nafion polymer composites

NASA Astrophysics Data System (ADS)

Bennett, Matthew; Leo, Donald

2005-05-01

Ionic liquids have shown promise as replacements for water in ionic polymer transducers. Ionic liquids are non-volatile and have a larger electrochemical stability window than water. Therefore, transducers employing ionic liquids can be operated for long periods of time in air and can be actuated with higher voltages. Furthermore, transducers based on ionic liquids do not exhibit the characteristic back relaxation that is common with water-swollen materials. However, the physics of transduction in the ionic liquid-swollen materials is not well understood. In this paper, the morphology of Nafion/ionic liquid composites is characterized using small-angle X-ray scattering (SAXS). The electromechanical transduction behavior of the composites is also investigated. For this testing, five different counterions and two ionic liquids are used. The results reveal that both the morphology and transduction performance of the composites is affected by the identity of the ionic liquid, the cation, and the swelling level of ionic liquid within the membrane. Specifically, speed of response is found to be lower for the membranes that were exchanged with the smaller lithium and potassium ions. The response speed is also found to increase with increased content of ionic liquid. Furthermore, for the two ionic liquids studied, the actuators swollen with the less viscous ionic liquid exhibited a slower response. The slower speed of response corresponds to less contrast between the ionically conductive phase and the inert phase of the polymer. This suggests that disruption of the clustered morphology in the ionic liquid-swollen membranes as compared to water-swollen membranes attenuates ion mobility within the polymer. This attenuation is attributed to swelling of the non-conductive phase by the ionic liquids.

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.

Natural Indices for the Chemical Hardness/Softness of Metal Cations and Ligands

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

Xu, Huifang; Xu, David C.; Wang, Yifeng

Quantitative understanding of reactivity and stability for a chemical species is fundamental to chemistry. The concept has undergone many changes and additions throughout the history of chemistry, stemming from the ideas such as Lewis acids and bases. For a given complexing ligand (Lewis base) and a group of isovalent metal cations (Lewis acids), the stability constants of metal–ligand (ML) complexes can simply correlate to the known properties of metal ions [ionic radii (r Mn+), Gibbs free energy of formation (ΔG° f,Mn+), and solvation energy (ΔG° s,Mn+)] by 2.303RT log K ML = (α* MLΔG° f,Mn+ – β* MLr Mn+ +more » γ* MLΔG° s,Mn+ – δ* ML), where the coefficients (α* ML, β* ML, γ* ML, and intercept δ* ML) are determined by fitting the equation to the existing experimental data. Coefficients β* ML and γ* ML have the same sign and are in a linear relationship through the origin. Gibbs free energies of formation of cations (ΔG° f,Mn+) are found to be natural indices for the softness or hardness of metal cations, with positive values corresponding to soft acids and negative values to hard acids. The coefficient α* ML is an index for the softness or hardness of a complexing ligand. Proton (H +) with the softness index of zero is a unique acid that has strong interactions with both soft and hard bases. The stability energy resulting from the acid–base interactions is determined by the term α* MLΔG° f,Mn+; a positive product of α* ML and ΔG° f,Mn+ indicates that the acid–base interaction between the metal cation and the complexing ligand stabilizes the complex. The terms β* MLr Mn+ and γ* MLΔG° s,Mn+, which are related to ionic radii of metal cations, represent the steric and solvation effects of the cations. The new softness indices proposed here will help to understand the interactions of ligands (Lewis bases) with metal cations (Lewis acids) and provide guidelines for engineering materials with desired chemical reactivity and selectivity. As a result, the new correlation can also enhance our ability for predicting the speciation, mobility, and toxicity of heavy metals in the earth environments and biological systems.« less

Natural Indices for the Chemical Hardness/Softness of Metal Cations and Ligands

DOE PAGES

Xu, Huifang; Xu, David C.; Wang, Yifeng

2017-10-26

Quantitative understanding of reactivity and stability for a chemical species is fundamental to chemistry. The concept has undergone many changes and additions throughout the history of chemistry, stemming from the ideas such as Lewis acids and bases. For a given complexing ligand (Lewis base) and a group of isovalent metal cations (Lewis acids), the stability constants of metal–ligand (ML) complexes can simply correlate to the known properties of metal ions [ionic radii (r Mn+), Gibbs free energy of formation (ΔG° f,Mn+), and solvation energy (ΔG° s,Mn+)] by 2.303RT log K ML = (α* MLΔG° f,Mn+ – β* MLr Mn+ +more » γ* MLΔG° s,Mn+ – δ* ML), where the coefficients (α* ML, β* ML, γ* ML, and intercept δ* ML) are determined by fitting the equation to the existing experimental data. Coefficients β* ML and γ* ML have the same sign and are in a linear relationship through the origin. Gibbs free energies of formation of cations (ΔG° f,Mn+) are found to be natural indices for the softness or hardness of metal cations, with positive values corresponding to soft acids and negative values to hard acids. The coefficient α* ML is an index for the softness or hardness of a complexing ligand. Proton (H +) with the softness index of zero is a unique acid that has strong interactions with both soft and hard bases. The stability energy resulting from the acid–base interactions is determined by the term α* MLΔG° f,Mn+; a positive product of α* ML and ΔG° f,Mn+ indicates that the acid–base interaction between the metal cation and the complexing ligand stabilizes the complex. The terms β* MLr Mn+ and γ* MLΔG° s,Mn+, which are related to ionic radii of metal cations, represent the steric and solvation effects of the cations. The new softness indices proposed here will help to understand the interactions of ligands (Lewis bases) with metal cations (Lewis acids) and provide guidelines for engineering materials with desired chemical reactivity and selectivity. As a result, the new correlation can also enhance our ability for predicting the speciation, mobility, and toxicity of heavy metals in the earth environments and biological systems.« less

Highly efficient conductivity modulation of cinnamate-based light-responsive ionic liquids in aqueous solutions.

PubMed

Yang, Jie; Wang, Huiyong; Wang, Jianji; Zhang, Yue; Guo, Zhongjia

2014-12-11

A new class of cinnamate-based light-responsive ionic liquids was synthesized and characterized, and these ionic liquids with longer alkyl chains showed a remarkable increase in ionic conductivity under UV light irradiation in aqueous solutions.

Exploring the Cr{sup 2+} doping effect on structural, vibrational and dielectric properties of Mn-Zn ferrites

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

Choudhary, Pankaj; Dar, M. A.; Varshney, Dinesh, E-mail: vdinesh33@rediffmail.com, E-mail: ty.ru123@gmail.com

2016-05-23

A series of Cr doped Mn-Zn ferrites with compositional formula Mn{sub 0.5}Zn{sub 0.5-x}Cr{sub x}Fe{sub 2}O{sub 4} (x = 0, 0.3, 0.5) were prepared by solid-state reaction route. X-ray diffraction (XRD) analysis reveals that the samples prepared are polycrystalline cubic spinel in structure (Fd3m) with some secondary phase of α–Fe{sub 2}O{sub 3}. Slight variation in the lattice parameter of Cr doped Mn{sub 0.5}Zn{sub 0.5}Fe{sub 2}O{sub 4} has been observed due to difference in ionic radii of cations. Small shift in Raman modes towards higher wave number has been observed. Further the line width decreases with the doping ions. A giant dielectricmore » constant ~10{sup 4} is observed for parent Mn{sub 0.5}Zn{sub 0.5}Fe{sub 2}O{sub 4} which is found to decrease with increase in Cr{sup 2+} doping. Low dielectric loss is observed for Mn{sub 0.5}Zn{sub 0.5}Fe{sub 2}O{sub 4} and improves with Cr{sup 2+} doping at Zn{sup 2+} site.« less

Effect of Zn doping on structural and dielectric properties of tetragonal Ni{sub 1-x}Zn{sub x}Fe{sub 2}O{sub 4} (0.0 ≤ x ≤ 0.5)

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

Lone, S. A.; Dar, M. A.; Kumar, A.

2015-06-24

A series of Ni-Zn ferrite with compositional formula Ni{sub 1-x}Zn{sub x}Fe{sub 2}O{sub 4} (0.0 ≤ x ≤ 0.5) were prepared by solid-state reaction route. The influence of the Zn content on the structural and dielectric properties of NiFe{sub 2}O{sub 4} was investigated using X-ray powder diffraction (XRD), Raman spectroscopy and dielectric measurements. XRD analysis reveals that the samples are polycrystalline single-phase cubic spinel in structure excluding the presence of any secondary phase corresponding to any structure. Slight variation in the lattice parameter of Zn doped NiFe{sub 2}O{sub 4} has been observed due to difference in ionic radii of cations. Ramanmore » analysis reveals the doublet like nature of A{sub 1g} mode for all synthesized samples. Small shift in Raman modes and increment in the line width has been observed with the doping ions. Furthermore, room temperature dielectric properties of all the prepared samples have been reported. It is observed that for each sample the dielectric constant decreases with an increase of frequency and becomes constant at higher frequencies.« 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.

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

A New Class of Ternary Compound for Lithium-Ion Battery: from Composite to Solid Solution.

PubMed

Wang, Jiali; Wu, Hailong; Cui, Yanhua; Liu, Shengzhou; Tian, Xiaoqing; Cui, Yixiu; Liu, Xiaojiang; Yang, Yin

2018-02-14

Searching for high-performance cathode materials is a crucial task to develop advanced lithium-ion batteries (LIBs) with high-energy densities for electrical vehicles (EVs). As a promising lithium-rich material, Li 2 MnO 3 delivers high capacity over 200 mAh g -1 but suffers from poor structural stability and electronic conductivity. Replacing Mn 4+ ions by relatively larger Sn 4+ ions is regarded as a possible strategy to improve structural stability and thus cycling performance of Li 2 MnO 3 material. However, large difference in ionic radii of Mn 4+ and Sn 4+ ions leads to phase separation of Li 2 MnO 3 and Li 2 SnO 3 during high-temperature synthesis. To prepare solid-solution phase of Li 2 MnO 3 -Li 2 SnO 3 , a buffer agent of Ru 4+ , whose ionic radius is in between that of Mn 4+ and Sn 4+ ions, is introduced to assist the formation of a single solid-solution phase. The results show that the Li 2 RuO 3 -Li 2 MnO 3 -Li 2 SnO 3 ternary system evolves from mixed composite phases into a single solid-solution phase with increasing Ru content. Meanwhile, discharge capacity of this ternary system shows significantly increase at the transformation point which is ascribed to the improvement of Li + /e - transportation kinetics and anionic redox chemistry for solid-solution phase. The role of Mn/Sn molar ratio of Li 2 RuO 3 -Li 2 MnO 3 -Li 2 SnO 3 ternary system has also been studied. It is revealed that higher Sn content benefits cycling stability of the system because Sn 4+ ions with larger sizes could partially block the migration of Mn 4+ and Ru 4+ from transition metal layer to Li layer, thus suppressing structural transformation of the system from layered-to-spinel phase. These findings may enable a new route for exploring ternary or even quaternary lithium-rich cathode materials for LIBs.

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

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

Das, S.; Ghosh, A., E-mail: sspag@iacs.res.in

We have studied ionic conductivity and dielectric permittivity of PEO-LiClO{sub 4} solid polymer electrolyte plasticized with propylene carbonate. Differential scanning calorimetry and X-ray diffraction studies confirm minimum volume fraction of crystalline phase for the polymer electrolyte with 40 wt. % propylene carbonate. The ionic conductivity exhibits a maximum for the same composition. The temperature dependence of the ionic conductivity has been well interpreted using Vogel-Tamman-Fulcher equation. Ion-ion interactions in the polymer electrolytes have been studied using Raman spectra and the concentrations of free ions, ion-pairs and ion-aggregates have been determined. The ionic conductivity increases due to the increase of freemore » ions with the increase of propylene carbonate content. But for higher content of propylene carbonate, the ionic conductivity decreases due to the increase of concentrations of ion-pairs and ion-aggregates. To get further insights into the ion dynamics, the experimental data for the complex dielectric permittivity have been studied using Havriliak–Negami function. The variation of relaxation time with temperature obtained from this formalism follows Vogel-Tamman-Fulcher equation similar to the ionic conductivity.« less

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.

Crystal chemistry of M{sup II}M′{sup IV}(PO{sub 4}){sub 2} double monophosphates

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

Bregiroux, Damien, E-mail: damien.bregiroux@upmc.fr; Popa, Karin; Wallez, Gilles

2015-10-15

M{sup II}M′{sup IV}(PO{sub 4}){sub 2} compounds have been extensively studied for several decades for their potential applications in the field of several domains such as matrices for actinides conditioning, phosphors etc. In this paper, the relationships between composition and crystal structure of these compounds are established. A review of the various processes used for the synthesis of these compounds is also proposed, as well as their most reported properties. M{sup II}M′{sup IV}(PO{sub 4}){sub 2} structures stem from two different archetypes: the cheralite and the yavapaiite structures, with some exceptions that are also described in this article. The ratio of themore » cations radii appears to be the most relevant parameter. The high ratio between the ionic radii of the divalent and tetravalent cations in yavapaiite derivates results in the ordering of these cations into well-differentiated polyhedra whereas cheralite is the only non-ordered structure encountered for M{sup II}M′{sup IV}(PO{sub 4}){sub 2} compounds. - Graphical abstract: In this paper, the relationships between composition and crystal structure of M{sup II}M′{sup IV}(PO{sub 4}){sub 2} compounds are established. A review of the various processes used for the synthesis of these compounds is also proposed, as well as their most reported properties. - Highlights: • Crystal structure–composition relationships of MIIM′IV(PO4)2 compounds. • Review of the various processes used for the synthesis of these compounds. • Their most reported properties are described and discussed.« less

Broad hexagonal columnar mesophases formation in bioinspired transition-metal complexes of simple fatty acid meta-octaester derivatives of meso-tetraphenyl porphyrins.

PubMed

Wu, Bin; Chen, Keyang; Deng, Yuchen; Chen, Jian; Liu, Chengjie; Cheng, Rongshi; Chen, Dongzhong

2015-02-23

A series of meta-substituted fatty acid octaester derivatives and their transition-metal complexes of meso- tetraphenyl porphyrins (TPP-8OOCR, with R = C(n-1)H(2n-1), n = 8, 12, or 16) have been prepared through very simple synthesis protocols. The thermotropic phase behavior and the liquid crystalline (LC) organization structures of the synthesized porphyrin derivatives were systematically investigated by a combination of differential scanning calorimetry (DSC), polarized optical microscopy (POM), and variable-temperature small-angle X-ray scattering/wide-angle X-ray scattering (SAXS/WAXS) techniques. The shorter octanoic acid ester substituted porphyrin (C8-TPP) did not show liquid crystallinity and its metal porphyrins exhibited an uncommon columnar mesophase. The lauric acid octaester (C12-TPP) and the palmitic acid octaester (C16-TPP) series porphyrins generated hexagonal columnar mesophase Colh. Moreover, the metal porphyrins C12-TPPM and C16-TPPM with M = Zn, Cu, or Ni, exhibited well-organized Colh mesophases of broad LC temperature ranges increasing in the order of TPPNi

EXAFS analysis of cations distribution in structure of Co1-xNixFe2O4 nanoparticles obtained by hydrothermal method in aloe vera extract solution

NASA Astrophysics Data System (ADS)

Wongpratat, Unchista; Maensiri, Santi; Swatsitang, Ekaphan

2016-09-01

Effect of cations distribution upon EXAFS analysis on magnetic properties of Co1-xNixFe2O4 (x = 0, 0.25, 0.50, 0.75 and 1.0) nanoparticles prepared by the hydrothermal method in aloe vera extract solution were studied. XRD analysis confirmed a pure phase of cubic spinel ferrite of all samples. Changes in lattice parameter and particle size depended on the Ni content with partial substitution and site distributions of Co2+, Ni2+ ions of different ionic radii at both tetrahedral and octahedral sites in the crystal structure. Particle sizes of samples estimated by TEM images were found to be in the range of 10.87-62.50 nm. The VSM results at room temperature indicated the ferrimagnetic behavior of all samples. Superparamagnetic behavior was observed in NiFe2O4 sample. The coercivity (Hc) and remanance (Mr) values were related to the particle sizes of samples. The saturation magnetization (Ms) was increased by a factor of 1.4 to a value of 57.57 emu/g, whereas the coercivity (Hc) was decreased by a factor of 20 to a value of 63.15 Oe for a sample with x = 0.75. In addition to the cations distribution, the increase of aspect ratio (surface to volume ratio) due to the decrease of particle size could significantly affect the magnetic properties of the materials.

Bose-Einstein correlations in p p ,   p Pb , and PbPb collisions at s N N = 0.9 – 7 TeV

DOE PAGES

Sirunyan, A. M.; Tumasyan, A.; Adam, W.; ...

2018-06-14

Here, quantum-statistical (Bose-Einstein) two-particle correlations are measured in pp collisions at √s = 0.9, 2.76, and 7 TeV, as well as in pPb and peripheral PbPb collisions at nucleon-nucleon center-of-mass energies of 5.02 and 2.76 TeV, respectively, using the CMS detector at the Large Hadron Collider. Separate analyses are performed for same-sign unidentified charged particles as well as for same-sign pions and kaons identified via their energy loss in the silicon tracker. The characteristics of the one-, two-, and three-dimensional correlation functions are studied as functions of the pair average transverse momentum (k T) and the charged-particle multiplicity in themore » event. For all systems, the extracted correlation radii steadily increase with the event multiplicity, and decrease with increasing k T. The radii are in the range 1–5 fm, the largest values corresponding to very high multiplicity pPb interactions and to peripheral PbPb collisions with multiplicities similar to those seen in pPb data. It is also observed that the dependencies of the radii on multiplicity and k T largely factorize. At the same multiplicity, the radii are relatively independent of the colliding system and center-of-mass energy.« less

Bose-Einstein correlations in $$pp, p\\mathrm{Pb}$$, and PbPb collisions at $$\\sqrt{{s}_{NN}}=0.9-7$$ TeV

DOE PAGES

Sirunyan, Albert M; et al.

2018-06-15

Quantum-statistical (Bose-Einstein) two-particle correlations are measured in pp collisions at s=0.9, 2.76, and 7 TeV, as well as in pPb and peripheral PbPb collisions at nucleon-nucleon center-of-mass energies of 5.02 and 2.76 TeV, respectively, using the CMS detector at the Large Hadron Collider. Separate analyses are performed for same-sign unidentified charged particles as well as for same-sign pions and kaons identified via their energy loss in the silicon tracker. The characteristics of the one-, two-, and three-dimensional correlation functions are studied as functions of the pair average transverse momentum (kT) and the charged-particle multiplicity in the event. For all systems, the extractedmore » correlation radii steadily increase with the event multiplicity, and decrease with increasing kT. The radii are in the range 1–5 fm, the largest values corresponding to very high multiplicity pPb interactions and to peripheral PbPb collisions with multiplicities similar to those seen in pPb data. It is also observed that the dependencies of the radii on multiplicity and kT largely factorize. At the same multiplicity, the radii are relatively independent of the colliding system and center-of-mass energy.« less

Bose-Einstein correlations in $$pp, p\\mathrm{Pb}$$, and PbPb collisions at $$\\sqrt{{s}_{NN}}=0.9-7$$ TeV

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

Sirunyan, Albert M; et al.

Quantum-statistical (Bose-Einstein) two-particle correlations are measured in pp collisions at s=0.9, 2.76, and 7 TeV, as well as in pPb and peripheral PbPb collisions at nucleon-nucleon center-of-mass energies of 5.02 and 2.76 TeV, respectively, using the CMS detector at the Large Hadron Collider. Separate analyses are performed for same-sign unidentified charged particles as well as for same-sign pions and kaons identified via their energy loss in the silicon tracker. The characteristics of the one-, two-, and three-dimensional correlation functions are studied as functions of the pair average transverse momentum (kT) and the charged-particle multiplicity in the event. For all systems, the extractedmore » correlation radii steadily increase with the event multiplicity, and decrease with increasing kT. The radii are in the range 1–5 fm, the largest values corresponding to very high multiplicity pPb interactions and to peripheral PbPb collisions with multiplicities similar to those seen in pPb data. It is also observed that the dependencies of the radii on multiplicity and kT largely factorize. At the same multiplicity, the radii are relatively independent of the colliding system and center-of-mass energy.« less

Bose-Einstein correlations in p p ,   p Pb , and PbPb collisions at s N N = 0.9 – 7 TeV

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

Sirunyan, A. M.; Tumasyan, A.; Adam, W.

Here, quantum-statistical (Bose-Einstein) two-particle correlations are measured in pp collisions at √s = 0.9, 2.76, and 7 TeV, as well as in pPb and peripheral PbPb collisions at nucleon-nucleon center-of-mass energies of 5.02 and 2.76 TeV, respectively, using the CMS detector at the Large Hadron Collider. Separate analyses are performed for same-sign unidentified charged particles as well as for same-sign pions and kaons identified via their energy loss in the silicon tracker. The characteristics of the one-, two-, and three-dimensional correlation functions are studied as functions of the pair average transverse momentum (k T) and the charged-particle multiplicity in themore » event. For all systems, the extracted correlation radii steadily increase with the event multiplicity, and decrease with increasing k T. The radii are in the range 1–5 fm, the largest values corresponding to very high multiplicity pPb interactions and to peripheral PbPb collisions with multiplicities similar to those seen in pPb data. It is also observed that the dependencies of the radii on multiplicity and k T largely factorize. At the same multiplicity, the radii are relatively independent of the colliding system and center-of-mass energy.« less

Measurements of the Total Reaction Cross Sections for 6,8He and 8,9Li Nuclei with Energies of (25-45)A Mev on natAl, natTa and natPb

NASA Astrophysics Data System (ADS)

Erdemchimeg, B.; Artukh, A. G.; Klygin, S. A.; Kononenko, G. A.; Kyslukha, D. A.; Sereda, Yu. M.; Vorontzov, A. N.; Lukyanov, S. M.; Penionzhkevich, Yu. E.; Davaa, S.; Khuukhenkhuu, G.; Borcea, C.; Rotaru, F.; Stanoiu, M.; Martina, L.; Saillant, F.; Raine, B.

2015-06-01

The total nuclear reaction cross sections (σR) measurements have long been of interest since they tell us about the radii and transparency of these nuclei and give clues to understanding of their structure. For studies of unstable nuclei, in particular the physical properties of halo nuclei and the neutron skin thickness, it is valuable to know not only the root-mean-square radii (rms) but it is important to know the details of nucleusnucleus potentials. Our goal was to study total reaction cross sections (σR) by a direct measurement technique (the so-called beam attenuation or transmission method) which allows to extract model independent information. The interaction radii for 6He, 8,9Li were extracted, which are in agreement with the previous measurement at the similar energies (about a few tens of AMeV) Our results show a tendency of increasing radii as function of mass of the secondary targets.

Solubilization of octane in cationic surfactant-anionic polymer complexes: Effect of ionic strength.

PubMed

Zhang, Hui; Deng, Lingli; Sun, Ping; Que, Fei; Weiss, Jochen

2016-01-01

Polymers may alter the ability of oppositely charged surfactant micelles to solubilize hydrophobic molecules depending on surfactant-polymer interactions. This study was conducted to investigate the effect of ionic strength on the solubilization thermodynamics of an octane oil-in-water emulsion in mixtures of an anionic polymer (carboxymethyl cellulose) and cationic cetyltrimethylammonium bromide (CTAB) surfactant micelles using isothermal titration calorimetry (ITC). Results indicated that the CTAB binding capacity of carboxymethyl cellulose increased with increasing NaCl concentrations up to 100 mM, and the thermodynamic behavior of octane solubilization in CTAB micelles, either in the absence or presence of polymer, was found to have a strong dependence on ionic strength. The increasing ionic strength caused the solubilization in CTAB micelles to be less endothermic or even exothermic, but increased the solubilization capacity. Based on the phase separation model, the solubilization was suggested to be driven by enthalpy. It is indicated that increasing ionic strength gave rise to a larger Gibbs energy decrease but a smaller unfavorable entropy increase for octane solubilization in cationic surfactant micelles. Copyright © 2015 Elsevier Inc. All rights reserved.

Ionic Liquids in Electro-active Devices (ILED)

DTIC Science & Technology

2013-12-12

Polyesters: Structure-Property Relationships in Thermal Behavior, Ionic Conductivity , and Morphology , Advanced Functional Materials, (01 2010...and Ionic Conductivities , Macromolecular Chemistry and Physics, (10 2011): . doi: M. Green, C. Schreiner, T. Long. Thermal , Rheological, and Ion...block giving thermal stability and ionic conductivity . Table 1 shows the molecular weight analysis of the triblock copolymers with increasing

The effect of pH and ionic strength of dissolution media on in-vitro release of two model drugs of different solubilities from HPMC matrices.

PubMed

Asare-Addo, Kofi; Conway, Barbara R; Larhrib, Hassan; Levina, Marina; Rajabi-Siahboomi, Ali R; Tetteh, John; Boateng, Joshua; Nokhodchi, Ali

2013-11-01

The evaluation of the effects of different media ionic strengths and pH on the release of hydrochlorothiazide, a poorly soluble drug, and diltiazem hydrochloride, a cationic and soluble drug, from a gel forming hydrophilic polymeric matrix was the objective of this study. The drug to polymer ratio of formulated tablets was 4:1. Hydrochlorothiazide or diltiazem HCl extended release (ER) matrices containing hypromellose (hydroxypropyl methylcellulose (HPMC)) were evaluated in media with a pH range of 1.2-7.5, using an automated USP type III, Bio-Dis dissolution apparatus. The ionic strength of the media was varied over a range of 0-0.4M to simulate the gastrointestinal fed and fasted states and various physiological pH conditions. Sodium chloride was used for ionic regulation due to its ability to salt out polymers in the midrange of the lyotropic series. The results showed that the ionic strength had a profound effect on the drug release from the diltiazem HCl K100LV matrices. The K4M, K15M and K100M tablets however withstood the effects of media ionic strength and showed a decrease in drug release to occur with an increase in ionic strength. For example, drug release after the 1h mark for the K100M matrices in water was 36%. Drug release in pH 1.2 after 1h was 30%. An increase of the pH 1.2 ionic strength to 0.4M saw a reduction of drug release to 26%. This was the general trend for the K4M and K15M matrices as well. The similarity factor f2 was calculated using drug release in water as a reference. Despite similarity occurring for all the diltiazem HCl matrices in the pH 1.2 media (f2=64-72), increases of ionic strength at 0.2M and 0.4M brought about dissimilarity. The hydrochlorothiazide tablet matrices showed similarity at all the ionic strength tested for all polymers (f2=56-81). The values of f2 however reduced with increasing ionic strengths. DSC hydration results explained the hydrochlorothiazide release from their HPMC matrices. There was an increase in bound water as ionic strengths increased. Texture analysis was employed to determine the gel strength and also to explain the drug release for the diltiazem hydrochloride. This methodology can be used as a valuable tool for predicting potential ionic effects related to in vivo fed and fasted states on drug release from hydrophilic ER matrices. Copyright © 2013 Elsevier B.V. All rights reserved.

RE-INFLATED WARM JUPITERS AROUND RED GIANTS

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

Lopez, Eric D.; Fortney, Jonathan J.

2016-02-10

Since the discovery of the first transiting hot Jupiters, models have sought to explain the anomalously large radii of highly irradiated gas giants. We now know that the size of hot Jupiter radius anomalies scales strongly with a planet's level of irradiation and numerous models like tidal heating, ohmic dissipation, and thermal tides have since been developed to help explain these inflated radii. In general, however, these models can be grouped into two broad categories: models that directly inflate planetary radii by depositing a fraction of the incident irradiation into the interior and models that simply slow a planet's radiativemore » cooling, allowing it to retain more heat from formation and thereby delay contraction. Here we present a new test to distinguish between these two classes of models. Gas giants orbiting at moderate orbital periods around post-main-sequence stars will experience enormous increases to their irradiation as their host stars move up the sub-giant and red-giant branches. If hot Jupiter inflation works by depositing irradiation into the planet's deep interiors then planetary radii should increase in response to the increased irradiation. This means that otherwise non-inflated gas giants at moderate orbital periods of >10 days can re-inflate as their host stars evolve. Here we explore the circumstances that can lead to the creation of these “re-inflated” gas giants and examine how the existence or absence of such planets can be used to place unique constraints on the physics of the hot Jupiter inflation mechanism. Finally, we explore the prospects for detecting this potentially important undiscovered population of planets.« less

High-energy X-ray powder diffraction and atomic-pair distribution-function studies of charged/discharged structures in carbon-hybridized Li2MnSiO4 nanoparticles as a cathode material for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Moriya, Maki; Miyahara, Masahiko; Hokazono, Mana; Sasaki, Hirokazu; Nemoto, Atsushi; Katayama, Shingo; Akimoto, Yuji; Hirano, Shin-ichi; Ren, Yang

2014-10-01

The stable cycling performance with a high discharge capacity of ∼190 mAh g-1 in a carbon-hybridized Li2MnSiO4 nanostructured powder has prompted an experimental investigation of the charged/discharged structures using synchrotron-based and laboratory-based X-rays and atomic-pair distribution-function (PDF) analyses. A novel method of in-situ spray pyrolysis of a precursor solution with glucose as a carbon source enabled the successful synthesis of the carbon-hybridized Li2MnSiO4 nanoparticles. The XRD patters of the discharged (lithiated) samples exhibit a long-range ordered structure characteristic of the (β) Li2MnSiO4 crystalline phase (space group Pmn21) which dissipates in the charged (delithiated) samples. However, upon discharging the long-range ordered structure recovers in each cycle. The disordered structure, according to the PDF analysis, is mainly due to local distortions of the MnO4 tetrahedra which show a mean Mn-O nearest neighbor distance shorter than that of the long-range ordered phase. These results corroborate the notion of the smaller Mn3+/Mn4+ ionic radii in the Li extracted phase versus the larger Mn2+ ionic radius in Li inserted phase. Thus Li extraction/insertion drives the fluctuation between the disordered and the long-range ordered structures.

Electron detachment energies in high-symmetry alkali halide solvated-electron anions

NASA Astrophysics Data System (ADS)

Anusiewicz, Iwona; Berdys, Joanna; Simons, Jack; Skurski, Piotr

2003-07-01

We decompose the vertical electron detachment energies (VDEs) in solvated-electron clusters of alkali halides in terms of (i) an electrostatic contribution that correlates with the dipole moment (μ) of the individual alkali halide molecule and (ii) a relaxation component that is related to the polarizability (α) of the alkali halide molecule. Detailed numerical ab initio results for twelve species (MX)n- (M=Li,Na; X=F,Cl,Br; n=2,3) are used to construct an interpolation model that relates the clusters' VDEs to their μ and α values as well as a cluster size parameter r that we show is closely related to the alkali cation's ionic radius. The interpolation formula is then tested by applying it to predict the VDEs of four systems [i.e., (KF)2-, (KF)3-, (KCl)2-, and (KCl)3-] that were not used in determining the parameters of the model. The average difference between the model's predicted VDEs and the ab initio calculated electron binding energies is less than 4% (for the twelve species studied). It is concluded that one can easily estimate the VDE of a given high-symmetry solvated electron system by employing the model put forth here if the α, μ and cation ionic radii are known. Alternatively, if VDEs are measured for an alkali halide cluster and the α and μ values are known, one can estimate the r parameter, which, in turn, determines the "size" of the cluster anion.

Advances in the analysis of biological samples using ionic liquids.

PubMed

Clark, Kevin D; Trujillo-Rodríguez, María J; Anderson, Jared L

2018-02-12

Ionic liquids are a class of solvents and materials that hold great promise in bioanalytical chemistry. Task-specific ionic liquids have recently been designed for the selective extraction, separation, and detection of proteins, peptides, nucleic acids, and other physiologically relevant analytes from complex biological samples. To facilitate rapid bioanalysis, ionic liquids have been integrated in miniaturized and automated procedures. Bioanalytical separations have also benefited from the modification of nonspecific magnetic materials with ionic liquids or the implementation of ionic liquids with inherent magnetic properties. Furthermore, the direct detection of the extracted molecules in the analytical instrument has been demonstrated with structurally tuned ionic liquids and magnetic ionic liquids, providing a significant advantage in the analysis of low-abundance analytes. This article gives an overview of these advances that involve the application of ionic liquids and derivatives in bioanalysis. Graphical abstract Ionic liquids, magnetic ionic liquids, and ionic liquid-based sorbents are increasing the speed, selectivity, and sensitivity in the analysis of biological samples.

Ionic bonding of lanthanides, as influenced by d- and f-atomic orbitals, by core-shells and by relativity.

PubMed

Ji, Wen-Xin; Xu, Wei; Schwarz, W H Eugen; Wang, Shu-Guang

2015-03-15

Lanthanide trihalide molecules LnX3 (X = F, Cl, Br, I) were quantum chemically investigated, in particular detail for Ln = Lu (lutetium). We applied density functional theory (DFT) at the nonrelativistic and scalar and SO-coupled relativistic levels, and also the ab initio coupled cluster approach. The chemically active electron shells of the lanthanide atoms comprise the 5d and 6s (and 6p) valence atomic orbitals (AO) and also the filled inner 4f semivalence and outer 5p semicore shells. Four different frozen-core approximations for Lu were compared: the (1s(2) -4d(10) ) [Pd] medium core, the [Pd+5s(2) 5p(6) = Xe] and [Pd+4f(14) ] large cores, and the [Pd+4f(14) +5s(2) 5p(6) ] very large core. The errors of LuX bonding are more serious on freezing the 5p(6) shell than the 4f(14) shell, more serious upon core-freezing than on the effective-core-potential approximation. The LnX distances correlate linearly with the AO radii of the ionic outer shells, Ln(3+) -5p(6) and X(-) -np(6) , characteristic for dominantly ionic Ln(3+) -X(-) binding. The heavier halogen atoms also bind covalently with the Ln-5d shell. Scalar relativistic effects contract and destabilize the LuX bonds, spin orbit coupling hardly affects the geometries but the bond energies, owing to SO effects in the free atoms. The relativistic changes of bond energy BE, bond length Re , bond force k, and bond stretching frequency vs do not follow the simple rules of Badger and Gordy (Re ∼BE∼k∼vs ). The so-called degeneracy-driven covalence, meaning strong mixing of accidentally near-degenerate, nearly nonoverlapping AOs without BE contribution is critically discussed. © 2015 Wiley Periodicals, Inc.

Hg⁰ removal from flue gas by ionic liquid/H₂O₂.

PubMed

Cheng, Guangwen; Bai, Bofeng; Zhang, Qiang; Cai, Ming

2014-09-15

1-Alkyl-3-methylimidazolium chloride ionic liquids ([Cnmim] Cl, n=4, 6, 8) were prepared. The ionic liquid was then mixed with hydrogen peroxide (H2O2) to form an absorbent. The Hg(0) removal performance of the absorbent was investigated in a gas/liquid scrubber using simulated flue gas. It was found that the ionic liquid/H2O2 mixture was an excellent absorbent and could be used to remove Hg(0) from flue gas. When the mass ratio of H2O2 to ionic liquid was 0.5, the absorbent showed high Hg(0) removal efficiency (up to 98%). The Hg(0) removal efficiency usually increased with the absorption temperature, while decreased with the increase of alkyl chain length in ionic liquid molecule. The Hg(0) removal mechanism involved with Hg(0) oxidation by H2O2 and Hg(2+) transfer from aqueous phase to ionic liquid phase. Copyright © 2014 Elsevier B.V. All rights reserved.

Oxygen, water, and sodium chloride transport in soft contact lenses materials.

PubMed

Gavara, Rafael; Compañ, Vicente

2017-11-01

Oxygen permeability, diffusion coefficient of the sodium ions and water flux and permeability in different conventional hydrogel (Hy) and silicone-hydrogel (Si-Hy) contact lenses have been measured experimentally. The results showed that oxygen permeability and transmissibility requirements of the lens have been addressed through the use of siloxane containing hydrogels. In general, oxygen and sodium chloride permeability values increased with the water content of the lens but there was a percolation phenomenon from a given value of water uptake mainly in the Si-Hy lenses which appeared to be related with the differences between free water and bound water contents. The increase of ion permeability with water content did not follow a unique trend indicating a possible dependence of the chemical structure of the polymer and character ionic and non-ionic of the lens. Indeed, the salt permeability values for silicone hydrogel contact lenses were one order of magnitude below those of conventional hydrogel contact lenses, which can be explained by a diffusion of sodium ions occurring only through the hydrophilic channels. The increase of the ionic permeability in Si-Hy materials may be due to the confinement of ions in nanoscale water channels involving possible decreased degrees of freedom for diffusion of both water and ions. In general, ionic lenses presented values of ionic permeability and diffusivity higher than most non-ionic lenses. The tortuosity of the ionic lenses is lower than the non-ionic Si-Hy lenses. Frequency 55 and PureVision exhibited the highest water permeability and flux values and, these parameters were greater for ionic Si-Hy lenses than for ionic conventional hydrogel lenses. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 2218-2231, 2017. © 2016 Wiley Periodicals, Inc.

Specialist gelator for ionic liquids.

PubMed

Hanabusa, Kenji; Fukui, Hiroaki; Suzuki, Masahiro; Shirai, Hirofusa

2005-11-08

Cyclo(l-beta-3,7-dimethyloctylasparaginyl-L-phenylalanyl) (1) and cyclo(L-beta-2-ethylhexylasparaginyl-L-phenylalanyl) (2), prepared from L-asparaginyl-L-phenylalanine methyl ester, have been found to be specialist gelators for ionic liquids. They can gel a wide variety of ionic liquids, including imizazolium, pyridinium, pyrazolidinium, piperidinium, morpholinium, and ammonium salts. The mean minimum gel concentrations (MGCs) necessary to make gels at 25 degrees C were determined for ionic liquids. The gel strength increased at a rate nearly proportional to the concentration of added gelator. The strength of the transparent gel of 1-butylpyridinium tetrafluoroborate ([C(4)py]BF(4)), prepared at a concentration of 60 g L(-1) (gelator 1/[C(4)py]BF(4)), was ca. 1500 g cm(-2). FT-IR spectroscopy indicated that a driving force for gelation was intermolecular hydrogen bonding between amides and that the phase transition from gel to liquid upon heating was brought about by the collapse of hydrogen bonding. The gels formed from ionic liquids were very thermally stable; no melting occurs up to 140 degrees C when the gels were prepared at a concentration of 70 g L(-1) (gelator/ionic liquid). The ionic conductivities of the gels were nearly the same as those of pure ionic liquids. The gelator had electrochemical stability and a wide electrochemical window. When the gels were prepared from ionic liquids containing propylene carbonate, the ionic conductivities of the resulting gels increased to levels rather higher than those of pure ionic liquids. The gelators also gelled ionic liquids containing supporting electrolytes.

Synthesis of new solid polymer electrolyte and actuator based on PEDOT/NBR/ionic liquid

NASA Astrophysics Data System (ADS)

Cho, M. S.; Seo, H. J.; Nam, J. D.; Choi, H. R.; Koo, J. C.; Lee, Y.

2006-03-01

The conducting polymer actuator was presented. The solid polymer electrolyte based on nitrile rubber (NBR) activated with different ionic liquids was prepared. The three different grades of NBR films were synthesized by emulsion polymerization with different amount of acrylonitrile, 23, 35, and 40 mol. %, respectively. The effect of acrylonitrile content on the ionic conductivity and dielectric constant of solid polymer electrolytes was characterized. A conducting polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), was synthesized on the surface of the NBR layer by using a chemical oxidation polymerization technique, and room temperature ionic liquids (RTIL) based on imidazolium salts, e.g. 1-butyl-3-methyl imidazolium X [where X= BF 4 -, PF 6 -, (CF 3SO II) IIN -], were absorbed into the composite film. The effects of the anion size of the ionic liquids on the displacement of the actuator were examined. The displacement increased with increasing the anion-size of the ionic liquids.

Ionic Liquids for Advanced Materials

DTIC Science & Technology

2008-12-01

optical clarity to completely opacity with increased amounts of ionic liquid . This transition was not previously observed in Nafion ® membranes swollen...1 IONIC LIQUIDS FOR ADVANCED MATERIALS Timothy E. Long, Sean M. Ramirez, Randy Heflin, Harry W. Gibson, Louis A. Madsen, Donald J. Leo, Nakhiah...is to develop a micromechanical model for the electrochemomechanical transduction mechanisms in newly synthesized ionic liquid polymers in order to

Electropolymerized polyazulene as active material in flexible supercapacitors

NASA Astrophysics Data System (ADS)

Suominen, Milla; Lehtimäki, Suvi; Yewale, Rahul; Damlin, Pia; Tuukkanen, Sampo; Kvarnström, Carita

2017-07-01

We report the capacitive behavior of electrochemically polymerized polyazulene films in different ionic liquids. The ionic liquids in this study represent conventional imidazolium based ionic liquids with tetrafluoroborate and bis(trifluoromethylsulfonyl)imide anions as well as an unconventional choline based ionic liquid. The effect of different ionic liquids on the polymerization and capacitive performance of polyazulene films is demonstrated by cyclic voltammetry and electrochemical impedance spectroscopy in a 3-electrode cell configuration. The films exhibit the highest capacitances in the lowest viscosity ionic liquid (92 mF cm-2), while synthesis in high viscosity ionic liquid shortens the conjugation length and results in lower electroactivity (25 mF cm-2). The obtained films also show good cycling stabilities retaining over 90% of their initial capacitance over 1200 p-doping cycles. We also demonstrate, for the first time, flexible polyazulene supercapacitors of symmetric and asymmetric configurations using the choline based ionic liquid as electrolyte. In asymmetric configuration, capacitance of 55 mF (27 mF cm-2) with an equivalent series resistance of 19 Ω is obtained at operating voltage of 1.5 V. Upon increasing the operating voltage up to 2.4 V, the capacitance increases to 72 mF (36 mF cm-2).

Effect of Cerium(III) and ionic liquids on the clouding behavior of Triton X-100 micelles

NASA Astrophysics Data System (ADS)

Sen, Indrani Das; Negi, Charu; Jayaram, Radha V.

2018-04-01

In the present study, the effect of Ce(III) on the clouding behavior of Triton X-100 has been investigated in the presence and absence of imidazolium based ionic liquids of varying chain length and counter ions. Thermodynamic parameters of clouding were calculated to comprehend the underlying interactions between the surfactant and the additives. The cloud point (CP) of Triton X-100 was found to increase with the concentration of Ce(III) and that of the ionic liquids studied. This increase of CP reflects the solubilization of the ionic liquids in the micellar solution1.

Ion-Transport Design for High-Performance Na+-Based Electrochromics.

PubMed

Li, Ran; Li, Kerui; Wang, Gang; Li, Lei; Zhang, Qiangqiang; Yan, Jinhui; Chen, Yao; Zhang, Qinghong; Hou, Chengyi; Li, Yaogang; Wang, Hongzhi

2018-04-24

Sodium ion (Na + )-based electrochemical systems have been extensively investigated in batteries and supercapacitors and also can be quality candidates for electrochromic (EC) devices. However, poor diffusion kinetics and severe EC performance degradation occur during the intercalation/deintercalation processes because the ionic radii of Na + are larger than those of conventional intercalation ions. Here, through intentional design of ion-transport channels in metal-organic frameworks (MOFs), Na + serves as an efficient intercalation ion for incorporation into a nanostructured electrode with a high diffusion coefficient of approximately 10 -8 cm 2 s -1 . As a result, the well-designed MOF-based EC device demonstrates desirable Na + EC performance, including fast switching speed, multicolor switching, and high stability. A smart "quick response code" display is fabricated using a mask-free laser writing method for application in the "Internet of Things". In addition, the concept of ion transport pathway design can be widely adopted for fabricating high-performance ion intercalation materials and devices for consumer electronics.

Highly improved hydration level sensing properties of copper oxide films with sodium and potassium doping

NASA Astrophysics Data System (ADS)

Sahin, Bünyamin; Kaya, Tolga

2016-01-01

In this study, un-doped, Na-doped, and K-doped nanostructured CuO films were successfully synthesized by the successive ionic layer adsorption and reaction (SILAR) technique and then characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and current-voltage (I-V) measurements. Structural properties of the CuO films were affected from doping. The XRD pattern indicates the formation of polycrystalline CuO films with no secondary phases. Furthermore, doping affected the crystal structure of the samples. The optimum conductivity values for both Na and K were obtained at 4 M% doping concentrations. The comparative hydration level sensing properties of the un-doped, Na-doped, and K-doped CuO nanoparticles were also investigated. A significant enhancement in hydration level sensing properties was observed for both 4 M% Na and K-doped CuO films for all concentration levels. Detailed discussions were reported in the study regarding atomic radii, crystalline structure, and conductivity.

Examination of ionic wind and cathode sheath effects in a E-field premixed flame with ion density measurements

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

Jacobs, Stewart V., E-mail: svj0001@uah.edu; Xu, Kunning G., E-mail: gabe.xu@uah.edu

2016-04-15

The effect of the ionic wind on a premixed methane-air flame under a DC electric field is studied via mapping of the ion density with Langmuir probes. Ion densities were observed to increase near the burner with increasing electrode voltage up to 6 kV. Past this electrode supply voltage, ion densities ceased increasing and began to decline in some locations within the premixed flame. The increased ion density is caused by an increase in ionic wind force and cathode sheath thickness. The plateau in density is due to the cathode sheath fully encompassing the flame front which is the ion source,more » thereby collecting all ions in the flame. The spatial density data support the ionic wind hypothesis and provide further explanation of its limits based on the plasma sheath.« less

Effect of additives on the clouding and aggregation behavior of Triton X-100

NASA Astrophysics Data System (ADS)

Semwal, Divyam; Sen, Indrani Das; Jayaram, Radha V.

2018-04-01

The present study investigates the effect of additives such as CsNO3 and imidazolium ionic liquids on the cloud point (CP) of Triton X-100. Thermodynamic parameters of the clouding process were determined in order to understand the interactions. CP was found to increase with the increase in concentration of most of the ionic liquids studied. This increase of CP reflects the solubilization of the ionic liquids in the micellar phase1. The thermodynamic parameters on the introduction of CsNO3 in TX-100 - ionic liquid system helps in understanding the different interactions occurring in the system. All ΔG values for clouding were found to be positive and hence made the process non spontaneous.

Ion Conduction in Polymerized Ionic Liquids with Different Pendant Groups

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

Fan, Fei; Wang, Yangyang; Hong, Tao

2015-07-17

Polymerized ionic liquids (PolyILs) are promising candidates for energy storage and electrochemical devices applications. Understanding their ionic transport mechanism is the key for designing highly conductive PolyILs. By using broadband dielectric spectroscopy (BDS), rheology, and differential scanning calorimetry (DSC), a systematic study has been carried out to provide a better understanding of the ionic transport mechanism in PolyILs with different pendant groups. The variation of pendant groups results in different dielectric, mechanical, and thermal properties of these PolyILs. The Walden plot analysis shows that the data points for all these PolyILs fall above the ideal Walden line, and the deviationmore » from the ideal line increases upon approaching the glass transition temperature (T g). Moreover, the conductivity for these PolyILs at their Tgs are much higher than the usually reported value 10 15 S/cm for polymer electrolytes, in which the ionic transport is closely coupled to the segmental dynamics. These results indicate a decoupling of ionic conductivity from the segmental relaxation in these materials. The degree of decoupling increases with the increase of the fragility of polymer segmental relaxation. Finally, we relate this observation to a decrease in polymer packing efficiency with an increase in fragility.« less

Effect of Co2+ and Y3+ ions insertion on the microstructure development and magnetic properties of Ni0.5Zn0.5Fe2O4 powders synthesized using Co-precipitation method

NASA Astrophysics Data System (ADS)

Rashad, M. M.; Rayan, D. A.; Turky, A. O.; Hessien, M. M.

2015-01-01

Nanocrystalline Ni0.5Zn0.5-xCoxFe2-zYzO4 powders (x=0-0.3 and z from 0 to 0.3) have been synthesized via a facile co-precipitation technique. X-ray diffraction (XRD), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM) are utilized in order to study the effect of variation of cobalt and yttrium substitutions and its impact on crystalline size, lattice parameter, X-ray density, microstructure and magnetic properties of the formed powders. X-ray diffraction data indicated that, after doping, all samples consisted of the main spinel phase for the formed precursors precipitated at pH 10 annealed at 1000 oC for 2 h. The lattice parameter and the unit cell were decreased linearly with increasing Co content whereas they were increased with increasing the Y incorporation. Additionally, the porosity was increased with increasing Co concentration while it was decreased with increasing the Y insertion. The mean ionic radii and hopping and bond lengths was decreased with the value of Co2+ and they were increased with the value of Y3+ ion as well as both of Y3+ and Co2+ ions. The microstructures of the produced powders were found to be cubic like structure. The addition of Y3+ ion suppressed the grain size whereas addition of Co2+ ion enhanced the grain growth availably. An examination of the magnetic properties revealed an increase in saturation magnetization with increasing Co and Y concentrations incorporation up to x=0.3. Meanwhile, the formed powders exhibited superparamagnetic characteristics. A high saturation magnetization (77.0 emu/g) was achieved for Ni0.5Zn0.2Co0.3Fe2O4 sample annealed at 1000 oC for 2 h.

Tension in Skinned Frog Muscle Fibers in Solutions of Varying Ionic Strength and Neutral Salt Composition

PubMed Central

Gordon, A. M.; Godt, R. E.; Donaldson, S. K. B.; Harris, C. E.

1973-01-01

The maximal calcium-activated isometric tension produced by a skinned frog single muscle fiber falls off as the ionic strength of the solution bathing this fiber is elevated declining to zero near 0.5 M as the ionic strength is varied using KCl. When other neutral salts are used, the tension always declines at high ionic strength, but there is some difference between the various neutral salts used. The anions and cations can be ordered in terms of their ability to inhibit the maximal calcium-activated tension. The order of increasing inhibition of tension (decreasing tension) at high ionic strength for anions is propionate- ≃ SO4 -- < Cl- < Br-. The order of increasing inhibition of calcium-activated tension for cations is K+ ≃ Na+ ≃ TMA+ < TEA+ < TPrA+ < TBuA+. The decline of maximal calcium-activated isometric tension with elevated salt concentration (ionic strength) can quantitatively explain the decline of isometric tetanic tension of a frog muscle fiber bathed in a hypertonic solution if one assumes that the internal ionic strength of a muscle fiber in normal Ringer's solution is 0.14–0.17 M. There is an increase in the base-line tension of a skinned muscle fiber bathed in a relaxing solution (no added calcium and 3 mM EGTA) of low ionic strength. This tension, which has no correlate in the intact fiber in hypotonic solutions, appears to be a noncalcium-activated tension and correlates more with a declining ionic strength than with small changes in [MgATP], [Mg], pH buffer, or [EGTA]. It is dependent upon the specific neutral salts used with cations being ordered in increasing inhibition of this noncalcium-activated tension (decreasing tension) as TPrA+ < TMA+ < K+ ≃ Na+. Measurements of potentials inside these skinned muscle fibers bathed in relaxing solutions produced occasional small positive values (<6 mV) which were not significantly different from zero. PMID:4543066

Dye-sensitized solar cells using ionic liquids as redox mediator

NASA Astrophysics Data System (ADS)

Denizalti, Serpil; Ali, Abdulrahman Khalaf; Ela, Çağatay; Ekmekci, Mesut; Erten-Ela, Sule

2018-01-01

In this research, the influence of ionic liquid on the conversion efficiency, incident photons to converted electrons (IPCE) and performance of fabricated solar cell was investigated using various ionic liquids. Ionic liquids with different substituents and ions were prepared and used as redox mediators in dye-sensitized solar cells (DSSCs). Ionic liquids were characterized 1H and 13C NMR spectra. We practically investigated the performance of ionic liquid salts were used as the mobile ions and found that the efficiencies of DSSCs were increased up to 40% comparing commercial electrolyte system. The ionic liquid compounds were incorporated in DSSCs to obtain an efficient charge transfer, solving the corrosion problem of platinum layer in counter electrode compared to commercial electrolyte.

Monovalent Cation Doping of CH3NH3PbI3 for Efficient Perovskite Solar Cells.

PubMed

Abdi-Jalebi, Mojtaba; Dar, M Ibrahim; Sadhanala, Aditya; Senanayak, Satyaprasad P; Grätzel, Michael; Friend, Richard H

2017-03-19

Here, we demonstrate the incorporation of monovalent cation additives into CH3NH3PbI3 perovskite in order to adjust the optical, excitonic, and electrical properties. The possibility of doping was investigated by adding monovalent cation halides with similar ionic radii to Pb 2+ , including Cu + , Na + , and Ag + . A shift in the Fermi level and a remarkable decrease of sub-bandgap optical absorption, along with a lower energetic disorder in the perovskite, was achieved. An order-of-magnitude enhancement in the bulk hole mobility and a significant reduction of transport activation energy within an additive-based perovskite device was attained. The confluence of the aforementioned improved properties in the presence of these cations led to an enhancement in the photovoltaic parameters of the perovskite solar cell. An increase of 70 mV in open circuit voltage for AgI and a 2 mA/cm 2 improvement in photocurrent density for NaI- and CuBr-based solar cells were achieved compared to the pristine device. Our work paves the way for further improvements in the optoelectronic quality of CH3NH3PbI3 perovskite and subsequent devices. It highlights a new avenue for investigations on the role of dopant impurities in crystallization and controls the electronic defect density in perovskite structures.

Monovalent Cation Doping of CH3NH3PbI3 for Efficient Perovskite Solar Cells

PubMed Central

Abdi-Jalebi, Mojtaba; Dar, M. Ibrahim; Sadhanala, Aditya; Senanayak, Satyaprasad P.; Grätzel, Michael; Friend, Richard H.

2017-01-01

Here, we demonstrate the incorporation of monovalent cation additives into CH3NH3PbI3 perovskite in order to adjust the optical, excitonic, and electrical properties. The possibility of doping was investigated by adding monovalent cation halides with similar ionic radii to Pb2+, including Cu+, Na+, and Ag+. A shift in the Fermi level and a remarkable decrease of sub-bandgap optical absorption, along with a lower energetic disorder in the perovskite, was achieved. An order-of-magnitude enhancement in the bulk hole mobility and a significant reduction of transport activation energy within an additive-based perovskite device was attained. The confluence of the aforementioned improved properties in the presence of these cations led to an enhancement in the photovoltaic parameters of the perovskite solar cell. An increase of 70 mV in open circuit voltage for AgI and a 2 mA/cm2 improvement in photocurrent density for NaI- and CuBr-based solar cells were achieved compared to the pristine device. Our work paves the way for further improvements in the optoelectronic quality of CH3NH3PbI3 perovskite and subsequent devices. It highlights a new avenue for investigations on the role of dopant impurities in crystallization and controls the electronic defect density in perovskite structures. PMID:28362369

Proteins in Ionic Liquids: Current Status of Experiments and Simulations.

PubMed

Schröder, Christian

2017-04-01

In the last two decades, while searching for interesting applications of ionic liquids as potent solvents, their solvation properties and their general impact on biomolecules, and in particular on proteins, gained interest. It turned out that ionic liquids are excellent solvents for protein refolding and crystallization. Biomolecules showed increased solubilities and stabilities, both operational and thermal, in ionic liquids, which also seem to prevent self-aggregation during solubilization. Biomolecules can be immobilized, e.g. in highly viscous ionic liquids, for particular biochemical processes and can be designed to some extent by the proper choice of the ionic liquid cations and anions, which can be characterized by the Hofmeister series.

A new approach combining different MRI methods to provide detailed view on swelling dynamics of xanthan tablets influencing drug release at different pH and ionic strength.

PubMed

Mikac, Ursa; Sepe, Ana; Kristl, Julijana; Baumgartner, Sasa

2010-08-03

The key element in drug release from hydrophilic matrix tablets is the gel layer that regulates the penetration of water and controls drug dissolution and diffusion. We have selected magnetic resonance imaging (MRI) as the method of choice for visualizing the dynamic processes occurring during the swelling of xanthan tablets in a variety of media. The aims were (i) to develop a new method using MRI for accurate determination of penetration, swelling and erosion fronts, (ii) to investigate the effects of pH and ionic strength on swelling, and (iii) to study the influence of structural changes in xanthan gel on drug release. Two dimensional (2D) MRI and one dimensional single point imaging (SPI) of swollen xanthan tablets were recorded, together with T(2) mapping. The border between dry and hydrated glassy xanthan-the penetration front-was determined from 1D SPI signal intensity profiles. The erosion front was obtained from signal intensity profiles of 2D MR images. The swelling front, where xanthan is transformed from a glassy to a rubbery state (gel formation), was determined from T(2) profiles. Further, the new combination of MRI methods for swelling front determination enables to explain the appearance of the unusual "bright front" observed on 2D MR images in tablets swollen in HCl pH 1.2 media, which represents the position of swelling front. All six media studied, differing in pH and ionic strength, penetrate through the whole tablet in 4h+/-0.3h, but formation of the gel layer is significantly delayed. Unexpectedly, the position of the swelling front was the same, independently of the different xanthan gel structures formed under different conditions of pH and ionic strength. The position of the erosion front, on the other hand, is strongly dependent on pH and ionic strength, as reflected in different thicknesses of the gel layers. The latter are seen to be the consequence of the different hydrodynamic radii of the xanthan molecules, which affect the drug release kinetics. The slowest release of pentoxifylline was observed in water where the thickest gel was formed, whereas the fastest release was observed in HCl pH 1.2, in which the gel layer was thinnest. Moreover, experiments simulating physiological conditions showed that changes of pH and ionic strength influence the xanthan gel structure relatively quickly, and consequently the drug release kinetics. It is therefore concluded that drug release is greatly influenced by changes in the xanthan molecular conformation, as reflected in changed thickness of the gel layer. A new method utilizing combination of SPI, multi-echo MRI and T(2) mapping eliminates the limitations of standard methods used in previous studies for determining moving fronts and improves current understanding of the dynamic processes involved in polymer swelling. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Hybrid Perovskite Phase Transition and Its Ionic, Electrical and Optical Properties

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

Hoque, Md Nadim Ferdous; Islam, Nazifah; Zhu, Kai

Hybrid perovskite solar cells (PSCs) under normal operation will reach a temperature above ~ 60 °C, across the tetragonal-cubic structural phase transition of methylammonium lead iodide (MAPbI 3). Whether the structural phase transition could result in dramatic changes of ionic, electrical and optical properties that may further impact the PSC performances should be studied. Herein, we report a structural phase transition temperature of MAPbI 3thin film at ~ 55 °C, but a striking contrast occurred at ~ 45 °C in the ionic and electrical properties of MAPbI 3due to a change of the ion activation energy from 0.7 eV tomore » 0.5 eV. The optical properties exhibited no sharp transition except for the steady increase of the bandgap with temperature. It was also observed that the activation energy for ionic migration steadily increased with increased grain sizes, and reduction of the grain boundary density reduced the ionic migration.« less

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.

Structural characteristics of methylsilsesquioxane based porous low-k thin films fabricated with increasing cross-linked particle porogen loading

NASA Astrophysics Data System (ADS)

Lee, Hae-Jeong; Soles, Christopher L.; Liu, Da-Wei; Bauer, Barry J.; Lin, Eric K.; Wu, Wen-Li; Gallagher, Michael

2006-09-01

Methylsilsesquioxane (MSQ) based porous low-k dielectric films are characterized by x-ray porosimetry (XRP) to determine their pore size distribution, average density, wall density, and porosity. By varying the porogen content from 1% to 30% by mass, the porosity changes from 12% to 34% by volume, indicating that the base MSQ matrix material contains approximately 10% by volume inherent microporosity. The wall density of this matrix material is measured to be 1.33-1.35g/cm3, independent of porosity. The average pore radii determined from the XRP adsorption isotherms increase from 6to27Å with increased porogen loadings. Small angle neutron scattering measurements confirm these XRP average pore radii for the films with porogen loading higher than 10% by mass.

Solid solubility of Yb 2Si 2O 7 in β-, γ- and δ-Y 2Si 2O 7

NASA Astrophysics Data System (ADS)

Fernández-Carrión, A. J.; Alba, M. D.; Escudero, A.; Becerro, A. I.

2011-07-01

This paper examines the structural changes with temperature and composition in the Yb 2Si 2O 7-Y 2Si 2O 7 system; members of this system are expected to form in the intergranular region of Si 3N 4 and SiC structural ceramics when sintered with the aid of Yb 2O 3 and Y 2O 3 mixtures. A set of different compositions have been synthesised using the sol-gel method to obtain a xerogel, which has been calcined at temperatures between 1300 and 1650 °C during different times. Isotherms at 1300 and 1600 °C have been analysed in detail to evaluate the solid solubility of Yb 2Si 2O 7 in β-Y 2Si 2O 7 and γ-Y 2Si 2O 7. Although Yb 2Si 2O 7 shows a unique stable polymorph (β), Yb 3+ is able to replace Y 3+ in γ-Y 2Si 2O 7 and δ-Y 2Si 2O 7 at high temperatures and low Yb contents. IR results confirm the total solid solubility in the system and suggest a constant SiOSi angle of 180° in the Si 2O 7 unit across the system. The temperature-composition diagram of the system, obtained from powder XRD data, is dominated by the β- RE2Si 2O 7 polymorph, with γ- RE2Si 2O 7 and δ- RE2Si 2O 7 showing reduced stability fields. The diagram is in accordance with Felsche's diagram if average ionic radii are assumed for the members of the solid solution at any temperature, as long as the β-γ phase boundary is slightly shifted towards higher radii.

The effect of addition of primary positive salts, complex salt, on the ionic strength and rate constant at various temperatures by reaction kinetics

NASA Astrophysics Data System (ADS)

Kurade, S. S.; Ramteke, A. A.

2018-05-01

In this work, we have investigated the rate of reaction by using ionic strength at different temperatures. The main goal of this experiment is to determine the relation between ionic strength with reaction rate, reaction time and rate constant with temperature. It is observed that the addition of positive salt indicate the increasing ionic strength with increase in run time at various temperatures. Thus the temperature affects the speed of reaction and mechanism by which chemical reaction occurs and time variable plays vital role in the progress of reaction at different temperatures.

Structure-Antibacterial Activity Relationships of Imidazolium-Type Ionic Liquid Monomers, Poly(ionic liquids) and Poly(ionic liquid) Membranes: Effect of Alkyl Chain Length and Cations.

PubMed

Zheng, Zhiqiang; Xu, Qiming; Guo, Jiangna; Qin, Jing; Mao, Hailei; Wang, Bin; Yan, Feng

2016-05-25

The structure-antibacterial activity relationship between the small molecular compounds and polymers are still elusive. Here, imidazolium-type ionic liquid (IL) monomers and their corresponding poly(ionic liquids) (PILs) and poly(ionic liquid) membranes were synthesized. The effect of chemical structure, including carbon chain length of substitution at the N3 position and charge density of cations (mono- or bis-imidazolium) on the antimicrobial activities against both Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) was investigated by determination of minimum inhibitory concentration (MIC). The antibacterial activities of both ILs and PILs were improved with the increase of the alkyl chain length and higher charge density (bis-cations) of imidazolium cations. Moreover, PILs exhibited lower MIC values relative to the IL monomers. However, the antibacterial activities of PIL membranes showed no correlation to those of their analogous small molecule IL monomers and PILs, which increased with the charge density (bis-cations) while decreasing with the increase of alkyl chain length. The results indicated that antibacterial property studies on small molecules and homopolymers may not provide a solid basis for evaluating that in corresponding polymer membranes.

Studies on structural, thermal and AC conductivity scaling of PEO-LiPF6 polymer electrolyte with added ionic liquid [BMIMPF6

NASA Astrophysics Data System (ADS)

Chaurasia, S. K.; Saroj, A. L.; Shalu, Singh, V. K.; Tripathi, A. K.; Gupta, A. K.; Verma, Y. L.; Singh, R. K.

2015-07-01

Preparation and characterization of polymer electrolyte films of PEO+10wt.% LiPF6 + xwt.% BMIMPF6 (1-butyl-3-methylimidazolium hexafluorophosphate) containing dopant salt lithium hexafluorophosphate (LiPF6) and ionic liquid (BMIMPF6) having common anion PF6 - are reported. The ionic conductivity of the polymer electrolyte films has been found to increase with increasing concentration of BMIMPF6 in PEO+10 wt.% LiPF6 due to the plasticization effect of ionic liquid. DSC and XRD results show that the crystallinity of polymer electrolyte decreases with BMIMPF6 concentration which, in turn, is responsible for the increase in ionic conductivity. FTIR spectroscopic study shows the complexation of salt and/or ionic liquid cations with the polymer backbone. Ion dynamics behavior of PEO+LiPF6 as well as PEO+LiPF6 + BMIMPF6 polymer electrolytes was studied by frequency dependent conductivity, σ(f) measurements. The values σ(f) at various temperatures have been analyzed in terms of Jonscher power law (JPL) and scaled with respect to frequency which shows universal power law characteristics at all temperatures.

Commissioning of a new photon detection system for charge radii measurements of neutron-deficient Ca

NASA Astrophysics Data System (ADS)

Watkins, J.; Garand, D.; Miller, A. J.; Minamisono, K.; Everett, N.; Powel, R. C.; Maaß, B.; Nörtershäuser, W.; Kalman, C.; Lantis, J.; Kujawa, C.; Mantica, P.

2017-09-01

Calcium is unique for its possession of two stable isotopes of ``doubly magic'' nuclei at proton and neutron numbers (Z , N) = (20 , 20) and (20 , 28) . Recent charge radii measurements of neutron-rich calcium isotopes yielded an upward trend beyond current theoretical predictions. At the BECOLA facility at NSCL/MSU, Ca charge radii measurements will be extended to the neutron-deficient regime using collinear laser spectroscopy. A new photon detection system with an ellipsoidal reflector and a compound parabolic concentrator has been commissioned for the experiment. The system increases the signal-to-noise ratio by reducing background, which is critical for the low production rates of the Ca experiment. Details of the system and results of the characterization tests will be discussed. Work supported in part by NSF Grant PHY-15-65546, U.S. DOE Grant DE-NA0002924 and by the Deutsche Forschungsgemeinschaft Grant SFB 1245.

Two-pion femtoscopy in p -Pb collisions at s N N = 5.02 TeV

DOE PAGES

Adam, J.; Adamová, D.; Aggarwal, M. M.; ...

2015-03-24

Here, we report the results of the femtoscopic analysis of pairs of identical pions measured in p-Pb collisions at √s NN = 5.02 TeV. Femtoscopic radii are determined as a function of event multiplicity and pair momentum in three spatial dimensions. As in the pp collision system, the analysis is complicated by the presence of sizable background correlation structures in addition to the femtoscopic signal. The radii increase with event multiplicity and decrease with pair transverse momentum. When taken at comparable multiplicity, the radii measured in p-Pb collisions, at high multiplicity and low pair transverse momentum, are 10%–20% higher thanmore » those observed in pp collisions but below those observed in A–A collisions. The results are compared to hydrodynamic predictions at large event multiplicity as well as discussed in the context of calculations based on gluon saturation.« less

Correlating morphology to dc conductivity in polymerized ionic liquids

NASA Astrophysics Data System (ADS)

Iacob, Ciprian; Matusmoto, Atsushi; Inoue, Tadashi; Runt, James

Polymerized ionic liquids (PILs) combine the attractive mechanical characteristics of polymers and unique physico-chemical properties of low molecular weight ionic liquids in the same material. PILs have shown remarkable advantages when employed in electrochemical devices such as dye-sensitized solar cells and lithium batteries, among others. Understanding their ionic transport mechanism is the key for designing highly conductive PILs. In the current study, the correlation between morphology and charge transport in two homologous series of PILs with systematic variation of the alkyl chain length and anions is investigated using broadband dielectric spectroscopy, rheology, differential scanning calorimetry and X-ray scattering. As the alkyl chain length increases, the backbone-to-backbone separation increases, and dc-conductivity consequently decreases. The cations dominate structural dynamics since they are attached to the polymer chains, while the anions are smaller and more mobile ionic species thereby controlling the ionic conductivity. Further interpretation of decoupling of dc conductivity from the segmental relaxation enabled the correlation between polymer morphology and dc conductivity. Supported by the National Science Foundation, Polymers Program.

Characterization of Highly Sulfonated SIBS Polymer Partially Neutralized With Mg(+2) Cations

DTIC Science & Technology

2008-08-01

protective clothing, block copolymer ionomer membranes emerge. They are highly ordered sequence of both ionic and nonionic blocks, in which the ionic ...incorporated into the ionic polymer. Fourier-transform infrared spectroscopy results revealed that a significant amount of ordering occurred as a result on...increasing Mg content. This band indicates Mg complexation formed when two or more sulfonate groups ionically bonded to the Mg+2 cation

Co0.6Zn0.4Cu0.2CdxFe1.8-xO4 (0.2 ⩽ x ⩽ 0.8) magnetic ferrite nano-particle: Synthesis, characterization and photo-catalytic degradation of methyl orange

NASA Astrophysics Data System (ADS)

Bhukal, Santosh; Bansal, S.; Singhal, Sonal

2014-02-01

Cd2+ ion substituted nano-crystalline cobalt-zinc ferrites having chemical formula Co0.6Zn0.4Cu0.2CdxFe1.8-xO4 (x = 0.2, 0.4, 0.6 and 0.8) have been prepared using sol-gel auto-combustion method. The X-ray diffraction analysis confirmed the crystalline structure and phase purity of all the prepared nano-ferrites. The lattice constant was found to vary linearly from 8.360 Å to 8.390 Å for cadmium ion concentration from 0.2 to 0.8 in accordance with Vegard's law. Ionic radii of tetrahedral site (rA) and octahedral site (rB) was found to increase with increase in the cadmium ion concentration because of larger size of Cd2+ ion (0.97 Å) as compared to that of Fe3+ ion (0.67 Å). Vibrating sample magnetometer (VSM) results revealed that the saturation magnetization, coercivity and anisotropy constant decrease with increase in the cadmium concentration. The distribution of cations among A and B sites of the lattice was estimated by the magnetic moments which were calculated from the magnetic data. Moreover resistivity was found to be decrease with increase in the cadmium concentration. There was increase in drift mobility with increase in temperature because of the enhanced mobility of charge carriers due to thermal activation. Co0.6Zn0.4Cu0.2CdxFe1.8-xO4 showed good catalytic activity towards methyl orange and easily recovered by magnetic separation after the reaction. The photo-catalytic degradation was enhanced as the concentration of cadmium ion increased from 0.2 to 0.8 may be due to decrease in band gap with increase in Cd2+ ion concentration.

Anomalous frequency-dependent ionic conductivity of lesion-laden human-brain tissue

NASA Astrophysics Data System (ADS)

Emin, David; Akhtari, Massoud; Fallah, Aria; Vinters, Harry V.; Mathern, Gary W.

2017-10-01

We study the effect of lesions on our four-electrode measurements of the ionic conductivity of (˜1 cm3) samples of human brain excised from patients undergoing pediatric epilepsy surgery. For most (˜94%) samples, the low-frequency ionic conductivity rises upon increasing the applied frequency. We attributed this behavior to the long-range (˜0.4 mm) diffusion of solvated sodium cations before encountering intrinsic impenetrable blockages such as cell membranes, blood vessels, and cell walls. By contrast, the low-frequency ionic conductivity of some (˜6%) brain-tissue samples falls with increasing applied frequency. We attribute this unusual frequency-dependence to the electric-field induced liberation of sodium cations from traps introduced by the unusually severe pathology observed in samples from these patients. Thus, the anomalous frequency-dependence of the ionic conductivity indicates trap-producing brain lesions.

The Effect of Lengthening Cation Ether Tails on Ionic Liquid Properties

DOE PAGES

Lall-Ramnarine, S.; Rodriguez, C.; Fernandez, R.; ...

2016-08-30

In order to explore the effect of multiple ether functionalities on ionic liquid properties, a series of ten pyrrolidinium ionic liquids and ten imidazolium ionic liquids bearing ether and alkyl side chains of varying lengths (4 to 10 atoms in length) were prepared for this study. Their physical properties, such as viscosity, conductivity and thermal profile were measured and compared. Consistent with earlier literature, a single ether substituent substantially decreases the viscosity of pyrrolidinium and imidazolium ILs compared to their alkyl congeners. Remarkably, as the number of ether units in the pyrrolidinium ILs increases there is hardly any increase inmore » the viscosity, in contrast to alkylpyrrolidinium ILs where the viscosity increases steadily with chain length. Viscosities of imidazolium ether ILs increase with chain length but always remain well below their alkyl congeners. These results provide significant insight on the choice of starting materials for researchers designing ILs for specific applications.« less

Small angle neutron scattering from 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids ([Cnmim][PF6], n=4, 6, and 8)

NASA Astrophysics Data System (ADS)

Hardacre, Christopher; Holbrey, John D.; Mullan, Claire L.; Youngs, Tristan G. A.; Bowron, Daniel T.

2010-08-01

The presence of local anisotropy in the bulk, isotropic, and ionic liquid phases—leading to local mesoscopic inhomogeneity—with nanoscale segregation and expanding nonpolar domains on increasing the length of the cation alkyl-substituents has been proposed on the basis of molecular dynamics (MD) simulations. However, there has been little conclusive experimental evidence for the existence of intermediate mesoscopic structure between the first/second shell correlations shown by neutron scattering on short chain length based materials and the mesophase structure of the long chain length ionic liquid crystals. Herein, small angle neutron scattering measurements have been performed on selectively H/D-isotopically substituted 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids with butyl, hexyl, and octyl substituents. The data show the unambiguous existence of a diffraction peak in the low-Q region for all three liquids which moves to longer distances (lower Q), sharpens, and increases in intensity with increasing length of the alkyl substituent. It is notable, however, that this peak occurs at lower values of Q (longer length scale) than predicted in any of the previously published MD simulations of ionic liquids, and that the magnitude of the scattering from this peak is comparable with that from the remainder of the amorphous ionic liquid. This strongly suggests that the peak arises from the second coordination shells of the ions along the vector of alkyl-chain substituents as a consequence of increasing the anisotropy of the cation, and that there is little or no long-range correlated nanostructure in these ionic liquids.

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.

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.

Ionic Liquids and Relative Process Design

NASA Astrophysics Data System (ADS)

Zhang, S.; Lu, X.; Zhang, Y.; Zhou, Q.; Sun, J.; Han, L.; Yue, G.; Liu, X.; Cheng, W.; Li, S.

Ionic liquids have gained increasing attention in recent years due to their significant advantages, not only as alternative solvents but also as new materials and catalysts. Until now, most research work on ionic liquids has been at the laboratory or pilot scale. In view of the multifarious applications of ionic liquids, more new knowledge is needed and more systematic work on ionic liquids should be carried out deeply and broadly in order to meet the future needs of process design. For example, knowledge of the physicochemical properties is indispensable for the design of new ionic liquids and for the development of novel processes. The synthesis and application of ionic liquids are fundamental parts of engineering science, and the toxicity and environmental assessment of ionic liquids is critical importance for their large scale applications, especially for process design. These research aspects are closely correlated to the industrial applications of ionic liquids and to sustainable processes. However, material process design in the industrial applications of ionic liquids has hardly been implemented. Therefore, this chapter reviews several essential issues that are closely related to process design, such as the synthesis, structure-property relationships, important applications, and toxicity of ionic liquids.

Three regimes of extrasolar planet radius inferred from host star metallicities.

PubMed

Buchhave, Lars A; Bizzarro, Martin; Latham, David W; Sasselov, Dimitar; Cochran, William D; Endl, Michael; Isaacson, Howard; Juncher, Diana; Marcy, Geoffrey W

2014-05-29

Approximately half of the extrasolar planets (exoplanets) with radii less than four Earth radii are in orbits with short periods. Despite their sheer abundance, the compositions of such planets are largely unknown. The available evidence suggests that they range in composition from small, high-density rocky planets to low-density planets consisting of rocky cores surrounded by thick hydrogen and helium gas envelopes. Here we report the metallicities (that is, the abundances of elements heavier than hydrogen and helium) of more than 400 stars hosting 600 exoplanet candidates, and find that the exoplanets can be categorized into three populations defined by statistically distinct (∼4.5σ) metallicity regions. We interpret these regions as reflecting the formation regimes of terrestrial-like planets (radii less than 1.7 Earth radii), gas dwarf planets with rocky cores and hydrogen-helium envelopes (radii between 1.7 and 3.9 Earth radii) and ice or gas giant planets (radii greater than 3.9 Earth radii). These transitions correspond well with those inferred from dynamical mass estimates, implying that host star metallicity, which is a proxy for the initial solids inventory of the protoplanetary disk, is a key ingredient regulating the structure of planetary systems.

Three regimes of extrasolar planet radius inferred from host star metallicities

PubMed Central

Buchhave, Lars A.; Bizzarro, Martin; Latham, David W.; Sasselov, Dimitar; Cochran, William D.; Endl, Michael; Isaacson, Howard; Juncher, Diana; Marcy, Geoffrey W.

2014-01-01

Approximately half of the extrasolar planets (exoplanets) with radii less than four Earth radii are in orbits with short periods1. Despite their sheer abundance, the compositions of such planets are largely unknown. The available evidence suggests that they range in composition from small, high-density rocky planets to low-density planets consisting of rocky cores surrounded by thick hydrogen and helium gas envelopes. Here we report the metallicities (that is, the abundances of elements heavier than hydrogen and helium) of more than 400 stars hosting 600 exoplanet candidates, and find that the exoplanets can be categorized into three populations defined by statistically distinct (~4.5σ) metallicity regions. We interpret these regions as reflecting the formation regimes of terrestrial-like planets (radii less than 1.7 Earth radii), gas dwarf planets with rocky cores and hydrogen-helium envelopes (radii between 1.7 and 3.9 Earth radii) and ice or gas giant planets (radii greater than 3.9 Earth radii). These transitions correspond well with those inferred from dynamical mass estimates2,3, implying that host star metallicity, which is a proxy for the initial solids inventory of the protoplanetary disk, is a key ingredient regulating the structure of planetary systems. PMID:24870544

Consistent van der Waals Radii for the Whole Main Group

PubMed Central

Mantina, Manjeera; Chamberlin, Adam C.; Valero, Rosendo; Cramer, Christopher J.; Truhlar, Donald G.

2013-01-01

Atomic radii are not precisely defined but are nevertheless widely used parameters in modeling and understanding molecular structure and interactions. The van der Waals radii determined by Bondi from molecular crystals and noble gas crystals are the most widely used values, but Bondi recommended radius values for only 28 of the 44 main-group elements in the periodic table. In the present article we present atomic radii for the other 16; these new radii were determined in a way designed to be compatible with Bondi’s scale. The method chosen is a set of two-parameter correlations of Bondi’s radii with repulsive-wall distances calculated by relativistic coupled-cluster electronic structure calculations. The newly determined radii (in Å) are Be, 1.53; B, 1.92; Al, 1.84; Ca, 2.31; Ge, 2.11; Rb, 3.03; Sr, 2.50; Sb, 2.06; Cs, 3.43; Ba, 2.68; Bi, 2.07; Po, 1.97; At, 2.02; Rn, 2.20; Fr, 3.48; and Ra, 2.83. PMID:19382751

Consistent van der Waals radii for the whole main group.

PubMed

Mantina, Manjeera; Chamberlin, Adam C; Valero, Rosendo; Cramer, Christopher J; Truhlar, Donald G

2009-05-14

Atomic radii are not precisely defined but are nevertheless widely used parameters in modeling and understanding molecular structure and interactions. The van der Waals radii determined by Bondi from molecular crystals and data for gases are the most widely used values, but Bondi recommended radius values for only 28 of the 44 main-group elements in the periodic table. In the present Article, we present atomic radii for the other 16; these new radii were determined in a way designed to be compatible with Bondi's scale. The method chosen is a set of two-parameter correlations of Bondi's radii with repulsive-wall distances calculated by relativistic coupled-cluster electronic structure calculations. The newly determined radii (in A) are Be, 1.53; B, 1.92; Al, 1.84; Ca, 2.31; Ge, 2.11; Rb, 3.03; Sr, 2.49; Sb, 2.06; Cs, 3.43; Ba, 2.68; Bi, 2.07; Po, 1.97; At, 2.02; Rn, 2.20; Fr, 3.48; and Ra, 2.83.

Integration of uniform design and quantum-behaved particle swarm optimization to the robust design for a railway vehicle suspension system under different wheel conicities and wheel rolling radii

NASA Astrophysics Data System (ADS)

Cheng, Yung-Chang; Lee, Cheng-Kang

2017-10-01

This paper proposes a systematic method, integrating the uniform design (UD) of experiments and quantum-behaved particle swarm optimization (QPSO), to solve the problem of a robust design for a railway vehicle suspension system. Based on the new nonlinear creep model derived from combining Hertz contact theory, Kalker's linear theory and a heuristic nonlinear creep model, the modeling and dynamic analysis of a 24 degree-of-freedom railway vehicle system were investigated. The Lyapunov indirect method was used to examine the effects of suspension parameters, wheel conicities and wheel rolling radii on critical hunting speeds. Generally, the critical hunting speeds of a vehicle system resulting from worn wheels with different wheel rolling radii are lower than those of a vehicle system having original wheels without different wheel rolling radii. Because of worn wheels, the critical hunting speed of a running railway vehicle substantially declines over the long term. For safety reasons, it is necessary to design the suspension system parameters to increase the robustness of the system and decrease the sensitive of wheel noises. By applying UD and QPSO, the nominal-the-best signal-to-noise ratio of the system was increased from -48.17 to -34.05 dB. The rate of improvement was 29.31%. This study has demonstrated that the integration of UD and QPSO can successfully reveal the optimal solution of suspension parameters for solving the robust design problem of a railway vehicle suspension system.

Ionic Liquids in HPLC and CE: A Hope for Future.

PubMed

Ali, Imran; Suhail, Mohd; Sanagi, Mohd Marsin; Aboul-Enein, Hassan Y

2017-07-04

The ionic liquids (ILs) are salts with melting points below 100°C. These are called as ionic fluids, ionic melts, liquid electrolytes, fused salts, liquid salts, ionic glasses, designer solvents, green solvents and solvents of the future. These have a wide range of applications, including medical, pharmaceutical and chemical sciences. Nowadays, their use is increasing greatly in separation science, especially in chromatography and capillary electrophoresis due to their remarkable properties. The present article describes the importance of ILs in high-performance liquid chromatography and capillary electrophoresis. Efforts were also made to highlight the future expectations of ILs.

An electroactive conducting polymer actuator based on NBR/RTIL solid polymer electrolyte

NASA Astrophysics Data System (ADS)

Cho, M. S.; Seo, H. J.; Nam, J. D.; Choi, H. R.; Koo, J. C.; Lee, Y.

2007-04-01

This paper reports the fabrication of a dry-type conducting polymer actuator using nitrile rubber (NBR) as the base material in a solid polymer electrolyte. The conducting polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), was synthesized on the surface of the NBR layer by using a chemical oxidation polymerization technique. Room-temperature ionic liquids (RTIL) based on imidazolium salts, e.g. 1-butyl-3-methyl imidazolium X (where X = BF4-, PF6-, (CF3SO2)2N-), were absorbed into the composite film. The compatibility between the ionic liquids and the NBR polymer was confirmed by DMA. The effect of the anion size of the ionic liquids on the displacement of the actuator was examined. The displacement increased with increasing anion size of the ionic liquids. The cyclic voltammetry responses and the redox switching dynamics of the actuators were examined in different ionic liquids.

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

Extraction of S- and N-compounds from the mixture of hydrocarbons by ionic liquids as selective solvents.

PubMed

Gabrić, Beata; Sander, Aleksandra; Cvjetko Bubalo, Marina; Macut, Dejan

2013-01-01

Liquid-liquid extraction is an alternative method that can be used for desulfurization and denitrification of gasoline and diesel fuels. Recent approaches employ different ionic liquids as selective solvents, due to their general immiscibility with gasoline and diesel, negligible vapor pressure, and high selectivity to sulfur- and nitrogen-containing compounds. For that reason, five imidazolium-based ionic liquids and one pyridinium-based ionic liquid were selected for extraction of thiophene, dibenzothiophene, and pyridine from two model solutions. The influences of hydrodynamic conditions, mass ratio, and number of stages were investigated. Increasing the mass ratio of ionic liquid/model fuel and multistage extraction promotes the desulfurization and denitrification abilities of the examined ionic liquids. All selected ionic liquids can be reused and regenerated by means of vacuum evaporation.

Extraction of S- and N-Compounds from the Mixture of Hydrocarbons by Ionic Liquids as Selective Solvents

PubMed Central

Gabrić, Beata; Sander, Aleksandra; Cvjetko Bubalo, Marina; Macut, Dejan

2013-01-01

Liquid-liquid extraction is an alternative method that can be used for desulfurization and denitrification of gasoline and diesel fuels. Recent approaches employ different ionic liquids as selective solvents, due to their general immiscibility with gasoline and diesel, negligible vapor pressure, and high selectivity to sulfur- and nitrogen-containing compounds. For that reason, five imidazolium-based ionic liquids and one pyridinium-based ionic liquid were selected for extraction of thiophene, dibenzothiophene, and pyridine from two model solutions. The influences of hydrodynamic conditions, mass ratio, and number of stages were investigated. Increasing the mass ratio of ionic liquid/model fuel and multistage extraction promotes the desulfurization and denitrification abilities of the examined ionic liquids. All selected ionic liquids can be reused and regenerated by means of vacuum evaporation. PMID:23843736

X-Ray Crystallographic Studies of Electrostatic Effects in Cubic Insulin

NASA Astrophysics Data System (ADS)

Gursky, Olga

1992-09-01

Cubic crystals of bovine insulin were obtained at pH 9 from sodium phosphate buffer. Pathway dependence of crystallization was analysed and crystallization using controlled nucleation was developed. Crystal stability and solubility were surveyed by dialysing the crystals against salt solutions varying in salt composition and ionic strength. Crystals dialysed in 0.1-0.2M Li, Na, K, Rb, NH(4) or Tl salt solutions at pH 9 diffracted to beyond 2.8A, while crystals dialysed in Cs, Mg, Ca or La rapidly lost lattice order. Change in the solvent anion did not affect crystal stability. Electron density maps calculated from X-ray data to 2.8A resolution showed two specific cation binding sites which may be occupied by monovalent cations with ionic radii <1.5A. One site lies between insulin dimers near crystallographic two-fold axis without the close involvement of protein charged groups. Cation binding at this site is important for crystal stability. The other site is alternatively occupied by B10 His in one of its two conformations. At pH 7, the Tl occupancy at both sites was decreased, at pH 9.5 the Tl occupancy of the site near B10 His was increased. The structure was refined using the refined model of cubic porcine insulin and the X-ray data collected to 2A resolution from a bovine insulin crystal at pH 9, to R = 16.1% for the data extending from 10A to 2A. High -resolution data from crystals at pH 7 and pH 10 were collected and analysed. The weights of the two B10 His conformers and the cation occupancy near B10 vary in the pH range from 7 to 10, indicating histidine titration. Shifts in the positions of B1-B4 at pH 7 suggest titration of the B-chain terminal amino groups. Co-operative conformational changes in the surface charged residues A1, A4, B21, B29, B30 at pH 10.2 suggest titration of the A-chain terminal amino groups. In several crystals treated with dichloroethane, the syn-dichloroethane was bound in the niche across the two-fold axis connecting insulin monomers. Dichloroethane binding does not perturb the site geometry and probably leads to cubic insulin preparations of increased stability.

Hemodynamics of the renal artery ostia with implications for their structural development and efficiency of flow.

PubMed

McIntosh, William H; Ozturk, Mesude; Down, Linden A; Papavassiliou, Dimitrios V; O'Rear, Edgar A

2015-01-01

Energy losses at tube or blood vessel orifices depend on the extent of flare as measured by the dimensionless ratio of the fillet radius of curvature to diameter (r/D). The goal of this study was to assess the effect of ostial fillet radii on energy losses at the aorta-renal artery junctions since as much as a quarter of cardiac output passes through the kidneys. Pressure loss coefficients K for the renal artery ostia as a function of r/D have been determined for representative anatomical variants using finite volume simulations. Estimates of fillet radii in humans from image analysis were employed in simulations for comparison of loss coefficients. Values for K drop 45% as r/D increases over the range 0-1.3. Image analysis indicates that the ostia are not symmetric in humans with (r/D)superior much larger than (r/D)inferior. Simulations show the loss coefficient depends almost entirely on the superior fillet radius. Superior fillet radii for both renal arteries are similar to the optimal value to reduce energy losses while the inferior radii are not. Ostial asymmetry may have been induced by higher levels of shear stress present on the superior portion of a developing symmetric ostium of small r/D.

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.

Effects of Ionic Dependence of DNA Persistence Length on the DNA Condensation at Room Temperature

NASA Astrophysics Data System (ADS)

Mao, Wei; Liu, Yan-Hui; Hu, Lin; Xu, Hou-Qiang

2016-05-01

DNA persistence length is a key parameter for quantitative interpretation of the conformational properties of DNA and related to the bending rigidity of DNA. A series of experiments pointed out that, in the DNA condensation process by multivalent cations, the condensed DNA takes elongated coil or compact globule states and the population of the compact globule states increases with an increase in ionic concentration. At the same time, single molecule experiments carried out in solution with multivalent cations (such as spermidine, spermine) indicated that DNA persistence length strongly depends on the ionic concentration. In order to revolve the effects of ionic concentration dependence of persistence length on DNA condensation, a model including the ionic concentration dependence of persistence length and strong correlation of multivalent cation on DNA is provided. The autocorrelation function of the tangent vectors is found as an effective way to detect the ionic concentration dependence of toroidal conformations. With an increase in ion concentration, the first periodic oscillation contained in the autocorrelation function shifts, the number of segment contained in the first periodic oscillation decreases gradually. According to the experiments, the average long-axis length is defined to estimate the ionic concentration dependence of condensation process further. The relation between long-axis length and ionic concentration matches the experimental results qualitatively. Supported by National Natural Science Foundation of China under Grant Nos. 11047022, 11204045, 11464004 and 31360215; The Research Foundation from Ministry of Education of China (212152), Guizhou Provincial Tracking Key Program of Social Development (SY20123089, SZ20113069); The General Financial Grant from the China Postdoctoral Science Foundation (2014M562341); The Research Foundation for Young University Teachers from Guizhou University (201311); The West Light Foundation (2015) and College Innovation Talent Team of Guizhou Province, (2014) 32

Can the scaling behavior of electric conductivity be used to probe the self-organizational changes in solution with respect to the ionic liquid structure? The case of [C8MIM][NTf2].

PubMed

Paluch, Marian; Wojnarowska, Zaneta; Goodrich, Peter; Jacquemin, Johan; Pionteck, Jürgen; Hensel-Bielowka, Stella

2015-08-28

Electrical conductivity of the supercooled ionic liquid [C8MIM][NTf2], determined as a function of temperature and pressure, highlights strong differences in its ionic transport behavior between low and high temperature regions. To date, the crossover effect which is very well known for low molecular van der Waals liquids has been rarely described for classical ionic liquids. This finding highlights that the thermal fluctuations could be dominant mechanisms driving the dramatic slowing down of ion motions near Tg. An alternative way to analyze separately low and high temperature dc-conductivity data using a density scaling approach was then proposed. Based on which a common value of the scaling exponent γ = 2.4 was obtained, indicating that the applied density scaling is insensitive to the crossover effect. By comparing the scaling exponent γ reported herein along with literature data for other ionic liquids, it appears that γ decreases by increasing the alkyl chain length on the 1-alkyl-3-methylimidazolium-based ionic liquids. This observation may be related to changes in the interaction between ions in solution driven by an increase in the van der Waals type interaction by increasing the alkyl chain length on the cation. This effect may be related to changes in the ionic liquid nanostructural organization with the alkyl chain length on the cation as previously reported in the literature based on molecular dynamic simulations. In other words, the calculated scaling exponent γ may be then used as a key parameter to probe the interaction and/or self-organizational changes in solution with respect to the ionic liquid structure.

Femtosecond Raman-Induced Kerr Effect Study of Temperature-Dependent Intermolecular Dynamics in Molten Bis(trifluoromethylsulfonyl)amide Salts: Effects of Cation Species.

PubMed

Kakinuma, Shohei; Shirota, Hideaki

2018-05-25

In this study, we have investigated the effects of cation structures on the temperature dependence of the intermolecular vibrational dynamics of ionic liquids using femtosecond Raman-induced Kerr effect spectroscopy. The ionic liquids used in this study are bis(trifluoromethylsulfonyl)amide [NTf 2 ] - salts of the cations 1-butyl-3-methylimidazolium [C 4 MIm] + , 1-butyl-1-methylpyrrolidinium [Pyrr 14 ] + , 1-butylpyridinium [C 4 Py] + , butyldiethylmethylammonium [N 1224 ] + , triethyloctylammonium [N 2228 ] + , and triethyloctylphosphonium [P 2228 ] + . All of the ionic liquids show temperature-dependent low-frequency spectra. A difference in the temperature dependence between the spectra of the aromatic and nonaromatic cation based ionic liquids is especially significant. In the case of the aromatic cation based ionic liquids [C 4 MIm][NTf 2 ] and [C 4 Py][NTf 2 ], the spectral intensities in the low-frequency region below ca. 50 cm -1 increase and the high-frequency components at ca. 80 cm -1 shift to lower frequencies with rising temperature. In contrast, the ionic liquids based on nonaromatic cations only exhibit an increase in the low-frequency region below ca. 50 cm -1 with increasing temperature, while the high-frequency region of the spectra above ca. 50 cm -1 shows little change with variation of the temperature. These results suggest that the presence or absence of aromatic rings is the main factor in determining the temperature-dependent spectral features, particularly in the high-frequency region. We also found that the alkyl chain length and central atoms of the nonaromatic quaternary cations do not have much influence on the temperature-dependent spectral features. The first moments of the aromatic cation based ionic liquids are a little more sensitive to temperature than those of the nonaromatic cation based ionic liquids. The temperature-dependent viscosities and fragilities of the ionic liquids have also been examined.

Probing Lipid Bilayers under Ionic Imbalance.

PubMed

Lin, Jiaqi; Alexander-Katz, Alfredo

2016-12-06

Biological membranes are normally under a resting transmembrane potential (TMP), which originates from the ionic imbalance between extracellular fluids and cytosols, and serves as electric power storage for cells. In cell electroporation, the ionic imbalance builds up a high TMP, resulting in the poration of cell membranes. However, the relationship between ionic imbalance and TMP is not clearly understood, and little is known about the effect of ionic imbalance on the structure and dynamics of biological membranes. In this study, we used coarse-grained molecular dynamics to characterize a dipalmitoylphosphatidylcholine bilayer system under ionic imbalances ranging from 0 to ∼0.06 e charges per lipid (e/Lip). We found that the TMP displayed three distinct regimes: 1) a linear regime between 0 and 0.045 e/Lip, where the TMP increased linearly with ionic imbalance; 2) a yielding regime between ∼0.045 and 0.060 e/Lip, where the TMP displayed a plateau; and 3) a poration regime above ∼0.060 e/Lip, where we observed pore formation within the sampling time (80 ns). We found no structural changes in the linear regime, apart from a nonlinear increase in the area per lipid, whereas in the yielding regime the bilayer exhibited substantial thinning, leading to an excess of water and Na + within the bilayer, as well as significant misalignment of the lipid tails. In the poration regime, lipid molecules diffused slightly faster. We also found that the fluid-to-gel phase transition temperature of the bilayer dropped below the normal value with increased ionic imbalances. Our results show that a high ionic imbalance can substantially alter the essential properties of the bilayer, making the bilayer more fluid like, or conversely, depolarization of a cell could in principle lead to membrane stiffening. Copyright © 2016 Biophysical Society. Published by Elsevier Inc. All rights reserved.

The transverse momentum dependence of charged kaon Bose–Einstein correlations in the SELEX experiment

DOE PAGES

Nigmatkulov, G. A.; et al.

2015-12-18

We report the measurement of the one-dimensional charged kaon correlation functions using 600 GeV/c Σ –, π – and 540 GeV/C ρ beams from the SELEX (E781) experiment at the Fermilab Tevatron. K ±K ± correlation functions are studied for three transverse pair momentum, kT, ranges and parameterized by a Gaussian form. The emission source radii, R, and the correlation strength, λ, are extracted. Furthermore, the analysis shows a decrease of the source radii with increasing kaon transverse pair momentum for all beam types.

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

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

The relationship between bond ionicity, lattice energy, coefficient of thermal expansion and microwave dielectric properties of Nd(Nb(1-x)Sb(x))O4 ceramics.

PubMed

Zhang, Ping; Zhao, Yonggui; Wang, Xiuyu

2015-06-28

The crystalline structure refinement, chemical bond ionicity, lattice energy and coefficient of thermal expansion were carried out for Nd(Nb(1-x)Sb(x))O4 ceramics with a monoclinic fergusonite structure to investigate the correlations between the crystalline structure, phase stability, bond ionicity, lattice energy, coefficient of thermal expansion, and microwave dielectric properties. The bond ionicity, lattice energy, and coefficient of thermal expansion of Nd(Nb(1-x)Sb(x))O4 ceramics were calculated using a semiempirical method based on the complex bond theory. The phase structure stability varied with the lattice energy which was resulted by the substitution constant of Sb(5+). With the increasing of the Sb(5+) contents, the decrease of Nb/Sb-O bond ionicity was observed, which could be contributed to the electric polarization. The ε(r) had a close relationship with the Nb/Sb-O bond ionicity. The increase of the Q×f and |τ(f)| values could be attributed to the lattice energy and the coefficient of thermal expansion. The microwave dielectric properties of Nd(Nb(1-x)Sb(x))O4 ceramics with the monoclinic fergusonite structure were strongly dependent on the chemical bond ionicity, lattice energy and coefficient of thermal expansion.

Symmetric aluminum-wire arrays generate high-quality Z pinches at large array radii

NASA Astrophysics Data System (ADS)

Sanford, T. W. L.; Mock, R. C.; Spielman, R. B.; Peterson, D. L.; Mosher, D.; Roderick, N. F.

1998-10-01

A Saturn-accelerator study of annular, aluminum-wire array, Z-pinch implosions, in the calculated high-wire-number plasma-shell regime [Phys. Rev. Lett. 77, 5063 (1996)], shows that the radiated x-ray pulse width increases from about 4 nsec to about 7 nsec, when the radius of the array is increased from 8.75 to 20 mm at a fixed array mass of 0.6 mg. Eulerian radiation- magnetohydrodynamic code (E-RMHC) simulations in the r-z plane suggest that this pulse-width increase with radius is due to the faster growth of the shell thickness (that arises from a two-stage development in the magnetic Rayleigh-Taylor instability) relative to the increase in the shell implosion velocity. Over the array radii explored, the measured peak total x-ray power of ˜40 TW and energy of ˜325 kJ show little change outside of a ±15% shot-to-shot fluctuation and are consistent with the E-RMHC simulations. Similarly, the measured peak K-shell (lines plus continuum) power of ˜8 TW and energy of ˜70 kJ show little change with radius. The minimal change in K-shell yield is in agreement with simple K-shell radiation scaling models that assume a fixed radial compression for all initial array radii. These results suggest that the improved uniformity provided by the large number of wires in the initial array reduces the disruptive effects of the Rayleigh-Taylor instability observed in small-wire-number imploding loads.

The magnetic field of the equatorial magnetotail - AMPTE/CCE observations at R less than 8.8 earth radii

NASA Technical Reports Server (NTRS)

Fairfield, D. H.; Acuna, M. H.; Zanetti, L. J.; Potemra, T. A.

1987-01-01

The MPTE/CCE magnetic field experiment has been used to obtain a quantitative evaluation of the frequency and extent of magnetic field distortion in the near-tail region at less than 8.8 earth radii. The variation of this distortion with Kp, radial distance, longitude, and near-equatorial latitude is reported. It has been found that taillike distortions from the dipole field direction may reach 80 deg near the MPTE/CE apogee of 8.8 earth radii. The Bz field component in dipole coordinates was always positive within 0.5 earth radii of the equatorial current sheet, indicating the neutral lines were never seen inside of 8.8 earth radii. Fields were most taillike near midnight and during times of high Kp. At 8.5 earth radii the equatorial field magnitude depressions were roughly half the dipole field strength of 51 nT. These depressions are larger at lesser distances, reaching -40 nT at 3.4 earth radii for Kp of 2- or less and -80 nT and Kp of 3+ and greater.

Improvements for the stability of heavy-haul couplers with arc surface contact

NASA Astrophysics Data System (ADS)

Wu, Guosong; Wang, Huang; Yao, Yuan

2018-03-01

To investigate the stability mechanism of heavy-haul couplers with arc surface contact, the geometry and force analysis were conducted according to the friction circle theory. To improve the stability of the coupler, four improvements were proposed, which are increasing the secondary lateral stiffness of locomotives, adding a restoring bumpstop at the end of the coupler, increasing the arc surfaces radii and changing the clearance and stiffness of secondary lateral stopping block. A multi-body dynamics model with four heavy-haul locomotives and three detailed couplers were established to simulate the emergency braking. In addition, the coupler yaw instability was tested to investigate the effects of relevant parameters on the coupler stability. The results show that increasing the secondary lateral stiffness of locomotives, adding a bumpstop with a smaller bumpstop gap, increasing the arc surfaces radii, increasing the stiffness and decreasing the clearance of secondary lateral stopping block are conducive to improving the stability of the coupler with arc surface contact.

The effect of varying linker length on ion-transport properties in polymeric ionic liquids

NASA Astrophysics Data System (ADS)

Keith, Jordan; Mogurampelly, Santosh; Wheatle, Bill; Ganesan, Venkat

We report results of atomistic molecular dynamics simulations on polymerized 1-butyl-3-(n-alkyl)imidazolium ionic liquids with PF6- counterions. Consistent with experimental observations, we observe that the mobility of the PF6- ions increases with increasing n-alkyl linker length. Analysis of our results suggests that the motion of PF6- ions is driven by intermolecular ion hopping between chains, which in turn is influenced by ion-pair coordination numbers and intermolecular ionic separation distances. With increasing linker length, we observe 1) the anions coordinating less closely with cations and 2) intermolecular hopping distances decreasing.

Molecular dynamics simulation of the ionic liquid N-octylpyridinium tetrafluoroborate and acetonitrile: Thermodynamic and structural properties

NASA Astrophysics Data System (ADS)

Zhou, Siwen; Zhu, Guanglai; Kang, Xianqu; Li, Qiang; Sha, Maolin; Cui, Zhifeng; Xu, Xinsheng

2018-06-01

Using molecular dynamics simulation, the research obtained the thermodynamic properties and microstructures of the mixture of N-octylpyridinium tetrafluoroborate and acetonitrile, including density, self-diffusion coefficients, excess properties, radial distribution functions (RDFs) and spatial distribution functions (SDFs). Both RDFs and SDFs indicate that the local microstructure of the polar region is different from the nonpolar region with different mole fraction of ionic liquids. Acetonitrile could increase the order of the polar regions. While with acetonitrile increasing, the orderliness of the nonpolar region increases firstly and then decreases. In relatively dilute solution, ionic liquids were dispersed to form small aggregates wrapped by acetonitrile.

Alkaline earth-based coordination polymers derived from a cyclotriphosphazene-functionalized hexacarboxylate

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

Ling, Yajing; Bai, Dongjie; Feng, Yunlong

Combination of hexakis(4-carboxylatephenoxy)cyclotriphosphazene with alkaline earth ions of increasing ionic radii (Mg{sup 2+}, Ca{sup 2+} and Ba{sup 2+}) under different solvothermal conditions yielded three new coordination polymers, and their crystal structures were determined by single-crystal X-ray diffraction analysis. The magnesium compound displays a three dimensional (3D) network structure constructed from the deprotonated ligand and the secondary building block Mg(COO){sub 4}, which can be rationalized as a (4,6)-connected topological net with the Schläfli symbol of (4{sup 4}·6{sup 2}){sub 3}(4{sup 9}·6{sup 6}){sub 2}. The calcium compound consists of 1D infinite “Ca-O” inorganic chains connected by the deprotonated ligands to from a 3Dmore » framework. The barium compound exhibits a 3D framework in which 1D “Ba-O” inorganic chains are connected together by the deprotonated organic linkers. Due to the semi-rigid nature, the ligand adopts distinctly different conformations in the three compounds. The metal ions’ influence exerted on the final structure of the resulting coordination polymers is also discussed. When the radii of alkaline earth ions increases descending down the group from Mg(II) to Ba(II), the coordination number becomes larger and more versatile: from 6 in the magnesium compound, to 6,7 and 10 in the calcium compound, and to 8 and 9 in the barium compound, thus substantially influencing the resulting final framework structures. Also, the photophysical properties were investigated systematically, revealing that the three compounds are photoluminscent in the solid state at room temperature. This work demonstrates that although the multiplicity of conformation in the hexacarboxylate ligand based on the inorganic scaffold cyclotriphosphazene makes it difficult to predict how this ligand will form extended network, but provides unique opportunities for the formation of diverse inorganic-organic hybrids exhibiting rich structural topologies. - Graphical abstract: Three alkaline earth-based coordination polymers were constructed from a semirigid cyclotriphosphazene-functionalized hexacarboxylate exhibiting different inorganic nodes as well as distinct ligand conformations relying on the metal ions, which presents the first example of such a ligand incorporated into alkaline earth–based coordination polymers. - Highlights: • Three alkaline earth-based coordination polymers were synthesized. • The three compounds exhibit different inorganic nodes and ligand conformations. • The three compounds are photoluminscent in the solid state.« less

Conventional empirical law reverses in the phase transitions of 122-type iron-based superconductors

DOE PAGES

Yu, Zhenhai; Wang, Lin; Wang, Luhong; ...

2014-11-24

Phase transition of solid-state materials is a fundamental research topic in condensed matter physics, materials science and geophysics. It has been well accepted and widely proven that isostructural compounds containing different cations undergo same pressure-induced phase transitions but at progressively lower pressures as the cation radii increases. However, we discovered that this conventional law reverses in the structural transitions in 122-type iron-based superconductors. In this report, a combined low temperature and high pressure X-ray diffraction (XRD) measurement has identified the phase transition curves among the tetragonal (T), orthorhombic (O) and the collapsed-tetragonal (cT) phases in the structural phase diagram ofmore » the iron-based superconductor AFe 2As 2 (A = Ca, Sr, Eu, and Ba). As a result, the cation radii dependence of the phase transition pressure (T → cT) shows an opposite trend in which the compounds with larger ambient radii cations have a higher transition pressure.« less

Flexible Thick-Film Electrochemical Sensors: Impact of Mechanical Bending and Stress on the Electrochemical Behavior

PubMed Central

Cai, Jiaying; Cizek, Karel; Long, Brenton; McAferty, Kenyon; Campbell, Casey G.; Allee, David R.; Vogt, Bryan D.; La Belle, Jeff; Wang, Joseph

2009-01-01

The influence of the mechanical bending, rolling and crimping of flexible screen-printed electrodes upon their electrical properties and electrochemical behavior has been elucidated. Three different flexible plastic substrates, Mylar, polyethylene naphthalate (PEN), and Kapton, have been tested in connection to the printing of graphite ink working electrodes. Our data indicate that flexible printed electrodes can be bent to extremely small radii of curvature and still function well, despite a marginal increase the electrical resistance. Below critical radii of curvature of ~8 mm, full recovery of the electrical resistance occurs upon strain release. The electrochemical response is maintained for sub-mm bending radii and a 180° pinch of the electrode does not lead to device failure. The electrodes appear to be resistant to repeated bending. Such capabilities are demonstrated using model compounds, including ferrocyanide, trinitrotoluene (TNT) and nitronaphthalene (NN). These printed electrodes hold great promise for widespread applications requiring flexible, yet robust non-planar sensing devices. PMID:20160861

Resolving Size Distribution of Black Carbon Internally Mixed With Snow: Impact on Snow Optical Properties and Albedo

NASA Astrophysics Data System (ADS)

He, Cenlin; Liou, Kuo-Nan; Takano, Yoshi

2018-03-01

We develop a stochastic aerosol-snow albedo model that explicitly resolves size distribution of aerosols internally mixed with various snow grains. We use the model to quantify black carbon (BC) size effects on snow albedo and optical properties for BC-snow internal mixing. Results show that BC-induced snow single-scattering coalbedo enhancement and albedo reduction decrease by a factor of 2-3 with increasing BC effective radii from 0.05 to 0.25 μm, while polydisperse BC results in up to 40% smaller visible single-scattering coalbedo enhancement and albedo reduction compared to monodisperse BC with equivalent effective radii. We further develop parameterizations for BC size effects for application to climate models. Compared with a realistic polydisperse assumption and observed shifts to larger BC sizes in snow, respectively, assuming monodisperse BC and typical atmospheric BC effective radii could lead to overestimates of 24% and 40% in BC-snow albedo forcing averaged over different BC and snow conditions.

Unexpectedly large charge radii of neutron-rich calcium isotopes

DOE PAGES

Garcia Ruiz, R. F.; Bissell, M. L.; Blaum, K.; ...

2016-02-08

Here, despite being a complex many-body system, the atomic nucleus exhibits simple structures for certain ‘magic’ numbers of protons and neutrons. The calcium chain in particular is both unique and puzzling: evidence of doubly magic features are known in 40,48Ca, and recently suggested in two radioactive isotopes, 52,54Ca. Although many properties of experimentally known calcium isotopes have been successfully described by nuclear theory, it is still a challenge to predict the evolution of their charge radii. Here we present the first measurements of the charge radii of 49,51,52Ca, obtained from laser spectroscopy experiments at ISOLDE, CERN. The experimental results aremore » complemented by state-of-the-art theoretical calculations. The large and unexpected increase of the size of the neutron-rich calcium isotopes beyond N = 28 challenges the doubly magic nature of 52Ca and opens new intriguing questions on the evolution of nuclear sizes away from stability, which are of importance for our understanding of neutron-rich atomic nuclei.« less

Synthesis and characterization of ionic polymer networks in a room-temperature ionic liquid.

PubMed

Stanzione, Joseph F; Jensen, Robert E; Costanzo, Philip J; Palmese, Giuseppe R

2012-11-01

Ionic liquid gels (ILGs) for potential use in ion transport and separation applications were generated via a free radical copolymerization of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and N,N'-methylene(bis)acrylamide (MBA) using 1-ethyl-3-methylimidazolium ethylsulfate (IL) as a room temperature ionic liquid solvent medium. The AMPS and MBA monomer solubility window in the IL in the temperature range of 25 to 65 °C was determined. In situ ATR-FTIR showed near complete conversion of monomers to a cross-linked polymer network. ILGs with glass transition temperatures (T(g)s) near -50 °C were generated with T(g) decreasing with increasing IL content. The elastic moduli in compression (200 to 6600 kPa) decreased with increasing IL content and increasing AMPS content while the conductivities (0.35 to 2.14 mS cm⁻¹) increased with increasing IL content and decreasing MBA content. The polymer-IL interaction parameter (χ) (0.48 to 0.55) was determined via a modified version of the Bray and Merrill equation.

Quantum and Classical Molecular Dynamics of Ionic Liquid Electrolytes for Na/Li-based Batteries: Molecular Origins of the Conductivity Behavior.

PubMed

Vicent-Luna, Jose Manuel; Ortiz-Roldan, Jose Manuel; Hamad, Said; Tena-Zaera, Ramon; Calero, Sofia; Anta, Juan Antonio

2016-08-18

Compositional effects on the charge-transport properties of electrolytes for batteries based on room-temperature ionic liquids (RTILs) are well-known. However, further understanding is required about the molecular origins of these effects, in particular regarding the replacement of Li by Na. In this work, we investigate the use of RTILs in batteries, by means of both classical molecular dynamics (MD), which provides information about structure and molecular transport, and ab initio molecular dynamics (AIMD), which provides information about structure. The focus has been placed on the effect of adding either Na(+) or Li(+) to 1-methyl-1-butyl-pyrrolidinium [C4 PYR](+) bis(trifluoromethanesulfonyl)imide [Tf2 N](-) . Radial distribution functions show excellent agreement between MD and AIMD, which ensures the validity of the force fields used in the MD. This is corroborated by the MD results for the density, the diffusion coefficients, and the total conductivity of the electrolytes, which reproduce remarkably well the experimental observations for all studied Na/Li concentrations. By extracting partial conductivities, it is demonstrated that the main contribution to the conductivity is that of [C4 PYR](+) and [Tf2 N](-) . However, addition of Na(+) /Li(+) , although not significant on its own, produces a dramatic decrease in the partial conductivities of the RTIL ions. The origin of this indirect effect can be traced to the modification of the microscopic structure of the liquid as observed from the radial distribution functions, owing to the formation of [Na(Tf2 N)n ]((n-1)-) and [Li(Tf2 N)n ]((n-1)-) clusters at high concentrations. This formation hinders the motion of the large ions, hence reducing the total conductivity. We demonstrate that this clustering effect is common to both Li and Na, showing that both ions behave in a similar manner at a microscopic level in spite of their distinct ionic radii. This is an interesting finding for extending Li-ion and Li-air technologies to their potentially cheaper Na-based counterparts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gelatinization kinetic of waxy starches under pressure according to ionic strength

NASA Astrophysics Data System (ADS)

Simonin, Hélène; Guyon, Claire; de Lamballerie, Marie; Lebail, Alain

2010-12-01

High pressure is a potential technology for the texturization of food products at ambient temperature. In this area, waxy starches are particularly interesting because they gelatinize quickly under sufficient pressure. However, gelatinization may be influenced by other components in the food matrix. Here, we investigate the influence of increasing ionic strength on gelatinization rate and kinetics at 500 MPa for waxy corn and waxy rice starches. We show that increasing ionic strength strongly retards and inhibits starch gelatinization under pressure and leads to heterogeneous gels with remnant granules.

Effect of SiO2 addition and gamma irradiation on the lithium borate glasses

NASA Astrophysics Data System (ADS)

Raut, A. P.; Deshpande, V. K.

2018-01-01

The physical properties like density, glass transition temperature (Tg), and ionic conductivity of lithium borate (LB) glasses with SiO2 addition were measured before and after gamma irradiation. Remarkable changes in properties have been obtained in the physical properties of LB glasses with SiO2 addition and after gamma irradiation. The increase in density and glass transition temperature of LB glasses with SiO2 addition has been explained with the help of increase in density of cross linking due to SiO4 tetrahedra formation. The increase in ionic conductivity with SiO2 addition was explained with the help of ‘mixed glass former effect’. The increase in density and Tg of LB glasses with SiO2 addition after gamma irradiation has been attributed to fragmentation of bigger ring structure into smaller rings, which increases the density of cross linking and hence compaction. The exposure of gamma irradiation has lead to decrease in ionic conductivity of LB glasses with SiO2 addition. The atomic displacement caused by gamma irradiation resulted in filling of interstices and decrease in trapping sites. This explains the obtained decrease in ionic conductivity after gamma irradiation of glasses. The obtained results of effect of SiO2 addition and gamma irradiation on the density, Tg and ionic conductivity has been supported by FTIR results.

Strength determination of brittle materials as curved monolithic structures.

PubMed

Hooi, P; Addison, O; Fleming, G J P

2014-04-01

The dental literature is replete with "crunch the crown" monotonic load-to-failure studies of all-ceramic materials despite fracture behavior being dominated by the indenter contact surface. Load-to-failure data provide no information on stress patterns, and comparisons among studies are impossible owing to variable testing protocols. We investigated the influence of nonplanar geometries on the maximum principal stress of curved discs tested in biaxial flexure in the absence of analytical solutions. Radii of curvature analogous to elements of complex dental geometries and a finite element analysis method were integrated with experimental testing as a surrogate solution to calculate the maximum principal stress at failure. We employed soda-lime glass discs, a planar control (group P, n = 20), with curvature applied to the remaining discs by slump forming to different radii of curvature (30, 20, 15, and 10 mm; groups R30-R10). The mean deflection (group P) and radii of curvature obtained on slumping (groups R30-R10) were determined by profilometry before and after annealing and surface treatment protocols. Finite element analysis used the biaxial flexure load-to-failure data to determine the maximum principal stress at failure. Mean maximum principal stresses and load to failure were analyzed with one-way analyses of variance and post hoc Tukey tests (α = 0.05). The measured radii of curvature differed significantly among groups, and the radii of curvature were not influenced by annealing. Significant increases in the mean load to failure were observed as the radius of curvature was reduced. The maximum principal stress did not demonstrate sensitivity to radius of curvature. The findings highlight the sensitivity of failure load to specimen shape. The data also support the synergistic use of bespoke computational analysis with conventional mechanical testing and highlight a solution to complications with complex specimen geometries.

[Effect of Radii barrier sleeves on cure depth of composite resin].

PubMed

Wang, Binping; DU, Yongxiu

2009-01-01

To explore the effect of Radii barrier sleeves on the cure depth of composite resin. Cylinder mold was prepared, and the resin was filled strictly into the mold. The surface was flattened and then cured with plastic engraver's knife.The depth of composite resin which was cured by QHL75TM with or without Radii barrier sleeves was compared. The cure depth of composite resin which were cured by QHL75TM with or without Radii barrier sleeves of photo-curing machine was 4.38 mm and 4.27 mm respectively,with no statistical difference. The cure depth of composite resin is not influenced by Radii barrier sleeves under the same light condition.

The Isophotal Structure of Star-forming Galaxies at 0.5 < z < 1.8 in CANDELS: Implications for the Evolution of Galaxy Structure

NASA Astrophysics Data System (ADS)

Jiang, Dongfei; Liu, F. S.; Zheng, Xianzhong; Yesuf, Hassen M.; Koo, David C.; Faber, S. M.; Guo, Yicheng; Koekemoer, Anton M.; Wang, Weichen; Fang, Jerome J.; Barro, Guillermo; Jia, Meng; Tong, Wei; Liu, Lu; Meng, Xianmin; Kocevski, Dale; McGrath, Elizabeth J.; Hathi, Nimish P.

2018-02-01

We have measured the radial profiles of isophotal ellipticity (ε) and disky/boxy parameter A 4 out to radii of about three times the semimajor axes for ∼4600 star-forming galaxies (SFGs) between redshift 0.5 and 1.8 in the CANDELS/GOODS-S and UDS fields. Based on the average size–mass relation in each redshift bin, we divide our galaxies at a given mass into Small SFGs (SSFGs; smaller than the average) and Large SFGs (LSFGs; larger than the average). We show that, at low masses ({M}* < {10}10{M}ȯ ), the SSFGs generally have nearly flat ε and A 4 profiles in both edge-on and face-on views, especially at z> 1. Moreover, the median A 4 values at all radii are almost zero. In contrast, the highly inclined low-mass LSFGs in the same mass-redshift bins generally have monotonically increasing ε profiles with radius and disky feature dominated in the intermediate regions. These findings imply that at these redshifts, the low-mass SSFGs are not disk-like, whereas the low-mass LSFGs likely harbour disk-like components flattened by significant rotations. At high masses ({M}* > {10}10{M}ȯ ), both highly inclined SSFGs and LSFGs generally exhibit distinct trends in both ε and A 4 profiles, which increase at lower radii, reach maxima, then decrease at larger radii. Such the feature is more prevalent for more massive ({M}* > {10}10.5{M}ȯ ) galaxies or at lower redshifts (z< 1.4). This feature can be simply explained if galaxies possess all three components: central bulges, disks in the intermediate regions, and halo-like stellar components in the outskirts.

Temperature dependent dielectric properties and ion transportation in solid polymer electrolyte for lithium ion batteries

NASA Astrophysics Data System (ADS)

Sengwa, R. J.; Dhatarwal, Priyanka; Choudhary, Shobhna

2016-05-01

Solid polymer electrolyte (SPE) film consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend matrix with lithium tetrafluroborate (LiBF4) as dopant ionic salt and poly(ethylene glycol) (PEG) as plasticizer has been prepared by solution casting method followed by melt pressing. Dielectric properties and ionic conductivity of the SPE film at different temperatures have been determined by dielectric relaxation spectroscopy. It has been observed that the dc ionic conductivity of the SPE film increases with increase of temperature and also the decrease of relaxation time. The temperature dependent relaxation time and ionic conductivity values of the electrolyte are governed by the Arrhenius relation. Correlation observed between dc conductivity and relaxation time confirms that ion transportation occurs with polymer chain segmental dynamics through hopping mechanism. The room temperature ionic conductivity is found to be 4 × 10-6 S cm-1 which suggests the suitability of the SPE film for rechargeable lithium batteries.

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.

Temperature dependent dielectric properties and ion transportation in solid polymer electrolyte for lithium ion batteries

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

Sengwa, R. J., E-mail: rjsengwa@rediffmail.com; Dhatarwal, Priyanka, E-mail: dhatarwalpriyanka@gmail.com; Choudhary, Shobhna, E-mail: shobhnachoudhary@rediffmail.com

2016-05-06

Solid polymer electrolyte (SPE) film consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend matrix with lithium tetrafluroborate (LiBF{sub 4}) as dopant ionic salt and poly(ethylene glycol) (PEG) as plasticizer has been prepared by solution casting method followed by melt pressing. Dielectric properties and ionic conductivity of the SPE film at different temperatures have been determined by dielectric relaxation spectroscopy. It has been observed that the dc ionic conductivity of the SPE film increases with increase of temperature and also the decrease of relaxation time. The temperature dependent relaxation time and ionic conductivity values of the electrolyte are governedmore » by the Arrhenius relation. Correlation observed between dc conductivity and relaxation time confirms that ion transportation occurs with polymer chain segmental dynamics through hopping mechanism. The room temperature ionic conductivity is found to be 4 × 10{sup −6} S cm{sup −1} which suggests the suitability of the SPE film for rechargeable lithium batteries.« less

Engineering polyelectrolyte multilayer structure at the nanometer length scale by tuning polymer solution conformation.

NASA Astrophysics Data System (ADS)

Boddohi, Soheil; Killingsworth, Christopher; Kipper, Matt

2008-03-01

Chitosan (a weak polycation) and heparin (a strong polyanion) are used to make polyelectrolyte multilayers (PEM). PEM thickness and composition are determined as a function of solution pH (4.6 to 5.8) and ionic strength (0.1 to 0.5 M). Over this range, increasing pH increases the PEM thickness; however, the sensitivity to changes in pH is a strong function of ionic strength. The PEM thickness data are correlated to the polymer conformation in solution. Polyelectrolyte conformation in solution is characterized by gel permeation chromatography (GPC). The highest sensitivity of PEM structure to pH is obtained at intermediate ionic strength. Different interactions govern the conformation and adsorption phenomena at low and high ionic strength, leading to reduced sensitivity to solution pH at extreme ionic strengths. The correspondence between PEM thickness and polymer solution conformation offers opportunities to tune polymer thin film structure at the nanometer length scale by controlling simple, reproducible processing conditions.

Predictive modeling studies for the ecotoxicity of ionic liquids towards the green algae Scenedesmus vacuolatus.

PubMed

Das, Rudra Narayan; Roy, Kunal

2014-06-01

Hazardous potential of ionic liquids is becoming an issue of high concern with increasing application of these compounds in various industrial processes. Predictive toxicological modeling on ionic liquids provides a rational assessment strategy and aids in developing suitable guidance for designing novel analogues. The present study attempts to explore the chemical features of ionic liquids responsible for their ecotoxicity towards the green algae Scenedesmus vacuolatus by developing mathematical models using extended topochemical atom (ETA) indices along with other categories of chemical descriptors. The entire study has been conducted with reference to the OECD guidelines for QSAR model development using predictive classification and regression modeling strategies. The best models from both the analyses showed that ecotoxicity of ionic liquids can be decreased by reducing chain length of cationic substituents and increasing hydrogen bond donor feature in cations, and replacing bulky unsaturated anions with simple saturated moiety having less lipophilic heteroatoms. Copyright © 2013 Elsevier Ltd. All rights reserved.

The Properties of HPMC:PEO Extended Release Hydrophilic Matrices and their Response to Ionic Environments.

PubMed

Hu, Anran; Chen, Chen; Mantle, Michael D; Wolf, Bettina; Gladden, Lynn F; Rajabi-Siahboomi, Ali; Missaghi, Shahrzad; Mason, Laura; Melia, Colin D

2017-05-01

Investigate the extended release behaviour of compacts containing mixtures of hydrophilic HPMC and PEO in hydrating media of differing ionic strengths. The extended release behaviour of various HPMC:PEO compacts was investigated using dissolution testing, confocal microscopy and magnetic resonance imaging, with respect to polymer ratio and ionic strength of the hydrating media. Increasing HPMC content gave longer extended release times, but a greater sensitivity to high ionic dissolution environments. Increasing PEO content reduced this sensitivity. The addition of PEO to a predominantly HPMC matrix reduced release rate sensitivity to high ionic environments. Confocal microscopy of early gel layer development showed the two polymers appeared to contribute independently to gel layer structure whilst together forming a coherent and effective diffusion barrier. There was some evidence that poorly swollen HPMC particles added a tortuosity barrier to the gel layer in high ionic strength environments, resulting in prolonged extended release. MRI provides unique, non-invasive spatially resolved information from within the HPMC:PEO compacts that furthers our understanding of USP 1 and USP 4 dissolution data. Confocal microscopy and MRI data show that combinations of HPMC and PEO have advantageous extended release properties, in comparison with matrices containing a single polymer.

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.

Rare earth metal-containing ionic liquids

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

Prodius, Denis; Mudring, Anja-Verena

As an innovative tool, ionic liquids (ILs) are widely employed as an alternative, smart, reaction media (vs. traditional solvents) offering interesting technology solutions for dissolving, processing and recycling of metal-containing materials. The costly mining and refining of rare earths (RE), combined with increasing demand for high-tech and energy-related applications around the world, urgently requires effective approaches to improve the efficiency of rare earth separation and recovery. In this context, ionic liquids appear as an attractive technology solution. Finally, this paper addresses the structural and coordination chemistry of ionic liquids comprising rare earth metals with the aim to add to understandingmore » prospects of ionic liquids in the chemistry of rare earths.« less

Rare earth metal-containing ionic liquids

DOE PAGES

Prodius, Denis; Mudring, Anja-Verena

2018-03-07

As an innovative tool, ionic liquids (ILs) are widely employed as an alternative, smart, reaction media (vs. traditional solvents) offering interesting technology solutions for dissolving, processing and recycling of metal-containing materials. The costly mining and refining of rare earths (RE), combined with increasing demand for high-tech and energy-related applications around the world, urgently requires effective approaches to improve the efficiency of rare earth separation and recovery. In this context, ionic liquids appear as an attractive technology solution. Finally, this paper addresses the structural and coordination chemistry of ionic liquids comprising rare earth metals with the aim to add to understandingmore » prospects of ionic liquids in the chemistry of rare earths.« less

Properties of the Nafion membrane impregnated with hydroxyl ammonium based ionic liquids

NASA Astrophysics Data System (ADS)

Garaev, Valeriy; Kleperis, Janis; Pavlovica, Sanita; Vaivars, Guntars

2012-08-01

In this work, the Nafion 112 membrane impregnated with nine various hydroxyl ammonium based ionic liquids have been investigated. The used ionic liquids were combined from hydroxyl ammonium cations (2-hydroxyethylammonium/HEA, bis(2- hydroxyethyl)ammonium/BHEA, tris(2-hydroxyethyl)ammonium/THEA) and carboxylate anions (formate, acetate, lactate). The membranes are characterized by conductivity and thermal stability measurements. It was found, that almost all composites have 10 times higher ion conductivity than a pure Nafion 112 at 90 °C in ambient environment due to the higher thermal stability. The thermal stability of Nafion membrane was increased by all studied nine ionic liquids. In this work, only biodegradable ionic liquids were used for composite preparation.

Switchable solvents and methods of use thereof

DOEpatents

Jessop, Philip G.; Eckert, Charles A.; Liotta, Charles L.; Heldebrant, David J.

2013-08-20

A solvent that reversibly converts from a nonionic liquid mixture to an ionic liquid upon contact with a selected trigger, e.g., contact with CO.sub.2, is described. In preferred embodiments, the ionic solvent is readily converted back to the nonionic liquid mixture. The nonionic liquid mixture includes an amidine or guanidine or both, and water, alcohol, or a combination thereof. Single component amine solvents that reversibly convert between ionic and non-ionic states are also described. Some embodiments require increased pressure to convert; others convert at 1 atmosphere.

Switchable solvents and methods of use thereof

DOEpatents

Jessop, Philip G [Kingston, CA; Eckert, Charles A [Atlanta, GA; Liotta, Charles L [Atlanta, GA; Heldebrant, David J [Richland, WA

2011-07-19

A solvent that reversibly converts from a nonionic liquid mixture to an ionic liquid upon contact with a selected trigger, e.g., contact with CO.sub.2, is described. In preferred embodiments, the ionic solvent is readily converted back to the nonionic liquid mixture. The nonionic liquid mixture includes an amidine or guanidine or both, and water, alcohol, or a combination thereof. Single component amine solvents that reversibly convert between ionic and non-ionic states are also described. Some embodiments require increased pressure to convert; others convert at 1 atmosphere.

Switchable solvents and methods of use thereof

DOEpatents

Jessop, Philip G; Eckert, Charles A; Liotta, Charles L; Heldebrant, David J

2014-04-29

A solvent that reversibly converts from a nonionic liquid mixture to an ionic liquid upon contact with a selected trigger, e.g., contact with CO.sub.2, is described. In preferred embodiments, the ionic solvent is readily converted back to the nonionic liquid mixture. The nonionic liquid mixture includes an amidine or guanidine or both, and water, alcohol, or a combination thereof. Single component amine solvents that reversibly convert between ionic and non-ionic states are also described. Some embodiments require increased pressure to convert; others convert at 1 atmosphere.

Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes

DOE PAGES

Kusuma, Victor A.; Macala, Megan K.; Liu, Jian; ...

2018-10-02

Ion gel films were prepared by incorporating eight commercially available ionic liquids in two different cross-linked polymer matrices to evaluate their phase miscibility, gas permeability and ionic conductivity for potential applications as gas separation membranes and solid electrolyte materials. The ionic liquids cations were 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-butyl-1-methylpyrrolidinium, tributylmethylphosphonium, and butyltrimethylammonium with a common anion (bis(trifluoromethylsulfonyl)imide). In addition, ionic liquids with 1-ethyl-3-methylimidazolium cation with acetate, dicyanamide and tetrafluoroborate counterions were evaluated. The two polymers were cross-linked poly(ethylene oxide) and cross-linked poly(ethylene oxide)/siloxane copolymer. Differential scanning calorimetry, X-ray diffractometry and visual observations were performed to evaluate the ion gels’ miscibility, thermal stabilitymore » and homogeneity. Ionic liquids with the least basic anion (bis(trifluoromethylsulfonyl)imide) and aromatic cations containing acidic proton (e.g. imidazolium and pyridinium) gave the most stable and miscible ion gels. Phase stability was shown to be a function of both ionic liquid content and temperature, with phase separation observed at elevated temperatures. In conclusion, gas permeability testing with carbon dioxide and nitrogen and ionic conductivity measurements confirmed that these ionic liquids increased the gas permeability and ionic conductivity of the polymers.« less

Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes

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

Kusuma, Victor A.; Macala, Megan K.; Liu, Jian

Ion gel films were prepared by incorporating eight commercially available ionic liquids in two different cross-linked polymer matrices to evaluate their phase miscibility, gas permeability and ionic conductivity for potential applications as gas separation membranes and solid electrolyte materials. The ionic liquids cations were 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-butyl-1-methylpyrrolidinium, tributylmethylphosphonium, and butyltrimethylammonium with a common anion (bis(trifluoromethylsulfonyl)imide). In addition, ionic liquids with 1-ethyl-3-methylimidazolium cation with acetate, dicyanamide and tetrafluoroborate counterions were evaluated. The two polymers were cross-linked poly(ethylene oxide) and cross-linked poly(ethylene oxide)/siloxane copolymer. Differential scanning calorimetry, X-ray diffractometry and visual observations were performed to evaluate the ion gels’ miscibility, thermal stabilitymore » and homogeneity. Ionic liquids with the least basic anion (bis(trifluoromethylsulfonyl)imide) and aromatic cations containing acidic proton (e.g. imidazolium and pyridinium) gave the most stable and miscible ion gels. Phase stability was shown to be a function of both ionic liquid content and temperature, with phase separation observed at elevated temperatures. In conclusion, gas permeability testing with carbon dioxide and nitrogen and ionic conductivity measurements confirmed that these ionic liquids increased the gas permeability and ionic conductivity of the polymers.« less

Correlation between ion diffusional motion and ionic conductivity for different electrolytes based on ionic liquid.

PubMed

Kaur, Dilraj Preet; Yamada, K; Park, Jin-Soo; Sekhon, S S

2009-04-23

Room temperature ionic liquid 2,3-dimethyl-1-hexylimidazolium bis(trifluoromethane sulfonyl)imide (DMHxImTFSI) has been synthesized and used in the preparation of polymer gel electrolytes containing polymethylmethacrylate and propylene carbonate (PC). The onset of ion diffusional motion has been studied by (1)H and (19)F NMR spectroscopy and the results obtained for ionic liquid, liquid electrolytes, and polymer gel electrolytes have been correlated with the ionic conductivity results for these electrolytes in the 100-400 K temperature range. The temperature at which (1)H and (19)F NMR lines show motional narrowing and hence ion diffusional motion starts has been found to be closely related to the temperature at which a large increase in ionic conductivity has been observed for these electrolytes. Polymer gel electrolytes have high ionic conductivity over a wide range of temperatures. Thermogravimetric analysis/differential scanning calorimetry studies show that the ionic liquid (DMHxImTFSI) used in the present study is thermally stable up to 400 degrees C, whereas the addition of PC lowers the thermal stability of polymer gel electrolytes containing the ionic liquid. Different electrolytes have been observed to show high ionic conductivity in different range of temperatures, which can be helpful in the design of polymer gel electrolytes for specific applications.

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.

Centrality dependence of pion freeze-out radii in Pb-Pb collisions at √{sN N}=2.76 TeV

NASA Astrophysics Data System (ADS)

Adam, J.; Adamová, D.; Aggarwal, M. M.; Aglieri Rinella, G.; Agnello, M.; Agrawal, N.; Ahammed, Z.; Ahn, S. U.; Aimo, I.; Aiola, S.; Ajaz, M.; Akindinov, A.; Alam, S. N.; Aleksandrov, D.; Alessandro, B.; Alexandre, D.; Alfaro Molina, R.; Alici, A.; Alkin, A.; Almaraz, J. R. M.; Alme, J.; Alt, T.; Altinpinar, S.; Altsybeev, I.; Alves Garcia Prado, C.; Andrei, C.; Andronic, A.; Anguelov, V.; Anielski, J.; Antičić, T.; Antinori, F.; Antonioli, P.; Aphecetche, L.; Appelshäuser, H.; Arcelli, S.; Armesto, N.; Arnaldi, R.; Arsene, I. C.; Arslandok, M.; Audurier, B.; Augustinus, A.; Averbeck, R.; Azmi, M. D.; Bach, M.; Badalà, A.; Baek, Y. W.; Bagnasco, S.; Bailhache, R.; Bala, R.; Baldisseri, A.; Baltasar Dos Santos Pedrosa, F.; Baral, R. C.; Barbano, A. M.; Barbera, R.; Barile, F.; Barnaföldi, G. G.; Barnby, L. S.; Barret, V.; Bartalini, P.; Barth, K.; Bartke, J.; Bartsch, E.; Basile, M.; Bastid, N.; Basu, S.; Bathen, B.; Batigne, G.; Batista Camejo, A.; Batyunya, B.; Batzing, P. C.; Bearden, I. G.; Beck, H.; Bedda, C.; Behera, N. K.; Belikov, I.; Bellini, F.; Bello Martinez, H.; Bellwied, R.; Belmont, R.; Belmont-Moreno, E.; Belyaev, V.; Bencedi, G.; Beole, S.; Berceanu, I.; Bercuci, A.; Berdnikov, Y.; Berenyi, D.; Bertens, R. A.; Berzano, D.; Betev, L.; Bhasin, A.; Bhat, I. R.; Bhati, A. K.; Bhattacharjee, B.; Bhom, J.; Bianchi, L.; Bianchi, N.; Bianchin, C.; Bielčík, J.; Bielčíková, J.; Bilandzic, A.; Biswas, R.; Biswas, S.; Bjelogrlic, S.; Blair, J. T.; Blanco, F.; Blau, D.; Blume, C.; Bock, F.; Bogdanov, A.; Bøggild, H.; Boldizsár, L.; Bombara, M.; Book, J.; Borel, H.; Borissov, A.; Borri, M.; Bossú, F.; Botta, E.; Böttger, S.; Braun-Munzinger, P.; Bregant, M.; Breitner, T.; Broker, T. A.; Browning, T. A.; Broz, M.; Brucken, E. J.; Bruna, E.; Bruno, G. E.; Budnikov, D.; Buesching, H.; Bufalino, S.; Buncic, P.; Busch, O.; Buthelezi, Z.; Butt, J. B.; Buxton, J. T.; Caffarri, D.; Cai, X.; Caines, H.; Calero Diaz, L.; Caliva, A.; Calvo Villar, E.; Camerini, P.; Carena, F.; Carena, W.; Carnesecchi, F.; Castillo Castellanos, J.; Castro, A. J.; Casula, E. A. R.; Cavicchioli, C.; Ceballos Sanchez, C.; Cepila, J.; Cerello, P.; Cerkala, J.; Chang, B.; Chapeland, S.; Chartier, M.; Charvet, J. L.; Chattopadhyay, S.; Chattopadhyay, S.; Chelnokov, V.; Cherney, M.; Cheshkov, C.; Cheynis, B.; Chibante Barroso, V.; Chinellato, D. D.; Chochula, P.; Choi, K.; Chojnacki, M.; Choudhury, S.; Christakoglou, P.; Christensen, C. H.; Christiansen, P.; Chujo, T.; Chung, S. U.; Chunhui, Z.; Cicalo, C.; Cifarelli, L.; Cindolo, F.; Cleymans, J.; Colamaria, F.; Colella, D.; Collu, A.; Colocci, M.; Conesa Balbastre, G.; Conesa Del Valle, Z.; Connors, M. E.; Contreras, J. G.; Cormier, T. M.; Corrales Morales, Y.; Cortés Maldonado, I.; Cortese, P.; Cosentino, M. R.; Costa, F.; Crochet, P.; Cruz Albino, R.; Cuautle, E.; Cunqueiro, L.; Dahms, T.; Dainese, A.; Danu, A.; Das, D.; Das, I.; Das, S.; Dash, A.; Dash, S.; de, S.; de Caro, A.; de Cataldo, G.; de Cuveland, J.; de Falco, A.; de Gruttola, D.; De Marco, N.; de Pasquale, S.; Deisting, A.; Deloff, A.; Dénes, E.; D'Erasmo, G.; di Bari, D.; di Mauro, A.; di Nezza, P.; Diaz Corchero, M. A.; Dietel, T.; Dillenseger, P.; Divià, R.; Djuvsland, Ø.; Dobrin, A.; Dobrowolski, T.; Domenicis Gimenez, D.; Dönigus, B.; Dordic, O.; Drozhzhova, T.; Dubey, A. K.; Dubla, A.; Ducroux, L.; Dupieux, P.; Ehlers, R. J.; Elia, D.; Engel, H.; Erazmus, B.; Erdemir, I.; Erhardt, F.; Eschweiler, D.; Espagnon, B.; Estienne, M.; Esumi, S.; Eum, J.; Evans, D.; Evdokimov, S.; Eyyubova, G.; Fabbietti, L.; Fabris, D.; Faivre, J.; Fantoni, A.; Fasel, M.; Feldkamp, L.; Felea, D.; Feliciello, A.; Feofilov, G.; Ferencei, J.; Fernández Téllez, A.; Ferreiro, E. G.; Ferretti, A.; Festanti, A.; Feuillard, V. J. G.; Figiel, J.; Figueredo, M. A. S.; Filchagin, S.; Finogeev, D.; Fiore, E. M.; Fleck, M. G.; Floris, M.; Foertsch, S.; Foka, P.; Fokin, S.; Fragiacomo, E.; Francescon, A.; Frankenfeld, U.; Fuchs, U.; Furget, C.; Furs, A.; Fusco Girard, M.; Gaardhøje, J. J.; Gagliardi, M.; Gago, A. M.; Gallio, M.; Gangadharan, D. R.; Ganoti, P.; Gao, C.; Garabatos, C.; Garcia-Solis, E.; Gargiulo, C.; Gasik, P.; Germain, M.; Gheata, A.; Gheata, M.; Ghosh, P.; Ghosh, S. K.; Gianotti, P.; Giubellino, P.; Giubilato, P.; Gladysz-Dziadus, E.; Glässel, P.; Goméz Coral, D. M.; Gomez Ramirez, A.; González-Zamora, P.; Gorbunov, S.; Görlich, L.; Gotovac, S.; Grabski, V.; Graczykowski, L. K.; Graham, K. L.; Grelli, A.; Grigoras, A.; Grigoras, C.; Grigoriev, V.; Grigoryan, A.; Grigoryan, S.; Grinyov, B.; Grion, N.; Grosse-Oetringhaus, J. F.; Grossiord, J.-Y.; Grosso, R.; Guber, F.; Guernane, R.; Guerzoni, B.; Gulbrandsen, K.; Gulkanyan, H.; Gunji, T.; Gupta, A.; Gupta, R.; Haake, R.; Haaland, Ø.; Hadjidakis, C.; Haiduc, M.; Hamagaki, H.; Hamar, G.; Hansen, A.; Harris, J. W.; Hartmann, H.; Harton, A.; Hatzifotiadou, D.; Hayashi, S.; Heckel, S. T.; Heide, M.; Helstrup, H.; Herghelegiu, A.; Herrera Corral, G.; Hess, B. A.; Hetland, K. F.; Hilden, T. E.; Hillemanns, H.; Hippolyte, B.; Hosokawa, R.; Hristov, P.; Huang, M.; Humanic, T. J.; Hussain, N.; Hussain, T.; Hutter, D.; Hwang, D. S.; Ilkaev, R.; Ilkiv, I.; Inaba, M.; Ippolitov, M.; Irfan, M.; Ivanov, M.; Ivanov, V.; Izucheev, V.; Jacobs, P. M.; Jadlovska, S.; Jahnke, C.; Jang, H. J.; Janik, M. A.; Jayarathna, P. H. S. Y.; Jena, C.; Jena, S.; Jimenez Bustamante, R. T.; Jones, P. G.; Jung, H.; Jusko, A.; Kalinak, P.; Kalweit, A.; Kamin, J.; Kang, J. H.; Kaplin, V.; Kar, S.; Karasu Uysal, A.; Karavichev, O.; Karavicheva, T.; Karayan, L.; Karpechev, E.; Kebschull, U.; Keidel, R.; Keijdener, D. L. D.; Keil, M.; Khan, K. H.; Khan, M. M.; Khan, P.; Khan, S. A.; Khanzadeev, A.; Kharlov, Y.; Kileng, B.; Kim, B.; Kim, D. W.; Kim, D. J.; Kim, H.; Kim, J. S.; Kim, M.; Kim, M.; Kim, S.; Kim, T.; Kirsch, S.; Kisel, I.; Kiselev, S.; Kisiel, A.; Kiss, G.; Klay, J. L.; Klein, C.; Klein, J.; Klein-Bösing, C.; Kluge, A.; Knichel, M. L.; Knospe, A. G.; Kobayashi, T.; Kobdaj, C.; Kofarago, M.; Kollegger, T.; Kolojvari, A.; Kondratiev, V.; Kondratyeva, N.; Kondratyuk, E.; Konevskikh, A.; Kopcik, M.; Kour, M.; Kouzinopoulos, C.; Kovalenko, O.; Kovalenko, V.; Kowalski, M.; Koyithatta Meethaleveedu, G.; Kral, J.; Králik, I.; Kravčáková, A.; Krelina, M.; Kretz, M.; Krivda, M.; Krizek, F.; Kryshen, E.; Krzewicki, M.; Kubera, A. M.; Kučera, V.; Kugathasan, T.; Kuhn, C.; Kuijer, P. G.; Kulakov, I.; Kumar, A.; Kumar, J.; Kumar, L.; Kurashvili, P.; Kurepin, A.; Kurepin, A. B.; Kuryakin, A.; Kushpil, S.; Kweon, M. J.; Kwon, Y.; La Pointe, S. L.; La Rocca, P.; Lagana Fernandes, C.; Lakomov, I.; Langoy, R.; Lara, C.; Lardeux, A.; Lattuca, A.; Laudi, E.; Lea, R.; Leardini, L.; Lee, G. R.; Lee, S.; Legrand, I.; Lehas, F.; Lemmon, R. C.; Lenti, V.; Leogrande, E.; León Monzón, I.; Leoncino, M.; Lévai, P.; Li, S.; Li, X.; Lien, J.; Lietava, R.; Lindal, S.; Lindenstruth, V.; Lippmann, C.; Lisa, M. A.; Ljunggren, H. M.; Lodato, D. F.; Loenne, P. I.; Loginov, V.; Loizides, C.; Lopez, X.; López Torres, E.; Lowe, A.; Luettig, P.; Lunardon, M.; Luparello, G.; Luz, P. H. F. N. D.; Maevskaya, A.; Mager, M.; Mahajan, S.; Mahmood, S. M.; Maire, A.; Majka, R. D.; Malaev, M.; Maldonado Cervantes, I.; Malinina, L.; Mal'Kevich, D.; Malzacher, P.; Mamonov, A.; Manko, V.; Manso, F.; Manzari, V.; Marchisone, M.; Mareš, J.; Margagliotti, G. V.; Margotti, A.; Margutti, J.; Marín, A.; Markert, C.; Marquard, M.; Martin, N. A.; Martin Blanco, J.; Martinengo, P.; Martínez, M. I.; Martínez García, G.; Martinez Pedreira, M.; Martynov, Y.; Mas, A.; Masciocchi, S.; Masera, M.; Masoni, A.; Massacrier, L.; Mastroserio, A.; Masui, H.; Matyja, A.; Mayer, C.; Mazer, J.; Mazzoni, M. A.; McDonald, D.; Meddi, F.; Melikyan, Y.; Menchaca-Rocha, A.; Meninno, E.; Mercado Pérez, J.; Meres, M.; Miake, Y.; Mieskolainen, M. M.; Mikhaylov, K.; Milano, L.; Milosevic, J.; Minervini, L. M.; Mischke, A.; Mishra, A. N.; Miśkowiec, D.; Mitra, J.; Mitu, C. M.; Mohammadi, N.; Mohanty, B.; Molnar, L.; Montaño Zetina, L.; Montes, E.; Morando, M.; Moreira de Godoy, D. A.; Moretto, S.; Morreale, A.; Morsch, A.; Muccifora, V.; Mudnic, E.; Mühlheim, D.; Muhuri, S.; Mukherjee, M.; Mulligan, J. D.; Munhoz, M. G.; Murray, S.; Musa, L.; Musinsky, J.; Nandi, B. K.; Nania, R.; Nappi, E.; Naru, M. U.; Nattrass, C.; Nayak, K.; Nayak, T. K.; Nazarenko, S.; Nedosekin, A.; Nellen, L.; Ng, F.; Nicassio, M.; Niculescu, M.; Niedziela, J.; Nielsen, B. S.; Nikolaev, S.; Nikulin, S.; Nikulin, V.; Noferini, F.; Nomokonov, P.; Nooren, G.; Noris, J. C. C.; Norman, J.; Nyanin, A.; Nystrand, J.; Oeschler, H.; Oh, S.; Oh, S. K.; Ohlson, A.; Okatan, A.; Okubo, T.; Olah, L.; Oleniacz, J.; Oliveira da Silva, A. C.; Oliver, M. H.; Onderwaater, J.; Oppedisano, C.; Orava, R.; Ortiz Velasquez, A.; Oskarsson, A.; Otwinowski, J.; Oyama, K.; Ozdemir, M.; Pachmayer, Y.; Pagano, P.; Paić, G.; Pajares, C.; Pal, S. K.; Pan, J.; Pandey, A. K.; Pant, D.; Papcun, P.; Papikyan, V.; Pappalardo, G. S.; Pareek, P.; Park, W. J.; Parmar, S.; Passfeld, A.; Paticchio, V.; Patra, R. N.; Paul, B.; Peitzmann, T.; Pereira da Costa, H.; Pereira de Oliveira Filho, E.; Peresunko, D.; Pérez Lara, C. E.; Perez Lezama, E.; Peskov, V.; Pestov, Y.; Petráček, V.; Petrov, V.; Petrovici, M.; Petta, C.; Piano, S.; Pikna, M.; Pillot, P.; Pinazza, O.; Pinsky, L.; Piyarathna, D. B.; Płoskoń, M.; Planinic, M.; Pluta, J.; Pochybova, S.; Podesta-Lerma, P. L. M.; Poghosyan, M. G.; Polichtchouk, B.; Poljak, N.; Poonsawat, W.; Pop, A.; Porteboeuf-Houssais, S.; Porter, J.; Pospisil, J.; Prasad, S. K.; Preghenella, R.; Prino, F.; Pruneau, C. A.; Pshenichnov, I.; Puccio, M.; Puddu, G.; Pujahari, P.; Punin, V.; Putschke, J.; Qvigstad, H.; Rachevski, A.; Raha, S.; Rajput, S.; Rak, J.; Rakotozafindrabe, A.; Ramello, L.; Raniwala, R.; Raniwala, S.; Räsänen, S. S.; Rascanu, B. T.; Rathee, D.; Read, K. F.; Real, J. S.; Redlich, K.; Reed, R. J.; Rehman, A.; Reichelt, P.; Reidt, F.; Ren, X.; Renfordt, R.; Reolon, A. R.; Reshetin, A.; Rettig, F.; Revol, J.-P.; Reygers, K.; Riabov, V.; Ricci, R. A.; Richert, T.; Richter, M.; Riedler, P.; Riegler, W.; Riggi, F.; Ristea, C.; Rivetti, A.; Rocco, E.; Rodríguez Cahuantzi, M.; Rodriguez Manso, A.; Røed, K.; Rogochaya, E.; Rohr, D.; Röhrich, D.; Romita, R.; Ronchetti, F.; Ronflette, L.; Rosnet, P.; Rossi, A.; Roukoutakis, F.; Roy, A.; Roy, C.; Roy, P.; Rubio Montero, A. J.; Rui, R.; Russo, R.; Ryabinkin, E.; Ryabov, Y.; Rybicki, A.; Sadovsky, S.; Šafařík, K.; Sahlmuller, B.; Sahoo, P.; Sahoo, R.; Sahoo, S.; Sahu, P. K.; Saini, J.; Sakai, S.; Saleh, M. A.; Salgado, C. A.; Salzwedel, J.; Sambyal, S.; Samsonov, V.; Sanchez Castro, X.; Šándor, L.; Sandoval, A.; Sano, M.; Sarkar, D.; Scapparone, E.; Scarlassara, F.; Scharenberg, R. P.; Schiaua, C.; Schicker, R.; Schmidt, C.; Schmidt, H. R.; Schuchmann, S.; Schukraft, J.; Schulc, M.; Schuster, T.; Schutz, Y.; Schwarz, K.; Schweda, K.; Scioli, G.; Scomparin, E.; Scott, R.; Seger, J. E.; Sekiguchi, Y.; Sekihata, D.; Selyuzhenkov, I.; Senosi, K.; Seo, J.; Serradilla, E.; Sevcenco, A.; Shabanov, A.; Shabetai, A.; Shadura, O.; Shahoyan, R.; Shangaraev, A.; Sharma, A.; Sharma, M.; Sharma, M.; Sharma, N.; Shigaki, K.; Shtejer, K.; Sibiriak, Y.; Siddhanta, S.; Sielewicz, K. M.; Siemiarczuk, T.; Silvermyr, D.; Silvestre, C.; Simatovic, G.; Simonetti, G.; Singaraju, R.; Singh, R.; Singha, S.; Singhal, V.; Sinha, B. C.; Sinha, T.; Sitar, B.; Sitta, M.; Skaali, T. B.; Slupecki, M.; Smirnov, N.; Snellings, R. J. M.; Snellman, T. W.; Søgaard, C.; Soltz, R.; Song, J.; Song, M.; Song, Z.; Soramel, F.; Sorensen, S.; Spacek, M.; Spiriti, E.; Sputowska, I.; Spyropoulou-Stassinaki, M.; Srivastava, B. K.; Stachel, J.; Stan, I.; Stefanek, G.; Steinpreis, M.; Stenlund, E.; Steyn, G.; Stiller, J. H.; Stocco, D.; Strmen, P.; Suaide, A. A. P.; Sugitate, T.; Suire, C.; Suleymanov, M.; Sultanov, R.; Šumbera, M.; Symons, T. J. M.; Szabo, A.; Szanto de Toledo, A.; Szarka, I.; Szczepankiewicz, A.; Szymanski, M.; Takahashi, J.; Tambave, G. J.; Tanaka, N.; Tangaro, M. A.; Tapia Takaki, J. D.; Tarantola Peloni, A.; Tarhini, M.; Tariq, M.; Tarzila, M. G.; Tauro, A.; Tejeda Muñoz, G.; Telesca, A.; Terasaki, K.; Terrevoli, C.; Teyssier, B.; Thäder, J.; Thomas, D.; Tieulent, R.; Timmins, A. R.; Toia, A.; Trogolo, S.; Trubnikov, V.; Trzaska, W. H.; Tsuji, T.; Tumkin, A.; Turrisi, R.; Tveter, T. S.; Ullaland, K.; Uras, A.; Usai, G. L.; Utrobicic, A.; Vajzer, M.; Vala, M.; Valencia Palomo, L.; Vallero, S.; van der Maarel, J.; van Hoorne, J. W.; van Leeuwen, M.; Vanat, T.; Vande Vyvre, P.; Varga, D.; Vargas, A.; Vargyas, M.; Varma, R.; Vasileiou, M.; Vasiliev, A.; Vauthier, A.; Vechernin, V.; Veen, A. M.; Veldhoen, M.; Velure, A.; Venaruzzo, M.; Vercellin, E.; Vergara Limón, S.; Vernet, R.; Verweij, M.; Vickovic, L.; Viesti, G.; Viinikainen, J.; Vilakazi, Z.; Villalobos Baillie, O.; Vinogradov, A.; Vinogradov, L.; Vinogradov, Y.; Virgili, T.; Vislavicius, V.; Viyogi, Y. P.; Vodopyanov, A.; Völkl, M. A.; Voloshin, K.; Voloshin, S. A.; Volpe, G.; von Haller, B.; Vorobyev, I.; Vranic, D.; Vrláková, J.; Vulpescu, B.; Vyushin, A.; Wagner, B.; Wagner, J.; Wang, H.; Wang, M.; Wang, Y.; Watanabe, D.; Watanabe, Y.; Weber, M.; Weber, S. G.; Wessels, J. P.; Westerhoff, U.; Wiechula, J.; Wikne, J.; Wilde, M.; Wilk, G.; Wilkinson, J.; Williams, M. C. S.; Windelband, B.; Winn, M.; Yaldo, C. G.; Yang, H.; Yang, P.; Yano, S.; Yin, Z.; Yokoyama, H.; Yoo, I.-K.; Yurchenko, V.; Yushmanov, I.; Zaborowska, A.; Zaccolo, V.; Zaman, A.; Zampolli, C.; Zanoli, H. J. C.; Zaporozhets, S.; Zardoshti, N.; Zarochentsev, A.; Závada, P.; Zaviyalov, N.; Zbroszczyk, H.; Zgura, I. S.; Zhalov, M.; Zhang, H.; Zhang, X.; Zhang, Y.; Zhao, C.; Zhigareva, N.; Zhou, D.; Zhou, Y.; Zhou, Z.; Zhu, H.; Zhu, J.; Zhu, X.; Zichichi, A.; Zimmermann, A.; Zimmermann, M. B.; Zinovjev, G.; Zyzak, M.; Alice Collaboration

2016-02-01

We report on the measurement of freeze-out radii for pairs of identical-charge pions measured in Pb-Pb collisions at √{sNN}=2.76 TeV as a function of collision centrality and the average transverse momentum of the pair kT. Three-dimensional sizes of the system (femtoscopic radii), as well as direction-averaged one-dimensional radii are extracted. The radii decrease with kT, following a power-law behavior. This is qualitatively consistent with expectations from a collectively expanding system, produced in hydrodynamic calculations. The radii also scale linearly with 1 /3. This behavior is compared to world data on femtoscopic radii in heavy-ion collisions. While the dependence is qualitatively similar to results at smaller √{sNN}, a decrease in the ratio Rout/Rside is seen, which is in qualitative agreement with a specific prediction from hydrodynamic models: a change from inside-out to outside-in freeze-out configuration. The results provide further evidence for the production of a collective, strongly coupled system in heavy-ion collisions at the CERN Large Hadron Collider.

Centrality dependence of pion freeze-out radii in Pb-Pb collisions at s N N = 2.76  TeV

DOE PAGES

Adam, J.; Adamová, D.; Aggarwal, M. M.; ...

2016-02-04

Here, we report on the measurement of freeze-out radii for pairs of identical-charge pions measured in Pb-Pb collisions at √s NN = 2.76 TeV as a function of collision centrality and the average transverse momentum of the pair k T. Three-dimensional sizes of the system (femtoscopic radii), as well as direction-averaged one-dimensional radii are extracted. The radii decrease with k T, following a power-law behavior. This is qualitatively consistent with expectations from a collectively expanding system, produced in hydrodynamic calculations. The radii also scale linearly with < dN ch/d η > 1/3. We compare this behavior to world data onmore » femtoscopic radii in heavy-ion collisions. While the dependence is qualitatively similar to results at smaller √s NN, a decrease in the ratio R out/R side is seen, which is in qualitative agreement with a specific prediction from hydrodynamic models: a change from inside-out to outside-in freeze-out configuration. Furthermore, these results provide further evidence for the production of a collective, strongly coupled system in heavy-ion collisions at the CERN Large Hadron Collider.« less

Molecular mobility, morphology, and ion conduction in ionomers for electroactive devices

NASA Astrophysics Data System (ADS)

Tudryn, Gregory J.

A sequential study of ion-containing polymers capable of ion solvation with varied ion content, dielectric constant, and counterions is presented in this dissertation in order to compare ion transport properties in ionomers with various ionic interactions. Structure-property relationships in these ion containing polymers are defined using x-ray scattering, rheology and dielectric spectroscopy, enabling the quantification of ion transport dynamics. Poly(ethylene oxide), (PEO) based ionomers are investigated in order to probe the relation between ion conduction and segmental relaxation, and copolymers of PEO and Poly(tetramethylene oxide), (PTMO) further develop an understanding of the trade-off between ion solvation and segmental dynamics. Ionomers with ionic liquid counterions probe diffuse charge interactions and steric effects on ion transport, and incorporation of ionic liquids into ionomer membranes such as Nafion provides desirable thermal and ion conducting properties which extend the use of such membranes for electroactive devices. PEO ionomers exhibit a strong relation between ionic conductivity and segmental dynamics, providing insight that the glass transition temperature, Tg, dominates the ion conduction mechanism. Increasing temperature induces aggregation of ionic groups as evidenced by the static dielectric constant and X-ray scattering as a function of temperature, revealing the contribution of ionic dipoles in the measured dielectric constant. The trade-off between ion solvation and fast polymer segmental dynamics are quantified in copolymer ionomers of PEO and lower Tg PTMO. While conducting ion content remains nearly unchanged, conductivity is lowered upon incorporation of PTMO, because the vast majority of the PTMO microphase separates from the PEO-rich microdomain that remains continuous and contributes most of the ion conduction. Dielectric constants and X-ray scattering show consistent changes with temperature that suggest a cascading aggregation process in Na ionomers as ionic dipoles thermally randomize and lower the measured dielectric constant of the medium, leading to further aggregation. We observe amplified microphase-separation through ionic groups preferentially solvated by PEO chains, as seen in block copolymers with added salt. Even at 25%PEO / 75%PTMO the ionomers have VFT temperature dependence of conducting ion mobility, meaning that the 25% PEO/ion microphase is still continuous A model is developed to describe the frequency dependent storage and loss modulus and the delay in Rouse motion due to ion association lifetime, as functions of ion content and molecular weight for our low molecular weight ionomers. The ion rearrangement relaxation in dielectric spectroscopy is clearly the ion association lifetime that controls terminal dynamics in linear viscoelasticity, allowing a simple sticky Rouse model, using the most-probable distribution based on NMR Mn, to fully describe master curves of the frequency dependent storage and loss modulus. Using insight from ionic interaction strength, ionic liquids are used as counterions, effectively plasticizing the ionomers without added solvent. Ionic interactions were weakened with increasing counterion size, and with modification of cations using ether-oxygen, promoting self-solvation, which increases conducting ion density by an order of magnitude. Room temperature ionic liquids were subsequently used in combination with NafionRTM membranes as electroactive substrates to correlate ion transport to morphology as a function of volume fraction of ionic liquid. This study illuminated the critical volume uptake of ionic liquid in Nafion, identifying percolation of ionic pathways and a significant increase in dielectric constant at low frequencies, indicating an increase in the number density of ions capable of polarizing at the electrode surface. Consequently, the fundamental information obtained about the structure-property relations of ionomers can be used to predict and design advanced ion-containing polymers to be used in battery membranes and a variety of electroactive devices, including actuators and electromechanical sensors.

Anesthetic biotransformation and renal function in obese patients during and after methoxyflurane or halothane anesthesia.

PubMed

Young, S R; Stoelting, R K; Peterson, C; Madura, J A

1975-04-01

Anesthetic biotransformation and renal function were studied in obese adult patients (148 plus or minus 8 kg; mean plus or minus SE) anesthetized for three hours with 60 per cent nitrous oxide plus either methoxyflurane or halothane for elective jejunoileal small-bowel-bypass operations. There was no evidence of persistent renal dysfunction in any patient postoperatively, but serum osmolality was elevated 72 hours after methoxyflurane anesthesia. Urine concentrating ability was not determined. Peak serum ionic fluoride concentration was 55.8 plus or minus 5.8 muM/1 two hours after discontinuation of methoxyflurane. Urinary ionic fluoride and oxalate excretions increased postoperatively. Compared with previously reported data from nonobese patients, serum ionic fluoride concentrations in obese patients increased more rapidly during methoxyflurane anesthesia and peaked higher and sooner after discontinuation of methoxyflurane. The peak serum ionic fluoride concentration was 10.4 plus or minus 1.5 muM/1 at the conclusion of halothane anesthesia, significantly more than the corresponding value in nonobese patients. Intraoperative liver biopsies from 23 of 27 patients showed moderate to severe fatty metamorphosis. Fatty liver infiltration may have increased hepatic anesthetic uptake and exposed more methoxyflurane or halothane to hepatic microsomal enzymes. The more rapid elevation and higher peak levels of serum ionic fluoride following methoxyflurane, and to a lesser extent following halothane, may reflect increased anesthetic biotransformation in obese compared with nonobese patients. To avoid excessive serum ionic fluoride elevations the authors recommended limiting low-dose methoxyflurane anesthesia delivered to obese patients with potential fatty liver infiltration to no more than three hours.

Role of composition, bond covalency, and short-range order in the disordering of stannate pyrochlores by swift heavy ion irradiation

NASA Astrophysics Data System (ADS)

Tracy, Cameron L.; Shamblin, Jacob; Park, Sulgiye; Zhang, Fuxiang; Trautmann, Christina; Lang, Maik; Ewing, Rodney C.

2016-08-01

A2S n2O7 (A =Nd ,Sm,Gd,Er,Yb,and Y) materials with the pyrochlore structure were irradiated with 2.2 GeV Au ions to systematically investigate disordering of this system in response to dense electronic excitation. Structural modifications were characterized, over multiple length scales, by transmission electron microscopy, x-ray diffraction, and Raman spectroscopy. Transformations to amorphous and disordered phases were observed, with disordering dominating the structural response of materials with small A -site cation ionic radii. Both the disordered and amorphous phases were found to possess weberite-type local ordering, differing only in that the disordered phase exhibits a long-range, modulated arrangement of weberite-type structural units into an average defect-fluorite structure, while the amorphous phase remains fully aperiodic. Comparison with the behavior of titanate and zirconate pyrochlores showed minimal influence of the high covalency of the Sn-O bond on this phase behavior. An analytical model of damage accumulation was developed to account for simultaneous amorphization and recrystallization of the disordered phase during irradiation.

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

Beales, T.P.; Parberry, J.M.

(Bi{sub 0.33}Cd{sub 0.67})Sr{sub 2}YCu{sub 2}O{sub 7{minus}{delta}} can be synthesized single phase by XRD, between 800 and 950 C. It has a tetragonal structure, space group P4/mmm, and lattice parameters a = 3.802 {angstrom} and c = 11.96 {angstrom}. The Cd site can be fully replaced with an appropriate M{sup 11} ion and the Y site can be chemically substituted up to 100% by lanthanide ions with ionic radii falling between those of Nd and Gd, with a measurable shift in a and c axis lattice parameters. As synthesized, (Bi{sub 0.33}Cd{sub 0.67})Sr{sub 2}YCu{sub 2}O{sub 7{minus}{delta}} is semiconducting and paramagnetic down tomore » 4 K. Superconductivity can be induced by a post-synthesis annealing in high pressure oxygen to give {Tc} = 40 K. Thermopower measurements show that the material is underdoped with S{sub 290K} = 50 {mu}VK{sup {minus}1}. Introduction of extra charge carriers to raise {Tc} by doping Ca on the Y site is not chemically possible with the synthesis techniques used.« less

Lattice parameter functions of (AmyU1-y)O2-x based on XRD and XANES measurements

NASA Astrophysics Data System (ADS)

Nishi, Tsuyoshi; Nakada, Masami; Hirata, Masaru

2017-12-01

The lattice parameters of (Am0.50U0.50)O2.0, (Am0.37U0.63)O2.0, and (Am0.50U0.50)O2-x were determined by powder X-ray diffraction with Cu Kα radiation. In addition, the lattice parameter functions of (AmyU1-y)O2-x (0.00

Impact of concomitant Y and Mn substitution on superconductivity in La1 -yYyFe1 -xMnxAsO0.89F0.11

NASA Astrophysics Data System (ADS)

Kappenberger, Rhea; Hammerath, Franziska; Rousse, Pierre; Afrassa, Mesfin Asfaw; Haghighi, M. Hossein; Kamusella, Sirko; Prando, Giacomo; Lamura, Gianrico; Wolter, Anja U. B.; Moroni, Matteo; Sanna, Samuele; Carretta, Pietro; Hess, Christian; Grafe, Hans-Joachim; Klauss, Hans-Henning; Wurmehl, Sabine; Büchner, Bernd

2018-02-01

We discuss the impact of concomitant substitution of Fe by Mn and La by Y in optimally F-doped LaFeAsO0.89F0.11 . Mn has a known poisoning effect on superconductivity which is particularly strong in the La1111 system, where 0.2% of Mn were reported to completely suppress superconductivity. Through isovalent substitution of La by the much smaller Y we are able to inflict chemical pressure on the structure, which we show is stabilizing the superconducting state, resulting in a drastically larger amount of Mn needed to completely quench superconductivity. Interestingly, we find that the lattice parameter c changes significantly even for small amounts of Mn substitution within a series, which is unexpected taking only the differences between ionic radii into account. We discuss our findings in the light of electron localization caused by small amounts of paramagnetic Mn impurities in La1 -yYyFe1 -xMnxAsO0.89F0.11 also indicated by resistivity and Mößbauer measurements.

Biocompatible Er, Yb co-doped fluoroapatite upconversion nanoparticles for imaging applications

NASA Astrophysics Data System (ADS)

Anjana, R.; K. M., Kurias; M. K., Jayaraj

2017-08-01

Upconversion luminescence, visible emission on infra red (IR) excitation was achieved in a biocompatible material, fluoroapatite. Fluoroapatite crystals are well known biomaterials, which is a component of tooth enamel. Also it can be considered as an excellent host material for lanthanide doping since the ionic radii of lanthanide is similar to that of calcium ion(Ca2+) hence successful incorporation of dopants within the lattice is possible. Erbium (Er), Ytterbium (Yb) co-doped fluorapatite (FAp) nanoparticles were prepared by precipitation method. The particles show intense visible emission when excited with 980 nm laser. Since upconversion luminescence is a multiphoton process the excitation power dependence on emission will give number of photons involved in the emission of single photon. Excitation power dependence studies show that two photons are involved in the emission of single photons. The value of slope was different for different emission peak because of the difference in intermediate energy level involved. The crystal structure and morphology of the particle were determined using X-ray diffractometer (XRD) and field emission scanning electron microscope (FESEM). These particles with surface functionalisation can be used for live cell imaging.

Single-Crystal Growth of Cl-Doped n-Type SnS Using SnCl2 Self-Flux.

PubMed

Iguchi, Yuki; Inoue, Kazutoshi; Sugiyama, Taiki; Yanagi, Hiroshi

2018-06-05

SnS is a promising photovoltaic semiconductor owing to its suitable band gap energy and high optical absorption coefficient for highly efficient thin film solar cells. The most significant carnage is demonstration of n-type SnS. In this study, Cl-doped n-type single crystals were grown using SnCl 2 self-flux method. The obtained crystal was lamellar, with length and width of a few millimeters and thickness ranging between 28 and 39 μm. X-ray diffraction measurements revealed the single crystals had an orthorhombic unit cell. Since the ionic radii of S 2- and Cl - are similar, Cl doping did not result in substantial change in lattice parameter. All the elements were homogeneously distributed on a cleaved surface; the Sn/(S + Cl) ratio was 1.00. The crystal was an n-type degenerate semiconductor with a carrier concentration of ∼3 × 10 17 cm -3 . Hall mobility at 300 K was 252 cm 2 V -1 s -1 and reached 363 cm 2 V -1 s -1 at 142 K.

Dispersions of polymer ionomers: I.

PubMed

Capek, Ignác

2004-12-31

The principal subject discussed in the current paper is the effect of ionic functional groups in polymers on the formation of nontraditional polymer materials, polymer blends or polymer dispersions. Ionomers are polymers that have a small amount of ionic groups distributed along a nonionic hydrocarbon chain. Specific interactions between components in a polymer blend can induce miscibility of two or more otherwise immiscible polymers. Such interactions include hydrogen bonding, ion-dipole interactions, acid-base interactions or transition metal complexation. Ion-containing polymers provide a means of modifying properties of polymer dispersions by controlling molecular structure through the utilization of ionic interactions. Ionomers having a relatively small number of ionic groups distributed usually along nonionic organic backbone chains can agglomerate into the following structures: (1) multiplets, consisting of a small number of tightly packed ion pairs; and (2) ionic clusters, larger aggregates than multiplets. Ionomers exhibit unique solid-state properties as a result of strong associations among ionic groups attached to the polymer chains. An important potential application of ionomers is in the area of thermoplastic elastomers, where the associations constitute thermally reversible cross-links. The ionic (anionic, cationic or polar) groups are spaced more or less randomly along the polymer chain. Because in this type of ionomer an anionic group falls along the interior of the chain, it trails two hydrocarbon chain segments, and these must be accommodated sterically within any domain structure into which the ionic group enters. The primary effects of ionic functionalization of a polymer are to increase the glass transition temperature, the melt viscosity and the characteristic relaxation times. The polymer microstructure is also affected, and it is generally agreed that in most ionomers, microphase-separated, ion-rich aggregates form as a result of strong ion-dipole attractions. As a consequence of this new phase, additional relaxation processes are often observed in the viscoelastic behavior of ionomers. Light functionalization of polymers can increase the glass transition temperature and gives rise to two new features in viscoelastic behavior: (1) a rubbery plateau above T(g) and (2) a second loss process at elevated temperatures. The rubbery plateau was due to the formation of a physical network. The major effect of the ionic aggregate was to increase the longer time relaxation processes. This in turn increases the melt viscosity and is responsible for the network-like behavior of ionomers above the glass transition temperature. Ionomers rich in polar groups can fulfill the criteria for the self-assembly formation. The reported phenomenon of surface micelle formation has been found to be very general for these materials.

A review of the structure and dynamics of nanoconfined water and ionic liquids via molecular dynamics simulation.

PubMed

Foroutan, Masumeh; Fatemi, S Mahmood; Esmaeilian, Farshad

2017-02-01

During the past decade, the research on fluids in nanoconfined geometries has received considerable attention as a consequence of their wide applications in different fields. Several nanoconfined systems such as water and ionic liquids, together with an equally impressive array of nanoconfining media such as carbon nanotube, graphene and graphene oxide have received increasingly growing interest in the past years. Water is the first system that has been reviewed in this article, due to its important role in transport phenomena in environmental sciences. Water is often considered as a highly nanoconfined system, due to its reduction to a few layers of water molecules between the extended surface of large macromolecules. The second system discussed here is ionic liquids, which have been widely studied in the modern green chemistry movement. Considering the great importance of ionic liquids in industry, and also their oil/water counterpart, nanoconfined ionic liquid system has become an important area of research with many fascinating applications. Furthermore, the method of molecular dynamics simulation is one of the major tools in the theoretical study of water and ionic liquids in nanoconfinement, which increasingly has been joined with experimental procedures. In this way, the choice of water and ionic liquids in nanoconfinement is justified by applying molecular dynamics simulation approaches in this review article.

Long-range electrostatic screening in ionic liquids

PubMed Central

Gebbie, Matthew A.; Dobbs, Howard A.; Valtiner, Markus; Israelachvili, Jacob N.

2015-01-01

Electrolyte solutions with high concentrations of ions are prevalent in biological systems and energy storage technologies. Nevertheless, the high interaction free energy and long-range nature of electrostatic interactions makes the development of a general conceptual picture of concentrated electrolytes a significant challenge. In this work, we study ionic liquids, single-component liquids composed solely of ions, in an attempt to provide a novel perspective on electrostatic screening in very high concentration (nonideal) electrolytes. We use temperature-dependent surface force measurements to demonstrate that the long-range, exponentially decaying diffuse double-layer forces observed across ionic liquids exhibit a pronounced temperature dependence: Increasing the temperature decreases the measured exponential (Debye) decay length, implying an increase in the thermally driven effective free-ion concentration in the bulk ionic liquids. We use our quantitative results to propose a general model of long-range electrostatic screening in ionic liquids, where thermally activated charge fluctuations, either free ions or correlated domains (quasiparticles), take on the role of ions in traditional dilute electrolyte solutions. This picture represents a crucial step toward resolving several inconsistencies surrounding electrostatic screening and charge transport in ionic liquids that have impeded progress within the interdisciplinary ionic liquids community. More broadly, our work provides a previously unidentified way of envisioning highly concentrated electrolytes, with implications for diverse areas of inquiry, ranging from designing electrochemical devices to rationalizing electrostatic interactions in biological systems. PMID:26040001

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.

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.

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

Pawellek, Nicole; Krivov, Alexander V.; Marshall, Jonathan P.

The radii of debris disks and the sizes of their dust grains are important tracers of the planetesimal formation mechanisms and physical processes operating in these systems. Here we use a representative sample of 34 debris disks resolved in various Herschel Space Observatory (Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA) programs to constrain the disk radii and the size distribution of their dust. While we modeled disks with both warm and cold components, and identified warm inner disks around about two-thirds of the stars, we focusmore » our analysis only on the cold outer disks, i.e., Kuiper-belt analogs. We derive the disk radii from the resolved images and find a large dispersion for host stars of any spectral class, but no significant trend with the stellar luminosity. This argues against ice lines as a dominant player in setting the debris disk sizes, since the ice line location varies with the luminosity of the central star. Fixing the disk radii to those inferred from the resolved images, we model the spectral energy distribution to determine the dust temperature and the grain size distribution for each target. While the dust temperature systematically increases toward earlier spectral types, the ratio of the dust temperature to the blackbody temperature at the disk radius decreases with the stellar luminosity. This is explained by a clear trend of typical sizes increasing toward more luminous stars. The typical grain sizes are compared to the radiation pressure blowout limit s {sub blow} that is proportional to the stellar luminosity-to-mass ratio and thus also increases toward earlier spectral classes. The grain sizes in the disks of G- to A-stars are inferred to be several times s {sub blow} at all stellar luminosities, in agreement with collisional models of debris disks. The sizes, measured in the units of s {sub blow}, appear to decrease with the luminosity, which may be suggestive of the disk's stirring level increasing toward earlier-type stars. The dust opacity index β ranges between zero and two, and the size distribution index q varies between three and five for all the disks in the sample.« less

Understanding the impact of nanoscale aggregation on charge transport and structural dynamics in room temperature ionic liquids

NASA Astrophysics Data System (ADS)

Griffin, Philip; Holt, Adam; Wang, Yangyang; Sokolov, Alexei

2015-03-01

Amphiphilic room temperature ionic liquids (ILs) segregate on the nanoscale, forming intricate networks of charge-rich ionic domains intercalated with charge-poor aliphatic domains. While this structural phenomenon has been well established through x-ray diffraction studies and atomistic MD simulations, the precise effects of nanophase segregation on ion transport and structural dynamics in ILs remains poorly understood. Using a combination of broadband dielectric spectroscopy, light scattering spectroscopy, and rheology, we have characterized the ionic conductivity, structural dynamics, and shear viscosity of a homologous series of quaternary ammonium ionic liquids over a wide temperature range. Upon increasing the length and volume fraction of the alkyl side chains of these quaternary ammonium ILs, ionic conductivity decreases precipitously, although no corresponding slowing of the structural dynamics is observed. Instead, we identify the dynamical signature of supramolecular aggregates. Our results directly demonstrate the role that chemical structure and ionic aggregation plays in determining the charge transport properties of amphiphilic ILs.

Presence of a monoclinic (Pm) phase in the morphotropic phase boundary region of multiferroic (1 − x)Bi(Ni{sub 1/2}Ti{sub 1/2})O{sub 3}-xPbTiO{sub 3} solid solution: A Rietveld study

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

Pandey, Rishikesh, E-mail: akhilesh-bhu@yahoo.com, E-mail: aksingh.mst@itbhu.ac.in; Singh, Akhilesh Kumar, E-mail: akhilesh-bhu@yahoo.com, E-mail: aksingh.mst@itbhu.ac.in

2014-07-28

We present here the results of structural studies on multiferroic (1 − x)Bi(Ni{sub 1/2}Ti{sub 1/2})O{sub 3}-xPbTiO{sub 3} solid solution using Rietveld analysis on powder x-ray diffraction data in the composition range 0.35 ≤ x ≤ 0.55. The stability region of various crystallographic phases at room temperature for (1 − x)Bi(Ni{sub 1/2}Ti{sub 1/2})O{sub 3}-xPbTiO{sub 3} is determined precisely. Structural transformation from pseudo-cubic (x ≤ 0.40) to tetragonal (x ≥ 0.50) phase is observed via phase coexistence region demarcating the morphotropic phase boundary. The morphotropic phase boundary region consists of coexisting tetragonal and monoclinic structures with space group P4mm and Pm, respectively, stable in composition range 0.41 ≤ x ≤ 0.49 as confirmed by Rietveld analysis. The resultsmore » of Rietveld analysis completely rule out the coexistence of rhombohedral and tetragonal phases in the morphotropic phase boundary region reported by earlier workers. A comparison between the bond lengths for “B-site cations-oxygen anions” obtained after Rietveld refinement, with the bond length calculated using Shannon-Prewitt ionic radii, reveals the ionic nature of B-O (Ni/Ti-O) bonds for the cubic phase and partial covalent character for the other crystallographic phases.« less

Lidocaine self-sacrificially improves the skin permeation of the acidic and poorly water-soluble drug etodolac via its transformation into an ionic liquid.

PubMed

Miwa, Yasushi; Hamamoto, Hidetoshi; Ishida, Tatsuhiro

2016-05-01

Poor transdermal penetration of active pharmaceutical ingredients (APIs) impairs both bioavailability and therapeutic benefits and is a major challenge in the development of transdermal drug delivery systems. Here, we transformed a poorly water-soluble drug, etodolac, into an ionic liquid in order to improve its hydrophobicity, hydrophilicity and skin permeability. The ionic liquid was prepared by mixing etodolac with lidocaine (1:1, mol/mol). Both the free drug and the transformed ionic liquid were characterized by differential scanning colorimetry (DSC), infrared spectroscopy (IR), and saturation concentration measurements. In addition, in vitro skin-permeation testing was carried out via an ionic liquid-containing patch (Etoreat patch). The lidocaine and etodolac in ionic liquid form led to a relatively lower melting point than either lidocaine or etodolac alone, and this improved the lipophilicity/hydrophilicity of etodolac. In vitro skin-permeation testing demonstrated that the Etoreat patch significantly increased the skin permeation of etodolac (9.3-fold) compared with an etodolac alone patch, although an Etoreat patch did not increase the skin permeation of lidocaine, which was consistent with the results when using a lidocaine alone patch. Lidocaine appeared to self-sacrificially improve the skin permeation of etodolac via its transformation into an ionic liquid. The data suggest that ionic liquids composed of approved drugs may substantially expand the formulation preparation method to meet the challenges of drugs which are characterized by poor rates of transdermal absorption. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Specific binding of (/sup 3/H-Tyr8)physalaemin to rat submaxillary gland substance P receptor

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

Bahouth, S.W.; Lazaro, D.M.; Brundish, D.E.

1985-01-01

(/sup 3/H)Physalaemin ((/sup 3/H)PHY) binds to a single class of noninteracting sites on rat submaxillary gland membranes suspended in high ionic strength media with a KD of 2.7 nM, a Bmax of 240 fmol/mg of protein, and low nonspecific binding. The relative potencies of substance P (SP) and its fragments in competing with (/sup 3/H)PHY correlate with their relative salivation potencies. This indicates that (/sup 3/H)PHY interacts with a physiologically relevant SP receptor. In low ionic strength media, the KD of (/sup 3/H)PHY does not change, but SP and some of its fragments are more potent than PHY in competingmore » with (/sup 3/H) PHY. Computer-assisted analysis of (/sup 3/H)PHY and (/sup 3/H)SP binding in high and low ionic strength media demonstrated that both peptides are equipotent in high ionic strength but that the affinity of SP increases by 70-fold in low ionic strength. The SP fragments that contain a basic residue in positions 1 and/or 3 also display an increased affinity in low ionic strength. These findings document that (/sup 3/H)PHY binding in high ionic strength (mu . 0.6) accurately reflects the pharmacological potencies of agonists on the SP-P receptor. The binding of (/sup 3/H)PHY, like that of (/sup 3/H)SP, increases by the addition of divalent cations (Mg2+ greater than Ca2+ greater than Mn2+). Guanine nucleotides decrease (/sup 3/H)PHY binding by decreasing the Bmax to the same level (160 fmol/mg of protein), in the presence or absence of Mg2+.« less

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

Interfacial Structures of Trihexyltetradecylphosphonium-bis(mandelato)borate Ionic Liquid Confined between Gold Electrodes.

PubMed

Wang, Yong-Lei; Golets, Mikhail; Li, Bin; Sarman, Sten; Laaksonen, Aatto

2017-02-08

Atomistic molecular dynamics simulations have been performed to study microscopic the interfacial ionic structures, molecular arrangements, and orientational preferences of trihexyltetradecylphosphonium-bis(mandelato)borate ([P 6,6,6,14 ][BMB]) ionic liquid confined between neutral and charged gold electrodes. It was found that both [P 6,6,6,14 ] cations and [BMB] anions are coabsorbed onto neutral electrodes at different temperatures. The hexyl and tetradecyl chains in [P 6,6,6,14 ] cations lie preferentially flat on neutral electrodes. The oxalato and phenyl rings in [BMB] anions are characterized by alternative parallel-perpendicular orientations in the mixed innermost ionic layer adjacent to neutral electrodes. An increase in temperature has a marginal effect on the interfacial ionic structures and molecular orientations of [P 6,6,6,14 ][BMB] ionic species in a confined environment. Electrifying gold electrodes leads to peculiar changes in the interfacial ionic structures and molecular orientational arrangements of [P 6,6,6,14 ] cations and [BMB] anions in negatively and positively charged gold electrodes, respectively. As surface charge density increases (but lower than 20 μC/cm 2 ), the layer thickness of the mixed innermost interfacial layer gradually increases due to a consecutive accumulation of [P 6,6,6,14 ] cations and [BMB] anions at negatively and positively charged electrodes, respectively, before the formation of distinct cationic and anionic innermost layers. Meanwhile, the molecular orientations of two oxalato rings in the same [BMB] anions change gradually from a parallel-perpendicular feature to being partially characterized by a tilted arrangement at an angle of 45° from the electrodes and finally to a dominant parallel coordination pattern along positively charged electrodes. Distinctive interfacial distribution patterns are also observed accordingly for phenyl rings that are directly connected to neighboring oxalato rings in [BMB] anions.

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.

Coupled factors influencing detachment of nano- and micro-sized particles from primary minima.

PubMed

Shen, Chongyang; Lazouskaya, Volha; Jin, Yan; Li, Baoguo; Ma, Zhiqiang; Zheng, Wenjuan; Huang, Yuanfang

2012-06-01

This study examined the detachments of nano- and micro-sized colloids from primary minima in the presence of cation exchange by laboratory column experiments. Colloids were initially deposited in columns packed with glass beads at 0.2 M CaCl(2) in the primary minima of Derjaguin-Landau-Verwey-Overbeek (DLVO) interaction energies. Then, the columns were flushed with NaCl solutions with different ionic strengths (i.e., 0.001, 0.01, 0.1 and 0.2 M). Detachments were observed at all ionic strengths and were particularly significant for the nanoparticle. The detachments increased with increasing electrolyte concentration for the nanoparticle whereas increased from 0.001 M to 0.01 M and decreased with further increasing electrolyte concentration for the micro-sized colloid. The observations were attributed to coupled influence of cation exchange, short-range repulsion, surface roughness, surface charge heterogeneity, and deposition in the secondary minima. The detachments of colloids from primary minima challenge the common belief that colloid interaction in primary minimum is irreversible and resistant to disturbance in solution ionic strength and composition. Although the significance of surface roughness, surface charge heterogeneity, and secondary minima on colloid deposition has been widely recognized, our study implies that they also play important roles in colloid detachment. Whereas colloid detachment is frequently associated with decrease of ionic strength, our results show that increase of ionic strength can also cause detachment due to influence of cation exchange. Copyright © 2012 Elsevier B.V. All rights reserved.

Experimental Study on the Velocity and Efficiency Characteristics of a Serial Staged Needle Array-Mesh Type EHD Gas Pump

NASA Astrophysics Data System (ADS)

Qiu, Wei; Xia, Lingzhi; Yang, Lanjun; Zhang, Qiaogen; Xiao, Lei; Chen, Li

2011-12-01

The ionic wind has good application prospects in the fields of air flow control and heat transfer enhancement. The key for successful applications is how to improve the velocity and how to increase the active area of the ionic wind. This paper designed a needle array-mesh type electrohydrodynamic (EHD) gas pump. The use of needle array electrode where corona discharge started simultaneously could enlarge the active area. The velocity of the ionic wind could increase by placing several single-stage ionic wind generators in series appropriately, called as serial staged generator. The maximum average flow velocity of 16.1 m/s and volumetric flow of 303.5 L/min were achieved at the outlet of a 25-stage gas pump and the conversion efficiency was approximately 2.2%.

ATPase activity and light scattering of acto-heavy meromyosin: dependence on ATP concentration and on ionic strength.

PubMed

Dancker, P

1975-01-01

1. The dependence on ATP concentration of ATPase activity and light scattering decrease of acto-HMM could be described at very low ionic strength by one hyperbolic adsorption isotherm with a dissociation constant of 3 X 10(-6)M. Hence the increase of ATP ase activity was paralleled by a decrease in light scattering. At higher values of ionic strength ATPase activity stopped rising before HMM was completely saturated with ATP. Higher ionic strength prevented ATPase activity from further increasing when the rigor links (links between actin and nucleotide-free myosin), which have formerly protected the ATPase against the suppressing action of higher ionic strength have fallen below a certain amount. This protecting influence of rigor links did not require tropomyosin-troponin. 2. For complete activation of ATPase activity by actin less actin was needed when HMM was incompletely saturated with ATP than when it was completely saturated with ATP. 3. The apparent affinity of ATP to regulated acto-HMM (which contained tropomyosin-troponin) was lower than to unregulated acto-HMM (which was devoid of tropomyosin-troponin). In the presence of rigor complexes (indicated by an incomplete decrease of light scattering) the ATPase activity of regulated acto-HMM was higher than that of unregulated acto-HMM. At increasing ATP concentrations the ATPase activity of regulated acto-HMM stopped rising at a similar degree of saturation with ATP as the ATPase activity of unregulated acto-HMM at the same ionic strength.

The radiation chemistry of ionic liquids: A review

DOE PAGES

Mincher, Bruce J.; Wishart, James F.

2014-07-03

Ionic liquids have received increasing attention as media for radiochemical separations. Recent literature includes examinations of the efficiencies and mechanisms of the solvent extraction of lanthanides, actinides and fission products into ionic liquid solutions. For radiochemical applications, including as replacement solvents for nuclear fuel reprocessing, a thorough understanding of the radiation chemistry of ionic liquids will be required. Such an understanding can be achieved based on a combination of steady-state radiolysis experiments coupled with post-irradiation product identification and pulse-radiolysis experiments to acquire kinetic information. These techniques allow for the elucidation of radiolytic mechanisms. This contribution reviews the current ionic liquidmore » radiation chemistry literature as it affects separations, with these considerations in mind.« less

Investigating the evolution of local structure around Er and Yb in ZnO:Er and ZnO:Er, Yb on annealing using X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Anjana, R.; Jayaraj, M. K.; Yadav, A. K.; Jha, S. N.; Bhattacharyya, D.

2018-04-01

The local structure around Er and Yb centre in ZnO favouring upconversion luminescence was studied using EXAFS (Extended X-ray absorption fine structure spectroscopy). Due to the ionic radii difference between Zn and Er, Yb ions, the dopants cannot replace Zn in the ZnO lattice properly. Er2O3 and Yb2O3 impurity phases are formed at the grain boundaries of ZnO. It is found that the local structure around the Er centre in ZnO is modified on annealing in air. The symmetry around both erbium and ytterbium reduces with increase in annealing temperature. Symmetry reduction will favour the intra-4f transition and the energy transitions causing upconversion luminescence. By fitting the EXAFS data with theoretically simulated data, it is found that the Er centre forms a local structure similar to C4ν symmetry which is a distorted octahedron. On annealing the sample to 1200 °C, all the erbium centres are transformed to C4ν symmetry causing enhanced upconversion emission. Yb centre has also been modified on annealing. The decrease in co-ordination number with annealing temperature will decrease the symmetry and increase the near infrared absorption cross section. The decrease in symmetry around both the erbium and ytterbium centre and formation of C4ν symmetry around Er centre is the reason behind the activation of upconversion luminescence with high temperature annealing in both Er doped and Er, Yb co-doped ZnO samples. The study will be useful for the synthesis of high efficiency upconversion materials.

New Pb(Mg1/3Nb2/3)O3-Pb(In1/2Nb1/2)O3-PbZrO3-PbTiO3 Quaternary Ceramics: Morphotropic Phase Boundary Design and Electrical Properties.

PubMed

Luo, Nengneng; Zhang, Shujun; Li, Qiang; Xu, Chao; Yang, Zhanlue; Yan, Qingfeng; Zhang, Yiling; Shrout, Thomas R

2016-06-22

Four series of Pb(Mg1/3Nb2/3)O3-Pb(In1/2Nb1/2)O3-PbZrO3-PbTiO3 (PMN-PIN-PZ-PT) quaternary ceramics with compositions located at the morphotropic phase boundary (MPB) regions were prepared. The MPBs of the multicomponent system were predicted using a linear combination rule and experimentally confirmed by X-ray powder diffraction and electrical measurement. The positions of MPBs in multicomponent systems were found in linear correlation with the tolerance factor and ionic radii of non-PT end-members. The phase structure, piezoelectric coefficient, electromechanical coupling coefficient, unipolar strains, and dielectric properties of as-prepared ceramics were systematically investigated. The largest d33s were obtained at S36.8, L37.4, M39.6, and N35.8, with the corresponding values of 580, 450, 420, and 530 pC/N, respectively, while the largest kps were found at S34.8, L37.4, M39.6, and N35.8, with the respective values of 0.54, 0.50, 0.47, and 0.53. The largest unipolar strain Smax and high-field piezoelectric strain coefficients d33* were also observed around the respective MPB regions. The rhombohedral-to-tetragonal phase transition temperature Trt increased with increasing PIN and PZ contents. Of particular importance is that high Trt of 140-197 °C was achieved in the M series with PZ and PIN contents being around 0.208 and 0.158, which will broaden the temperature usage range.

Non-Surface Activity of Cationic Amphiphilic Diblock Copolymers

NASA Astrophysics Data System (ADS)

Ranjan Nayak, Rati; Yamada, Tasuku; Matsuoka, Hideki

2011-09-01

Cationic amphiphilic diblock copolymers containing quaternized poly (2-vinylpyridine) chain as a hydrophilic segment (PIp-b-PNMe2VP) were synthesized by living anionic polymerization. By IR measurement, we confirmed the quaternization of the polymer (PIp-b-PNMe2VP), and determined the degree of quaternization by conductometric titration. The surface tension experiment showed that the polymers are non-surface active in nature. The foam formation of the polymer solutions was also investigated with or without added salt. Almost no foam formation behavior was observed without added salt, while a little foam was observed in the presence of 1M NaCl. The critical micelle concentration (cmc) of the diblock copolymers with 3 different chain lengths was measured by the static light scattering method. The cmc values obtained in this study were much lower than the values obtained for anionic non-surface active diblock polymers studied previously. The hydrodynamic radii of the polymer micelle increased slightly in the presence of 1 M NaCl. The transmission electron microscopic images revealed spherical micelles in pure water. In the presence of salt, the cmc values increased as was the case for anionic polymers, which is unlike conventional surfactant systems but consistent with non-surface active anionic block copolymers. The microviscosity of the micelle core was evaluated using Coumarin-153 as a fluorescent anisotropy probe using steady-sate fluorescence depolarization. Non-surface activity has been proved to be universal for ionic amphiphilic block copolymers both for anionic and cationic. Hence, the origin of non-surface activity is not the charged state of water surface itself, but should be an image charge repulsion at the air/water interface.

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.

Ionic liquid-modified materials for solid-phase extraction and separation: a review.

PubMed

Vidal, Lorena; Riekkola, Marja-Liisa; Canals, Antonio

2012-02-17

In recent years, materials science has propelled to the research forefront. Ionic liquids with unique and fascinating properties have also left their footprints to the developments of materials science during the last years. In this review we highlight some of their recent advances and provide an overview at the current status of ionic liquid-modified materials applied in solid-phase extraction, liquid and gas chromatography and capillary electrochromatography with reference to recent applications. In addition, the potential of ionic liquids in the modification of capillary inner wall in capillary electrophoresis is demonstrated. The main target material modified with ionic liquids is silica, but polymers and monoliths have recently joined the studies. Although imidazolium is still clearly the most commonly used ionic liquid for the covalently modification of materials, the exploitation of pyridinium and phosphonium will most probably increase in the future. Copyright © 2011 Elsevier B.V. All rights reserved.

Corrosion Inhibition of Cast Iron in Arabian Gulf Seawater by Two Different Ionic Liquids

PubMed Central

Sherif, El-Sayed M.; Abdo, Hany S.; Zein El Abedin, Sherif

2015-01-01

In this paper we report on the corrosion inhibition of cast iron in Arabian Gulf seawater by two different ionic liquids namely, 1-ethyl-3-methylimidazolium chloride ([EMIm]Cl) and 1-butyl-1-methylpyrrolidinium chloride ([Py1,4]Cl). The inhibiting influence of the employed ionic liquids was investigated by weight loss, open circuit potential electrochemical impedance spectroscopy, and cyclic potentiodynamic polarization. The results show the corrosion inhibition impact of the employed ionic liquids (ILs). Compared with [Py1,4]Cl, [EMIm]Cl shows a higher inhibition efficiency at a short immersion time, for the examined ILs concentrations. However, [Py1,4]Cl exhibits a higher efficiency upon increasing the immersion time indicating the persistence of the inhibiting influence. The corrosion inhibition of the employed ionic liquids is attributed to the adsorption of the cations of the ionic liquids onto the surface of cast iron forming a corrosion barrier. PMID:28793413

Ionic liquid as an electrolyte additive for high performance lead-acid batteries

NASA Astrophysics Data System (ADS)

Deyab, M. A.

2018-06-01

The performance of lead-acid battery is improved in this work by inhibiting the corrosion of negative battery electrode (lead) and hydrogen gas evolution using ionic liquid (1-ethyl-3-methylimidazolium diethyl phosphate). The results display that the addition of ionic liquid to battery electrolyte (5.0 M H2SO4 solution) suppresses the hydrogen gas evolution to very low rate 0.049 ml min-1 cm-2 at 80 ppm. Electrochemical studies show that the adsorption of ionic liquid molecules on the lead electrode surface leads to the increase in the charge transfer resistance and the decrease in the double layer capacitance. I also notice a noteworthy improvement of battery capacity from 45 mAh g-1 to 83 mAh g-1 in the presence of ionic liquid compound. Scanning electron microscopy and energy dispersive X-ray analysis confirm the adsorption of ionic liquid molecules on the battery electrode surface.

Plasma observations near jupiter: initial results from voyager 1.

PubMed

Bridge, H S; Belcher, J W; Lazarus, A J; Sullivan, J D; McNutt, R L; Bagenal, F; Scudder, J D; Sittler, E C; Siscoe, G L; Vasyliunas, V M; Goertz, C K; Yeates, C M

1979-06-01

Extensive measurements of low-energy positive ions and electrons were made throughout the Jupiter encounter of Voyager 1. The bow shock and magneto-pause were crossed several times at distances consistent with variations in the upstream solar wind pressure measured on Voyager 2. During the inbound pass, the number density increased by six orders of magnitude between the innermost magnetopause crossing at approximately 47 Jupiter radii and near closest approach at approximately 5 Jupiter radii; the plasma flow during this period was predominately in the direction of corotation. Marked increases in number density were observed twice per planetary rotation, near the magnetic equator. Jupiterward of the Io plasma torus, a cold, corotating plasma was observed and the energylcharge spectra show well-resolved, heavy-ion peaks at mass-to-charge ratios A/Z* = 8, 16, 32, and 64.

Plasma observations near Jupiter - Initial results from Voyager 1

NASA Technical Reports Server (NTRS)

Bridge, H. S.; Belcher, J. W.; Lazarus, A. J.; Sullivan, J. D.; Mcnutt, R. L.; Bagenal, F.; Scudder, J. D.; Sittler, E. C.; Siscoe, G. L.; Vasyliunas, V. M.

1979-01-01

Extensive measurements of low-energy positive ions and electrons were made throughout the Jupiter encounter of Voyager 1. The bow shock and magnetopause were crossed several times at distances consistent with variations in the upstream solar wind pressure measured on Voyager 2. During the inbound pass, the number density increased by six orders of magnitude between the innermost magnetopause crossing at approximately 47 Jupiter radii and near closest approach at approximately 5 Jupiter radii; the plasma flow during this period was predominately in the direction of corotation. Marked increases in number density were observed twice per planetary rotation, near the magnetic equator. Jupiterward of the Io plasma torus, a cold, corotating plasma was observed and the energy/charge spectra show well-resolved, heavy-ion peaks at mass-to-charge ratios equal to 8, 16, 32, and 64.

Thermal power and heat energy of cloud-to-ground lightning process

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

Wang, Xuejuan; Yuan, Ping; Xue, Simin

2016-07-15

A cloud-to-ground lightning flash with nine return strokes has been recorded using a high speed slitless spectrograph and a system composed of a fast antenna and a slow antenna. Based on the spectral data and the synchronous electric field changes that were caused by the lightning, the electrical conductivity, the channel radii, the resistance per unit length, the peak current, the thermal power at the instant of peak current, and the heat energy per unit length during the first 5 μs in the discharge channel have all been calculated. The results indicate that the channel radii have linear relationships with themore » peak current. The thermal power at the peak current time increases with increasing resistance, but exponential decays with the square of the peak current.« less

Predictions of nuclear charge radii

NASA Astrophysics Data System (ADS)

Bao, M.; Lu, Y.; Zhao, Y. M.; Arima, A.

2016-12-01

The nuclear charge radius is a fundamental property of an atomic nucleus. In this article we study the predictive power of empirical relations for experimental nuclear charge radii of neighboring nuclei and predict the unknown charge radii of 1085 nuclei based on the experimental CR2013 database within an uncertainty of 0.03 fm.

Responses of articular and epiphyseal cartilage zones of developing avian radii to estrone treatment and a 2-G environment

NASA Technical Reports Server (NTRS)

Negulesco, J. A.; Kossler, T.

1978-01-01

Histological measurements of radii from chickens exposed to estrone and hypergravity are reported. Female chicks at two weeks post-hatch were maintained for two weeks at earth gravity or 2 G with daily injections of 0.2 or 0.4 mg estrone. Animals were sacrificed after the last injection, and the radii were processed by described histological techniques. The results suggest that proximal and distal epiphyses of developing radii show different morphological responses to estrone and hypergravity.

Experimental and computational study on the properties of pure and water mixed 1-ethyl-3-methylimidazolium L-(+)-lactate ionic liquid.

PubMed

Aparicio, Santiago; Alcalde, Rafael; Atilhan, Mert

2010-05-06

Ionic liquids have attracted great attention, from both industry and academe, as alternative fluids for a large collection of applications. Although the term green is used frequently to describe ionic liquids in general, it is obvious that it cannot be applied to the huge quantity of possible ionic liquids, and thus, those with adequate environmental and technological profiles must be selected for further and deeper studies, from both basic science and applied approaches. In this work, 1-ethyl-3-methylimidazolium L-(+)-lactate ionic liquid is studied, because of its remarkable properties, through a wide-ranging approach considering thermophysical, spectroscopic, and computational tools, to gain a deeper insight into its complex liquid structure, both pure and mixed with water, thus implying the main factors that would control the technological applications that could be designed using this fluid. The reported results shows a strongly structured pure ionic liquid, in which hydrogen bonding, because of the hydroxyl group of the lactate anion, develops a remarkable role, together with Coulombic forces to determine the fluid's behavior. Upon mixing with water, the ionic liquid retains its structure up to very high dilution levels, with the effect of the ionic liquid on the water structure being very large, even for very low ionic liquid mole fractions. Thus, in water solution, the studied ionic liquid evolves from noninteracting ions solvated by water molecules toward large interacting structures with increasing ionic liquid content.

Vibrational Spectroscopy of Ionic Liquids.

PubMed

Paschoal, Vitor H; Faria, Luiz F O; Ribeiro, Mauro C C

2017-05-24

Vibrational spectroscopy has continued use as a powerful tool to characterize ionic liquids since the literature on room temperature molten salts experienced the rapid increase in number of publications in the 1990's. In the past years, infrared (IR) and Raman spectroscopies have provided insights on ionic interactions and the resulting liquid structure in ionic liquids. A large body of information is now available concerning vibrational spectra of ionic liquids made of many different combinations of anions and cations, but reviews on this literature are scarce. This review is an attempt at filling this gap. Some basic care needed while recording IR or Raman spectra of ionic liquids is explained. We have reviewed the conceptual basis of theoretical frameworks which have been used to interpret vibrational spectra of ionic liquids, helping the reader to distinguish the scope of application of different methods of calculation. Vibrational frequencies observed in IR and Raman spectra of ionic liquids based on different anions and cations are discussed and eventual disagreements between different sources are critically reviewed. The aim is that the reader can use this information while assigning vibrational spectra of an ionic liquid containing another particular combination of anions and cations. Different applications of IR and Raman spectroscopies are given for both pure ionic liquids and solutions. Further issues addressed in this review are the intermolecular vibrations that are more directly probed by the low-frequency range of IR and Raman spectra and the applications of vibrational spectroscopy in studying phase transitions of ionic liquids.

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.

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.

A molecular dynamics study of lithium-containing aprotic heterocyclic ionic liquid electrolytes

NASA Astrophysics Data System (ADS)

Lourenço, Tuanan C.; Zhang, Yong; Costa, Luciano T.; Maginn, Edward J.

2018-05-01

Classical molecular dynamics simulations were performed on twelve different ionic liquids containing aprotic heterocyclic anions doped with Li+. These ionic liquids have been shown to be promising electrolytes for lithium ion batteries. Self-diffusivities, lithium transference numbers, densities, and free volumes were computed as a function of lithium concentration. The dynamics and free volume decreased with increasing lithium concentration, and the trends were rationalized by examining the changes to the liquid structure. Of those examined in the present work, it was found that (methyloxymethyl)triethylphosphonium triazolide ionic liquids have the overall best performance.

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.

Assessing the influence of media composition and ionic strength on drug release from commercial immediate-release and enteric-coated aspirin tablets.

PubMed

Karkossa, Frank; Klein, Sandra

2017-10-01

The objective of this test series was to elucidate the importance of selecting the right media composition for a biopredictive in-vitro dissolution screening of enteric-coated dosage forms. Drug release from immediate-release (IR) and enteric-coated (EC) aspirin formulations was assessed in phosphate-based and bicarbonate-based media with different pH, electrolyte composition and ionic strength. Drug release from aspirin IR tablets was unaffected by media composition. In contrast, drug release from EC aspirin formulations was affected by buffer species and ionic strength. In all media, drug release increased with increasing ionic strength, but in bicarbonate-based buffers was delayed when compared with that in phosphate-based buffers. Interestingly, the cation species in the dissolution medium had also a clear impact on drug release. Drug release profiles obtained in Blank CarbSIF, a new medium simulating pH and average ionic composition of small intestinal fluid, were different from those obtained in all other buffer compositions studied. Results from this study in which the impact of various media parameters on drug release of EC aspirin formulations was systematically screened clearly show that when developing predictive dissolution tests, it is important to simulate the ionic composition of intraluminal fluids as closely as possible. © 2017 Royal Pharmaceutical Society.

Protic ammonium carboxylate ionic liquids: insight into structure, dynamics and thermophysical properties by alkyl group functionalization.

PubMed

Reddy, Th Dhileep N; Mallik, Bhabani S

2017-04-19

This study is aimed at characterising the structure, dynamics and thermophysical properties of five alkylammonium carboxylate ionic liquids (ILs) from classical molecular dynamics simulations. The structural features of these ILs were characterised by calculating the site-site radial distribution functions, g(r), spatial distribution functions and structure factors. The structural properties demonstrate that ILs show greater interaction between cations and anions when alkyl chain length increases on the cation or anion. In all ILs, spatial distribution functions show that the anion is close to the acidic hydrogen atoms of the ammonium cation. We determined the role of alkyl group functionalization of the charged entities, cations and anions, in the dynamical behavior and the transport coefficients of this family of ionic liquids. The dynamics of ILs are described by studying the mean square displacement (MSD) of the centres of mass of the ions, diffusion coefficients, ionic conductivities and hydrogen bonds as well as residence dynamics. The diffusion coefficients and ionic conductivity decrease with an increase in the size of the cation or anion. The effect of alkyl chain length on ionic conductivity calculated in this article is consistent with the findings of other experimental studies. Hydrogen bond lifetimes and residence times along with structure factors were also calculated, and are related to alkyl chain length.

Supercapacitors based on modified graphene electrodes with poly(ionic liquid)

NASA Astrophysics Data System (ADS)

Trigueiro, João Paulo C.; Lavall, Rodrigo L.; Silva, Glaura G.

2014-06-01

The improved accessibility of the electrolyte to the surface of carbon nanomaterials is a challenge to be overcome in supercapacitors based on ionic liquid electrolytes. In this study, we report the preparation of supercapacitors based on reduced graphene oxide (RGO) electrodes and ionic liquid as the electrolyte (specifically, 1-methyl-1-propylpyrrolidinium bis(trifluoromethylsulfonyl)imide or [MPPy][TFSI]). Two types of electrodes were compared: the RGO-based electrode and a poly(ionic liquid)-modified RGO electrode (PIL:RGO). The supercapacitor produced with the PIL:RGO electrode and [MPPy][TFSI] showed an electrochemical stability of 3 V and provided a capacitance of 71.5 F g-1 at room temperature; this capacitance is 130% higher with respect to the RGO-based supercapacitor. The decrease of the specific capacitance after 2000 cycles is only 10% for the PIL:RGO-based device. The results revealed the potential of the PIL:RGO material as an electrode for supercapacitors. This composite electrode increases the compatibility with the ionic liquid electrolyte compared to an RGO electrode, promoting an increase in the effective surface area of the electrode accessible to the electrolyte ions.

Vector Analysis of Ionic Collision on CaCO3 Precipitation Based on Vibration Time History

NASA Astrophysics Data System (ADS)

Mangestiyono, W.; Muryanto, S.; Jamari, J.; Bayuseno, A. P.

2017-05-01

Vibration effects on the piping system can result from the internal factor of fluid or the external factor of the mechanical equipment operation. As the pipe vibrated, the precipitation process of CaCO3 on the inner pipe could be affected. In the previous research, the effect of vibration on CaCO3 precipitation in piping system was clearly verified. This increased the deposition rate and decreased the induction time. However, the mechanism of vibration control in CaCO3 precipitation process as the presence of vibration has not been recognized yet. In the present research, the mechanism of vibration affecting the CaCO3 precipitation was investigated through vector analysis of ionic collision. The ionic vector force was calculated based on the amount of the activation energy and the vibration force was calculated based on the vibration sensor data. The vector resultant of ionic collision based on the vibration time history was analyzed to prove that vibration brings ionic collision randomly to the planar horizontal direction and its collision model was suspected as the cause of the increasing deposition rate.

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.

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.

Ionic-Liquid-Infused Nanostructures as Repellent Surfaces.

PubMed

Galvan, Yaraset; Phillips, Katherine R; Haumann, Marco; Wasserscheid, Peter; Zarraga, Ramon; Vogel, Nicolas

2018-06-12

In order to prepare lubricant-infused repellent coatings on silica nanostructures using low vapor pressure ionic liquids as lubricants, we study the wetting behavior of a set of imidazolium-based ionic liquids with different alkyl side chains as a function of the applied surface functionalities. We take advantage of the structural color of inverse opals prepared from a colloidal coassembly technique to study the infiltration of ionic liquids into these nanoporous structures. We find that the more hydrophobic ionic liquids with butyl and hexyl side chains can completely infiltrate inverse opals functionalized with mixed self-assembled monolayers composed of imidazole groups and aliphatic hydrocarbon chains, which we introduce via silane chemistry. These molecular species reflect the chemical nature of the ionic liquid, thereby increasing the affinity between the liquid and solid surface. The mixed surface chemistry provides sufficiently small contact angles with the ionic liquid to infiltrate the nanopores while maximizing the contact angle with water. As a result, the mixed monolayers enable the design of a stable ionic liquid/solid interface that is able to repel water as a test liquid. Our results underline the importance of matching chemical affinities to predict and control the wetting behavior in complex, multiphase systems.

One-dimensional pion, kaon, and proton femtoscopy in Pb-Pb collisions at s NN = 2.76 TeV

DOE PAGES

Adam, J.; Adamová, D.; Aggarwal, M. M.; ...

2015-11-19

Tmore » he size of the particle emission region in high-energy collisions can be deduced using the femtoscopic correlations of particle pairs at low relative momentum. Such correlations arise due to quantum statistics and Coulomb and strong final state interactions. In this paper, results are presented from femtoscopic analyses of π ± π ±, K ± K ±, K$$0\\atop{S}$$K$$0\\atop{S}$$, pp , and $$\\overline{p}$$ $$\\overline{p}$$ correlations from Pb-Pb collisions at s NN = 2.76 eV by the ALICE experiment at the LHC. One-dimensional radii of the system are extracted from correlation functions in terms of the invariant momentum difference of the pair. he comparison of the measured radii with the predictions from a hydrokinetic model is discussed. he pion and kaon source radii display a monotonic decrease with increasing average pair transverse mass m which is consistent with hydrodynamic model predictions for central collisions. Lastly, the kaon and proton source sizes can be reasonably described by approximate m scaling.« less

One-dimensional pion, kaon, and proton femtoscopy in Pb-Pb collisions at √{sNN}=2.76 TeV

NASA Astrophysics Data System (ADS)

Adam, J.; Adamová, D.; Aggarwal, M. M.; Aglieri Rinella, G.; Agnello, M.; Agrawal, N.; Ahammed, Z.; Ahn, S. U.; Aimo, I.; Aiola, S.; Ajaz, M.; Akindinov, A.; Alam, S. N.; Aleksandrov, D.; Alessandro, B.; Alexandre, D.; Alfaro Molina, R.; Alici, A.; Alkin, A.; Alme, J.; Alt, T.; Altinpinar, S.; Altsybeev, I.; Alves Garcia Prado, C.; Andrei, C.; Andronic, A.; Anguelov, V.; Anielski, J.; Antičić, T.; Antinori, F.; Antonioli, P.; Aphecetche, L.; Appelshäuser, H.; Arcelli, S.; Armesto, N.; Arnaldi, R.; Arsene, I. C.; Arslandok, M.; Audurier, B.; Augustinus, A.; Averbeck, R.; Azmi, M. D.; Bach, M.; Badalà, A.; Baek, Y. W.; Bagnasco, S.; Bailhache, R.; Bala, R.; Baldisseri, A.; Baltasar Dos Santos Pedrosa, F.; Baral, R. C.; Barbano, A. M.; Barbera, R.; Barile, F.; Barnaföldi, G. G.; Barnby, L. S.; Barret, V.; Bartalini, P.; Barth, K.; Bartke, J.; Bartsch, E.; Basile, M.; Bastid, N.; Basu, S.; Bathen, B.; Batigne, G.; Batista Camejo, A.; Batyunya, B.; Batzing, P. C.; Bearden, I. G.; Beck, H.; Bedda, C.; Behera, N. K.; Belikov, I.; Bellini, F.; Bello Martinez, H.; Bellwied, R.; Belmont, R.; Belmont-Moreno, E.; Belyaev, V.; Bencedi, G.; Beole, S.; Berceanu, I.; Bercuci, A.; Berdnikov, Y.; Berenyi, D.; Bertens, R. A.; Berzano, D.; Betev, L.; Bhasin, A.; Bhat, I. R.; Bhati, A. K.; Bhattacharjee, B.; Bhom, J.; Bianchi, L.; Bianchi, N.; Bianchin, C.; Bielčík, J.; Bielčíková, J.; Bilandzic, A.; Biswas, R.; Biswas, S.; Bjelogrlic, S.; Blanco, F.; Blau, D.; Blume, C.; Bock, F.; Bogdanov, A.; Bøggild, H.; Boldizsár, L.; Bombara, M.; Book, J.; Borel, H.; Borissov, A.; Borri, M.; Bossú, F.; Botje, M.; Botta, E.; Böttger, S.; Braun-Munzinger, P.; Bregant, M.; Breitner, T.; Broker, T. A.; Browning, T. A.; Broz, M.; Brucken, E. J.; Bruna, E.; Bruno, G. E.; Budnikov, D.; Buesching, H.; Bufalino, S.; Buncic, P.; Busch, O.; Buthelezi, Z.; Butt, J. B.; Buxton, J. T.; Caffarri, D.; Cai, X.; Caines, H.; Calero Diaz, L.; Caliva, A.; Calvo Villar, E.; Camerini, P.; Carena, F.; Carena, W.; Castillo Castellanos, J.; Castro, A. J.; Casula, E. A. R.; Cavicchioli, C.; Ceballos Sanchez, C.; Cepila, J.; Cerello, P.; Cerkala, J.; Chang, B.; Chapeland, S.; Chartier, M.; Charvet, J. L.; Chattopadhyay, S.; Chattopadhyay, S.; Chelnokov, V.; Cherney, M.; Cheshkov, C.; Cheynis, B.; Chibante Barroso, V.; Chinellato, D. D.; Chochula, P.; Choi, K.; Chojnacki, M.; Choudhury, S.; Christakoglou, P.; Christensen, C. H.; Christiansen, P.; Chujo, T.; Chung, S. U.; Chunhui, Z.; Cicalo, C.; Cifarelli, L.; Cindolo, F.; Cleymans, J.; Colamaria, F.; Colella, D.; Collu, A.; Colocci, M.; Conesa Balbastre, G.; Conesa Del Valle, Z.; Connors, M. E.; Contreras, J. G.; Cormier, T. M.; Corrales Morales, Y.; Cortés Maldonado, I.; Cortese, P.; Cosentino, M. R.; Costa, F.; Crochet, P.; Cruz Albino, R.; Cuautle, E.; Cunqueiro, L.; Dahms, T.; Dainese, A.; Danu, A.; Das, D.; Das, I.; Das, S.; Dash, A.; Dash, S.; de, S.; de Caro, A.; de Cataldo, G.; de Cuveland, J.; de Falco, A.; de Gruttola, D.; De Marco, N.; de Pasquale, S.; Deisting, A.; Deloff, A.; Dénes, E.; D'Erasmo, G.; di Bari, D.; di Mauro, A.; di Nezza, P.; Diaz Corchero, M. A.; Dietel, T.; Dillenseger, P.; Divià, R.; Djuvsland, Ø.; Dobrin, A.; Dobrowolski, T.; Domenicis Gimenez, D.; Dönigus, B.; Dordic, O.; Dubey, A. K.; Dubla, A.; Ducroux, L.; Dupieux, P.; Ehlers, R. J.; Elia, D.; Engel, H.; Erazmus, B.; Erdemir, I.; Erhardt, F.; Eschweiler, D.; Espagnon, B.; Estienne, M.; Esumi, S.; Eum, J.; Evans, D.; Evdokimov, S.; Eyyubova, G.; Fabbietti, L.; Fabris, D.; Faivre, J.; Fantoni, A.; Fasel, M.; Feldkamp, L.; Felea, D.; Feliciello, A.; Feofilov, G.; Ferencei, J.; Fernández Téllez, A.; Ferreiro, E. G.; Ferretti, A.; Festanti, A.; Feuillard, V. J. G.; Figiel, J.; Figueredo, M. A. S.; Filchagin, S.; Finogeev, D.; Fionda, F. M.; Fiore, E. M.; Fleck, M. G.; Floris, M.; Foertsch, S.; Foka, P.; Fokin, S.; Fragiacomo, E.; Francescon, A.; Frankenfeld, U.; Fuchs, U.; Furget, C.; Furs, A.; Fusco Girard, M.; Gaardhøje, J. J.; Gagliardi, M.; Gago, A. M.; Gallio, M.; Gangadharan, D. R.; Ganoti, P.; Gao, C.; Garabatos, C.; Garcia-Solis, E.; Gargiulo, C.; Gasik, P.; Germain, M.; Gheata, A.; Gheata, M.; Ghosh, P.; Ghosh, S. K.; Gianotti, P.; Giubellino, P.; Giubilato, P.; Gladysz-Dziadus, E.; Glässel, P.; Gomez Ramirez, A.; González-Zamora, P.; Gorbunov, S.; Görlich, L.; Gotovac, S.; Grabski, V.; Graczykowski, L. K.; Graham, K. L.; Grelli, A.; Grigoras, A.; Grigoras, C.; Grigoriev, V.; Grigoryan, A.; Grigoryan, S.; Grinyov, B.; Grion, N.; Grosse-Oetringhaus, J. F.; Grossiord, J.-Y.; Grosso, R.; Guber, F.; Guernane, R.; Guerzoni, B.; Gulbrandsen, K.; Gulkanyan, H.; Gunji, T.; Gupta, A.; Gupta, R.; Haake, R.; Haaland, Ø.; Hadjidakis, C.; Haiduc, M.; Hamagaki, H.; Hamar, G.; Hansen, A.; Harris, J. W.; Hartmann, H.; Harton, A.; Hatzifotiadou, D.; Hayashi, S.; Heckel, S. T.; Heide, M.; Helstrup, H.; Herghelegiu, A.; Herrera Corral, G.; Hess, B. A.; Hetland, K. F.; Hilden, T. E.; Hillemanns, H.; Hippolyte, B.; Hosokawa, R.; Hristov, P.; Huang, M.; Humanic, T. J.; Hussain, N.; Hussain, T.; Hutter, D.; Hwang, D. S.; Ilkaev, R.; Ilkiv, I.; Inaba, M.; Ionita, C.; Ippolitov, M.; Irfan, M.; Ivanov, M.; Ivanov, V.; Izucheev, V.; Jacobs, P. M.; Jadlovska, S.; Jahnke, C.; Jang, H. J.; Janik, M. A.; Jayarathna, P. H. S. Y.; Jena, C.; Jena, S.; Jimenez Bustamante, R. T.; Jones, P. G.; Jung, H.; Jusko, A.; Kalinak, P.; Kalweit, A.; Kamin, J.; Kang, J. H.; Kaplin, V.; Kar, S.; Karasu Uysal, A.; Karavichev, O.; Karavicheva, T.; Karpechev, E.; Kebschull, U.; Keidel, R.; Keijdener, D. L. D.; Keil, M.; Khan, K. H.; Khan, M. M.; Khan, P.; Khan, S. A.; Khanzadeev, A.; Kharlov, Y.; Kileng, B.; Kim, B.; Kim, D. W.; Kim, D. J.; Kim, H.; Kim, J. S.; Kim, M.; Kim, M.; Kim, S.; Kim, T.; Kirsch, S.; Kisel, I.; Kiselev, S.; Kisiel, A.; Kiss, G.; Klay, J. L.; Klein, C.; Klein, J.; Klein-Bösing, C.; Kluge, A.; Knichel, M. L.; Knospe, A. G.; Kobayashi, T.; Kobdaj, C.; Kofarago, M.; Kollegger, T.; Kolojvari, A.; Kondratiev, V.; Kondratyeva, N.; Kondratyuk, E.; Konevskikh, A.; Kopcik, M.; Kouzinopoulos, C.; Kovalenko, O.; Kovalenko, V.; Kowalski, M.; Kox, S.; Koyithatta Meethaleveedu, G.; Kral, J.; Králik, I.; Kravčáková, A.; Krelina, M.; Kretz, M.; Krivda, M.; Krizek, F.; Kryshen, E.; Krzewicki, M.; Kubera, A. M.; Kučera, V.; Kugathasan, T.; Kuhn, C.; Kuijer, P. G.; Kulakov, I.; Kumar, J.; Kumar, L.; Kurashvili, P.; Kurepin, A.; Kurepin, A. B.; Kuryakin, A.; Kushpil, S.; Kweon, M. J.; Kwon, Y.; La Pointe, S. L.; La Rocca, P.; Lagana Fernandes, C.; Lakomov, I.; Langoy, R.; Lara, C.; Lardeux, A.; Lattuca, A.; Laudi, E.; Lea, R.; Leardini, L.; Lee, G. R.; Lee, S.; Legrand, I.; Lemmon, R. C.; Lenti, V.; Leogrande, E.; León Monzón, I.; Leoncino, M.; Lévai, P.; Li, S.; Li, X.; Lien, J.; Lietava, R.; Lindal, S.; Lindenstruth, V.; Lippmann, C.; Lisa, M. A.; Ljunggren, H. M.; Lodato, D. F.; Loenne, P. I.; Loggins, V. R.; Loginov, V.; Loizides, C.; Lopez, X.; López Torres, E.; Lowe, A.; Luettig, P.; Lunardon, M.; Luparello, G.; Luz, P. H. F. N. D.; Maevskaya, A.; Mager, M.; Mahajan, S.; Mahmood, S. M.; Maire, A.; Majka, R. D.; Malaev, M.; Maldonado Cervantes, I.; Malinina, L.; Mal'Kevich, D.; Malzacher, P.; Mamonov, A.; Manceau, L.; Manko, V.; Manso, F.; Manzari, V.; Marchisone, M.; Mareš, J.; Margagliotti, G. V.; Margotti, A.; Margutti, J.; Marín, A.; Markert, C.; Marquard, M.; Martin, N. A.; Martin Blanco, J.; Martinengo, P.; Martínez, M. I.; Martínez García, G.; Martinez Pedreira, M.; Martynov, Y.; Mas, A.; Masciocchi, S.; Masera, M.; Masoni, A.; Massacrier, L.; Mastroserio, A.; Masui, H.; Matyja, A.; Mayer, C.; Mazer, J.; Mazzoni, M. A.; McDonald, D.; Meddi, F.; Menchaca-Rocha, A.; Meninno, E.; Mercado Pérez, J.; Meres, M.; Miake, Y.; Mieskolainen, M. M.; Mikhaylov, K.; Milano, L.; Milosevic, J.; Minervini, L. M.; Mischke, A.; Mishra, A. N.; Miśkowiec, D.; Mitra, J.; Mitu, C. M.; Mohammadi, N.; Mohanty, B.; Molnar, L.; Montaño Zetina, L.; Montes, E.; Morando, M.; Moreira de Godoy, D. A.; Moretto, S.; Morreale, A.; Morsch, A.; Muccifora, V.; Mudnic, E.; Mühlheim, D.; Muhuri, S.; Mukherjee, M.; Mulligan, J. D.; Munhoz, M. G.; Murray, S.; Musa, L.; Musinsky, J.; Nandi, B. K.; Nania, R.; Nappi, E.; Naru, M. U.; Nattrass, C.; Nayak, K.; Nayak, T. K.; Nazarenko, S.; Nedosekin, A.; Nellen, L.; Ng, F.; Nicassio, M.; Niculescu, M.; Niedziela, J.; Nielsen, B. S.; Nikolaev, S.; Nikulin, S.; Nikulin, V.; Noferini, F.; Nomokonov, P.; Nooren, G.; Noris, J. C. C.; Norman, J.; Nyanin, A.; Nystrand, J.; Oeschler, H.; Oh, S.; Oh, S. K.; Ohlson, A.; Okatan, A.; Okubo, T.; Olah, L.; Oleniacz, J.; Oliveira da Silva, A. C.; Oliver, M. H.; Onderwaater, J.; Oppedisano, C.; Ortiz Velasquez, A.; Oskarsson, A.; Otwinowski, J.; Oyama, K.; Ozdemir, M.; Pachmayer, Y.; Pagano, P.; Paić, G.; Pajares, C.; Pal, S. K.; Pan, J.; Pandey, A. K.; Pant, D.; Papcun, P.; Papikyan, V.; Pappalardo, G. S.; Pareek, P.; Park, W. J.; Parmar, S.; Passfeld, A.; Paticchio, V.; Patra, R. N.; Paul, B.; Peitzmann, T.; Pereira da Costa, H.; Pereira de Oliveira Filho, E.; Peresunko, D.; Pérez Lara, C. E.; Perez Lezama, E.; Peskov, V.; Pestov, Y.; Petráček, V.; Petrov, V.; Petrovici, M.; Petta, C.; Piano, S.; Pikna, M.; Pillot, P.; Pinazza, O.; Pinsky, L.; Piyarathna, D. B.; Płoskoń, M.; Planinic, M.; Pluta, J.; Pochybova, S.; Podesta-Lerma, P. L. M.; Poghosyan, M. G.; Polichtchouk, B.; Poljak, N.; Poonsawat, W.; Pop, A.; Porteboeuf-Houssais, S.; Porter, J.; Pospisil, J.; Prasad, S. K.; Preghenella, R.; Prino, F.; Pruneau, C. A.; Pshenichnov, I.; Puccio, M.; Puddu, G.; Pujahari, P.; Punin, V.; Putschke, J.; Qvigstad, H.; Rachevski, A.; Raha, S.; Rajput, S.; Rak, J.; Rakotozafindrabe, A.; Ramello, L.; Raniwala, R.; Raniwala, S.; Räsänen, S. S.; Rascanu, B. T.; Rathee, D.; Read, K. F.; Real, J. S.; Redlich, K.; Reed, R. J.; Rehman, A.; Reichelt, P.; Reidt, F.; Ren, X.; Renfordt, R.; Reolon, A. R.; Reshetin, A.; Rettig, F.; Revol, J.-P.; Reygers, K.; Riabov, V.; Ricci, R. A.; Richert, T.; Richter, M.; Riedler, P.; Riegler, W.; Riggi, F.; Ristea, C.; Rivetti, A.; Rocco, E.; Rodríguez Cahuantzi, M.; Rodriguez Manso, A.; Røed, K.; Rogochaya, E.; Rohr, D.; Röhrich, D.; Romita, R.; Ronchetti, F.; Ronflette, L.; Rosnet, P.; Rossi, A.; Roukoutakis, F.; Roy, A.; Roy, C.; Roy, P.; Rubio Montero, A. J.; Rui, R.; Russo, R.; Ryabinkin, E.; Ryabov, Y.; Rybicki, A.; Sadovsky, S.; Šafařík, K.; Sahlmuller, B.; Sahoo, P.; Sahoo, R.; Sahoo, S.; Sahu, P. K.; Saini, J.; Sakai, S.; Saleh, M. A.; Salgado, C. A.; Salzwedel, J.; Sambyal, S.; Samsonov, V.; Sanchez Castro, X.; Šándor, L.; Sandoval, A.; Sano, M.; Santagati, G.; Sarkar, D.; Scapparone, E.; Scarlassara, F.; Scharenberg, R. P.; Schiaua, C.; Schicker, R.; Schmidt, C.; Schmidt, H. R.; Schuchmann, S.; Schukraft, J.; Schulc, M.; Schuster, T.; Schutz, Y.; Schwarz, K.; Schweda, K.; Scioli, G.; Scomparin, E.; Scott, R.; Seeder, K. S.; Seger, J. E.; Sekiguchi, Y.; Sekihata, D.; Selyuzhenkov, I.; Senosi, K.; Seo, J.; Serradilla, E.; Sevcenco, A.; Shabanov, A.; Shabetai, A.; Shadura, O.; Shahoyan, R.; Shangaraev, A.; Sharma, A.; Sharma, N.; Shigaki, K.; Shtejer, K.; Sibiriak, Y.; Siddhanta, S.; Sielewicz, K. M.; Siemiarczuk, T.; Silvermyr, D.; Silvestre, C.; Simatovic, G.; Simonetti, G.; Singaraju, R.; Singh, R.; Singha, S.; Singhal, V.; Sinha, B. C.; Sinha, T.; Sitar, B.; Sitta, M.; Skaali, T. B.; Slupecki, M.; Smirnov, N.; Snellings, R. J. M.; Snellman, T. W.; Søgaard, C.; Soltz, R.; Song, J.; Song, M.; Song, Z.; Soramel, F.; Sorensen, S.; Spacek, M.; Spiriti, E.; Sputowska, I.; Spyropoulou-Stassinaki, M.; Srivastava, B. K.; Stachel, J.; Stan, I.; Stefanek, G.; Steinpreis, M.; Stenlund, E.; Steyn, G.; Stiller, J. H.; Stocco, D.; Strmen, P.; Suaide, A. A. P.; Sugitate, T.; Suire, C.; Suleymanov, M.; Sultanov, R.; Šumbera, M.; Symons, T. J. M.; Szabo, A.; Szanto de Toledo, A.; Szarka, I.; Szczepankiewicz, A.; Szymanski, M.; Takahashi, J.; Tanaka, N.; Tangaro, M. A.; Tapia Takaki, J. D.; Tarantola Peloni, A.; Tarhini, M.; Tariq, M.; Tarzila, M. G.; Tauro, A.; Tejeda Muñoz, G.; Telesca, A.; Terasaki, K.; Terrevoli, C.; Teyssier, B.; Thäder, J.; Thomas, D.; Tieulent, R.; Timmins, A. R.; Toia, A.; Trogolo, S.; Trubnikov, V.; Trzaska, W. H.; Tsuji, T.; Tumkin, A.; Turrisi, R.; Tveter, T. S.; Ullaland, K.; Uras, A.; Usai, G. L.; Utrobicic, A.; Vajzer, M.; Vala, M.; Valencia Palomo, L.; Vallero, S.; van der Maarel, J.; van Hoorne, J. W.; van Leeuwen, M.; Vanat, T.; Vande Vyvre, P.; Varga, D.; Vargas, A.; Vargyas, M.; Varma, R.; Vasileiou, M.; Vasiliev, A.; Vauthier, A.; Vechernin, V.; Veen, A. M.; Veldhoen, M.; Velure, A.; Venaruzzo, M.; Vercellin, E.; Vergara Limón, S.; Vernet, R.; Verweij, M.; Vickovic, L.; Viesti, G.; Viinikainen, J.; Vilakazi, Z.; Villalobos Baillie, O.; Vinogradov, A.; Vinogradov, L.; Vinogradov, Y.; Virgili, T.; Vislavicius, V.; Viyogi, Y. P.; Vodopyanov, A.; Völkl, M. A.; Voloshin, K.; Voloshin, S. A.; Volpe, G.; von Haller, B.; Vorobyev, I.; Vranic, D.; Vrláková, J.; Vulpescu, B.; Vyushin, A.; Wagner, B.; Wagner, J.; Wang, H.; Wang, M.; Wang, Y.; Watanabe, D.; Watanabe, Y.; Weber, M.; Weber, S. G.; Wessels, J. P.; Westerhoff, U.; Wiechula, J.; Wikne, J.; Wilde, M.; Wilk, G.; Wilkinson, J.; Williams, M. C. S.; Windelband, B.; Winn, M.; Yaldo, C. G.; Yang, H.; Yang, P.; Yano, S.; Yin, Z.; Yokoyama, H.; Yoo, I.-K.; Yurchenko, V.; Yushmanov, I.; Zaborowska, A.; Zaccolo, V.; Zaman, A.; Zampolli, C.; Zanoli, H. J. C.; Zaporozhets, S.; Zardoshti, N.; Zarochentsev, A.; Závada, P.; Zaviyalov, N.; Zbroszczyk, H.; Zgura, I. S.; Zhalov, M.; Zhang, H.; Zhang, X.; Zhang, Y.; Zhao, C.; Zhigareva, N.; Zhou, D.; Zhou, Y.; Zhou, Z.; Zhu, H.; Zhu, J.; Zhu, X.; Zichichi, A.; Zimmermann, A.; Zimmermann, M. B.; Zinovjev, G.; Zyzak, M.; Alice Collaboration

2015-11-01

The size of the particle emission region in high-energy collisions can be deduced using the femtoscopic correlations of particle pairs at low relative momentum. Such correlations arise due to quantum statistics and Coulomb and strong final state interactions. In this paper, results are presented from femtoscopic analyses of π±π±,K±K±,KS0KS0,p p , and p ¯p ¯ correlations from Pb-Pb collisions at √{sNN}=2.76 TeV by the ALICE experiment at the LHC. One-dimensional radii of the system are extracted from correlation functions in terms of the invariant momentum difference of the pair. The comparison of the measured radii with the predictions from a hydrokinetic model is discussed. The pion and kaon source radii display a monotonic decrease with increasing average pair transverse mass mT which is consistent with hydrodynamic model predictions for central collisions. The kaon and proton source sizes can be reasonably described by approximate mT scaling.

A formulation of convection for stellar structure and evolution calculations without the mixing-length theory approximations. II - Application to Alpha Centauri A and B

NASA Technical Reports Server (NTRS)

Lydon, Thomas J.; Fox, Peter A.; Sofia, Sabatino

1993-01-01

We have constructed a series of models of Alpha Centauri A and Alpha Centauri B for the purposes of testing the effects of convection modeling both by means of the mixing-length theory (MLT), and by means of parameterization of energy fluxes based upon numerical simulations of turbulent compressible convection. We demonstrate that while MLT, through its adjustable parameter alpha, can be used to match any given values of luminosities and radii, our treatment of convection, which lacks any adjustable parameters, makes specific predictions of stellar radii. Since the predicted radii of the Alpha Centauri system fall within the errors of the observed radii, our treatment of convection is applicable to other stars in the H-R diagram in addition to the sun. A second set of models is constructed using MLT, adjusting alpha to yield not the 'measured' radii but, instead, the radii predictions of our revised treatment of convection. We conclude by assessing the appropriateness of using a single value of alpha to model a wide variety of stars.

Polymer Ni-MH battery based on PEO-PVA-KOH polymer electrolyte

NASA Astrophysics Data System (ADS)

Yang, Chun-Chen

An alkaline polymer electrolyte film has been prepared by a solvent-casting method. Poly(vinyl alcohol), PVA is added to improve the ionic conductivity of the electrolyte. The ionic conductivity increases from 10 -7 to 10 -2 S cm -1 at room temperature when the weight percent ratio of poly(ethylene oxide), PEO to PVA is increased from 10:0 to 5:5. The activation energy of the ionic conductivity for the PEO-PVA-KOH polymer electrolyte is 3-8 kJ mol -1. The properties of the electrolyte film are characterized by a wide variety of techniques and it is found that the film exhibits good mechanical stability and high ionic conductivity at room temperature. The application of such electrolyte films to nickel-metal-hydride (Ni-MH) batteries is examined and the electrochemical characteristics of a polymer Ni-MH battery are obtained.

Scaling effects in sodium zirconium silicate phosphate (Na 1+ xZr 2Si xP 3- xO 12) ion-conducting thin films

DOE PAGES

Ihlefeld, Jon F.; Gurniak, Emily; Jones, Brad H.; ...

2016-05-04

Preparation of sodium zirconium silicate phosphate (NaSICon), Na 1+xZr 2Si xP 3–xO 12 (0.25 ≤ x ≤ 1.0), thin films has been investigated via a chemical solution approach on platinized silicon substrates. Increasing the silicon content resulted in a reduction in the crystallite size and a reduction in the measured ionic conductivity. Processing temperature was also found to affect microstructure and ionic conductivity with higher processing temperatures resulting in larger crystallite sizes and higher ionic conductivities. The highest room temperature sodium ion conductivity was measured for an x = 0.25 composition at 2.3 × 10 –5 S/cm. In conclusion, themore » decreasing ionic conductivity trends with increasing silicon content and decreasing processing temperature are consistent with grain boundary and defect scattering of conducting ions.« less

Ionic liquids as solvents for Čerenkov counting and the effect of a wavelength shifter.

PubMed

Mirenda, M; Rodrigues, D; Ferreyra, C; Arenillas, P; Sarmiento, G P; Krimer, N; Japas, M L

2018-04-01

We study the wavelength shift of the Čerenkov light - generated in the ionic liquid (BMIMCl) - caused by the addition of the highly fluorescent ionic liquid (BMIMHPTS). 18 F and 32 P efficiencies increases up to 124% and 14%, respectively, compared with the values obtained with pure BMIMCl. With this improvement, ionic liquid mixtures become a good alternative - when using the TDCR-Cherenkov technique - to standardize radionuclides having electron emissions energies close to the threshold energy in water (∼ 260keV). As an advantage compared with other solvents, the Ionic liquid mixture can be reused, in the case of short-lived radionuclides, by simply removing all water content in a vacuum oven. Copyright © 2017 Elsevier Ltd. All rights reserved.

Protic ionic liquid as additive on lipase immobilization using silica sol-gel.

PubMed

de Souza, Ranyere Lucena; de Faria, Emanuelle Lima Pache; Figueiredo, Renan Tavares; Freitas, Lisiane dos Santos; Iglesias, Miguel; Mattedi, Silvana; Zanin, Gisella Maria; dos Santos, Onélia Aparecida Andreo; Coutinho, João A P; Lima, Álvaro Silva; Soares, Cleide Mara Faria

2013-03-05

Ionic liquids (ILs) have evolved as a new type of non-aqueous solvents for biocatalysis, mainly due to their unique and tunable physical properties. A number of recent review papers have described a variety of enzymatic reactions conducted in IL solutions, on the other hand, to improve the enzyme's activity and stability in ILs; major methods being explored include the enzyme immobilization (on solid support, sol-gel, etc.), protic ionic liquids used as an additive process. The immobilization of the lipase from Burkholderia cepacia by the sol-gel technique using protic ionic liquids (PIL) as additives to protect against inactivation of the lipase due to release of alcohol and shrinkage of the gel during the sol-gel process was investigated in this study. The influence of various factors such as the length of the alkyl chain of protic ionic liquids (monoethanolamine-based) and a concentration range between 0.5 and 3.0% (w/v) were evaluated. The resulting hydrophobic matrices and immobilized lipases were characterised with regard to specific surface area, adsorption-desorption isotherms, pore volume (V(p)) and size (d(p)) according to nitrogen adsorption and scanning electron microscopy (SEM), physico-chemical properties (thermogravimetric - TG, differential scanning calorimetry - DSC and Fourier transform infrared spectroscopy - FTIR) and the potential for ethyl ester and emulsifier production. The total activity yields (Y(a)) for matrices of immobilized lipase employing protic ionic liquids as additives always resulted in higher values compared with the sample absent the protic ionic liquids, which represents 35-fold increase in recovery of enzymatic activity using the more hydrophobic protic ionic liquids. Compared with arrays of the immobilized biocatalyst without additive, in general, the immobilized biocatalyst in the presence of protic ionic liquids showed increased values of surface area (143-245 m(2) g(-1)) and pore size (19-38 Å). Immobilization with protic ionic liquids also favoured reduced mass loss according to TG curves (always less than 42.9%) when compared to the immobilized matrix without protic ionic liquids (45.1%), except for the sample containing 3.0% protic ionic liquids (46.5%), verified by thermogravimetric analysis. Ionic liquids containing a more hydrophobic alkyl group in the cationic moiety were beneficial for recovery of the activity of the immobilized lipase. The physico-chemical characterization confirmed the presence of the enzyme and its immobilized derivatives obtained in this study by identifying the presence of amino groups, and profiling enthalpy changes of mass loss. Copyright © 2013 Elsevier Inc. All rights reserved.

Progress in Visualizing Atomic Size Effects with DFT-Chemical Pressure Analysis: From Isolated Atoms to Trends in AB5 Intermetallics.

PubMed

Berns, Veronica M; Engelkemier, Joshua; Guo, Yiming; Kilduff, Brandon J; Fredrickson, Daniel C

2014-08-12

The notion of atomic size poses an important challenge to chemical theory: empirical evidence has long established that atoms have spatial requirements, which are summarized in tables of covalent, ionic, metallic, and van der Waals radii. Considerations based on these radii play a central role in the design and interpretation of experiments, but few methods are available to directly support arguments based on atomic size using electronic structure methods. Recently, we described an approach to elucidating atomic size effects using theoretical calculations: the DFT-Chemical Pressure analysis, which visualizes the local pressures arising in crystal structures from the interactions of atomic size and electronic effects. Using this approach, a variety of structural phenomena in intermetallic phases have already been understood in terms that provide guidance to new synthetic experiments. However, the applicability of the DFT-CP method to the broad range of the structures encountered in the solid state is limited by two issues: (1) the difficulty of interpreting the intense pressure features that appear in atomic core regions and (2) the need to divide space among pairs of interacting atoms in a meaningful way. In this article, we describe general solutions to these issues. In addressing the first issue, we explore the CP analysis of a test case in which no core pressures would be expected to arise: isolated atoms in large boxes. Our calculations reveal that intense core pressures do indeed arise in these virtually pressure-less model systems and allow us to trace the issue to the shifts in the voxel positions relative to atomic centers upon expanding and contracting the unit cell. A compensatory grid unwarping procedure is introduced to remedy this artifact. The second issue revolves around the difficulty of interpreting the pressure map in terms of interatomic interactions in a way that respects the size differences of the atoms and avoids artificial geometrical constraints. In approaching this challenge, we have developed a scheme for allocating the grid pressures to contacts inspired by the Hirshfeld charge analysis. Here, each voxel is allocated to the contact between the two atoms whose free atom electron densities show the largest values at that position. In this way, the differing sizes of atoms are naturally included in the division of space without resorting to empirical radii. The use of the improved DFT-CP method is illustrated through analyses of the applicability of radius ratio arguments to Laves phase structures and the structural preferences of AB5 intermetallics between the CaCu5 and AuBe5 structure types.

Sensitivities of ionic explosives

NASA Astrophysics Data System (ADS)

Politzer, Peter; Lane, Pat; Murray, Jane S.

2017-03-01

We have investigated the relevance for ionic explosive sensitivity of three factors that have been demonstrated to be related to the sensitivities of molecular explosives. These are (1) the maximum available heat of detonation, (2) the amount of free space per molecule (or per formula unit) in the crystal lattice and (3) specific features of the electrostatic potential on the molecular or ionic surface. We find that for ionic explosives, just as for molecular ones, there is an overall tendency for impact sensitivity to increase as the maximum detonation heat release is greater. This means that the usual emphasis upon designing explosives with large heats of detonation needs to be tempered somewhat. We also show that a moderate detonation heat release does not preclude a high level of detonation performance for ionic explosives, as was already demonstrated for molecular ones. Relating the free space per formula unit to sensitivity may require a modified procedure for ionic explosives; this will continue to be investigated. Finally, an encouraging start has been made in linking impact sensitivities to the electrostatic potentials on ionic surfaces, although limited so far to ammonium salts.

Ionic structures and transport properties of hot dense W and U plasmas

NASA Astrophysics Data System (ADS)

Hou, Yong; Yuan, Jianmin

2016-10-01

We have combined the average-atom model with the hyper-netted chain approximation (AAHNC) to describe the electronic and ionic structure of uranium and tungsten in the hot dense matter regime. When the electronic structure is described within the average-atom model, the effects of others ions on the electronic structure are considered by the correlation functions. And the ionic structure is calculated though using the hyper-netted chain (HNC) approximation. The ion-ion pair potential is calculated using the modified Gordon-Kim model based on the electronic density distribution in the temperature-depended density functional theory. And electronic and ionic structures are determined self-consistently. On the basis of the ion-ion pair potential, we perform the classical (CMD) and Langevin (LMD) molecular dynamics to simulate the ionic transport properties, such as ionic self-diffusion and shear viscosity coefficients, through the ionic velocity correlation functions. Due that the free electrons become more and more with increasing the plasma temperature, the influence of the electron-ion collisions on the transport properties become more and more important.

Ionic Liquids as Electrolytes for Electrochemical Double-Layer Capacitors: Structures that Optimize Specific Energy.

PubMed

Mousavi, Maral P S; Wilson, Benjamin E; Kashefolgheta, Sadra; Anderson, Evan L; He, Siyao; Bühlmann, Philippe; Stein, Andreas

2016-02-10

Key parameters that influence the specific energy of electrochemical double-layer capacitors (EDLCs) are the double-layer capacitance and the operating potential of the cell. The operating potential of the cell is generally limited by the electrochemical window of the electrolyte solution, that is, the range of applied voltages within which the electrolyte or solvent is not reduced or oxidized. Ionic liquids are of interest as electrolytes for EDLCs because they offer relatively wide potential windows. Here, we provide a systematic study of the influence of the physical properties of ionic liquid electrolytes on the electrochemical stability and electrochemical performance (double-layer capacitance, specific energy) of EDLCs that employ a mesoporous carbon model electrode with uniform, highly interconnected mesopores (3DOm carbon). Several ionic liquids with structurally diverse anions (tetrafluoroborate, trifluoromethanesulfonate, trifluoromethanesulfonimide) and cations (imidazolium, ammonium, pyridinium, piperidinium, and pyrrolidinium) were investigated. We show that the cation size has a significant effect on the electrolyte viscosity and conductivity, as well as the capacitance of EDLCs. Imidazolium- and pyridinium-based ionic liquids provide the highest cell capacitance, and ammonium-based ionic liquids offer potential windows much larger than imidazolium and pyridinium ionic liquids. Increasing the chain length of the alkyl substituents in 1-alkyl-3-methylimidazolium trifluoromethanesulfonimide does not widen the potential window of the ionic liquid. We identified the ionic liquids that maximize the specific energies of EDLCs through the combined effects of their potential windows and the double-layer capacitance. The highest specific energies are obtained with ionic liquid electrolytes that possess moderate electrochemical stability, small ionic volumes, low viscosity, and hence high conductivity, the best performing ionic liquid tested being 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide.

EQUATION OF STATE FOR NUCLEONIC AND HYPERONIC NEUTRON STARS WITH MASS AND RADIUS CONSTRAINTS

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

Tolos, Laura; Centelles, Mario; Ramos, Angels

We obtain a new equation of state for the nucleonic and hyperonic inner core of neutron stars that fulfils the 2 M {sub ⊙} observations as well as the recent determinations of stellar radii below 13 km. The nucleonic equation of state is obtained from a new parameterization of the FSU2 relativistic mean-field functional that satisfies these latest astrophysical constraints and, at the same time, reproduces the properties of nuclear matter and finite nuclei while fulfilling the restrictions on high-density matter deduced from heavy-ion collisions. On the one hand, the equation of state of neutron star matter is softened aroundmore » saturation density, which increases the compactness of canonical neutron stars leading to stellar radii below 13 km. On the other hand, the equation of state is stiff enough at higher densities to fulfil the 2 M {sub ⊙} limit. By a slight modification of the parameterization, we also find that the constraints of 2 M {sub ⊙} neutron stars with radii around 13 km are satisfied when hyperons are considered. The inclusion of the high magnetic fields present in magnetars further stiffens the equation of state. Hyperonic magnetars with magnetic fields in the surface of ∼10{sup 15} G and with values of ∼10{sup 18} G in the interior can reach maximum masses of 2 M {sub ⊙} with radii in the 12–13 km range.« less

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.

Controlling adsorption and passivation properties of bovine serum albumin on silica surfaces by ionic strength modulation and cross-linking.

PubMed

Park, Jae Hyeon; Sut, Tun Naw; Jackman, Joshua A; Ferhan, Abdul Rahim; Yoon, Bo Kyeong; Cho, Nam-Joon

2017-03-29

Understanding the physicochemical factors that influence protein adsorption onto solid supports holds wide relevance for fundamental insights into protein structure and function as well as for applications such as surface passivation. Ionic strength is a key parameter that influences protein adsorption, although how its modulation might be utilized to prepare well-coated protein adlayers remains to be explored. Herein, we investigated how ionic strength can be utilized to control the adsorption and passivation properties of bovine serum albumin (BSA) on silica surfaces. As protein stability in solution can influence adsorption kinetics, the size distribution and secondary structure of proteins in solution were first characterized by dynamic light scattering (DLS), nanoparticle tracking analysis (NTA), and circular dichroism (CD) spectroscopy. A non-monotonic correlation between ionic strength and protein aggregation was observed and attributed to colloidal agglomeration, while the primarily α-helical character of the protein in solution was maintained in all cases. Quartz crystal microbalance-dissipation (QCM-D) experiments were then conducted in order to track protein adsorption onto silica surfaces as a function of ionic strength, and the measurement responses indicated that total protein uptake at saturation coverage is lower with increasing ionic strength. In turn, the QCM-D data and the corresponding Voigt-Voinova model analysis support that the surface area per bound protein molecule is greater with increasing ionic strength. While higher protein uptake under lower ionic strengths by itself did not result in greater surface passivation under subsequent physiologically relevant conditions, the treatment of adsorbed protein layers with a gluteraldehyde cross-linking agent stabilized the bound protein in this case and significantly improved surface passivation. Collectively, our findings demonstrate that ionic strength modulation influences BSA adsorption uptake on account of protein spreading and can be utilized in conjunction with covalent cross-linking strategies to prepare well-coated protein adlayers for improved surface passivation.

Thermostable cellulases, and mutants thereof, capable of hydrolyzing cellulose in ionic liquid

DOEpatents

Sapra, Rajat; Datta, Supratim; Chen, Zhiwei; Holmes, Bradley M.; Simmons, Blake A.; Blanch, Harvey W.

2016-04-26

The present invention provides for a composition comprising an ionic liquid and a thermostable cellulose, and a method of hydrolyzing a cellulose, comprising: (a) providing a composition comprising a solution comprising an ionic liquid and a cellulose, and (b) introducing a thermostable cellulase to the solution, such that the cellulose is hydrolyzed by the cellulase. The present invention also provides for a Thermatoga maritima thermostable cellulase mutant with increased cellulase activity.

Phase behavior of 1-dodecyl-3-methylimidazolium fluorohydrogenate salts (C12MIm(FH)(n)F, n = 1.0-2.3) and their anisotropic ionic conductivity as ionic liquid crystal electrolytes.

PubMed

Xu, Fei; Matsumoto, Kazuhiko; Hagiwara, Rika

2012-08-23

The effects of the HF composition, n, in 1-dodecyl-3-methylimidazolium fluorohydrogenate salts (C(12)MIm(FH)(n)F, n = 1.0-2.3) on their physicochemical and structural properties have been investigated using infrared spectroscopy, thermal analysis, polarized optical microscopy, X-ray diffraction, and anisotropic ionic conductivity measurements. The phase diagram of C(12)MIm(FH)(n)F (n vs transition temperature) suggests that C(12)MIm(FH)(n)F is a mixed crystal system that has a boundary around n = 1.9. For all compositions, a liquid crystalline mesophase with a smectic A interdigitated bilayer structure is observed. The temperature range of the mesophase decreases with increasing n value (from 61.8 °C for C(12)MIm(FH)(1.0)F to 37.0 °C for C(12)MIm(FH)(2.3)F). The layer spacing of the smectic structure decreases with increasing n value or increasing temperature. Two structural types with different layer spacings are observed in the crystalline phase (type I, 1.0 ≤ n ≤ 1.9, and type II, 1.9 ≤ n ≤ 2.3). Ionic conductivities parallel and perpendicular to the smectic layers (σ(||) and σ([perpendicular])) increase with increasing n value, whereas the anisotropy of the ionic conductivities (σ(||)/σ([perpendicular])) is independent of the n value, since the thickness of the insulating sheet formed by the dodecyl group remains nearly unchanged.

Absorption, distribution and excretion of inhaled hydrogen fluoride in the rat

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

Morris, J.B.

1979-01-01

Rats were subjected to whole body HF exposure for 6 hrs or to nose-only HF exposure for 1 hr. Total and/or ionic fluoride concentrations in selected tissues were determined at various times following exposure. In rats sacrificed 6 hrs after whole body exposure, dose-dependent increases in lung, plasma, and kidney total and ionic fluoride concentration occurred. Rats excreted more fluoride in the urine after whole body exposure than could be explained by the amount of HF inhaled. Considerable evidence suggests that airborne HF deposits on fur and is then ingested due to preening activity. Urinary fluoride excretion was increased bymore » nose-only exposure. The urinary fluoride excretion accounted for approximately twice the fluoride estimated to be inhaled during exposure. Tissue fluoride concentrations were elevated immediately after nose-only exposure. Fluoride concentrations in lung and kidney returned to control levels within 12 hrs. Plasma fluoride concentration was slightly elevated 24 hrs after the start of the 1 hr exposure but was at control levels at 96 hrs. Immediately following nose-only exposure, lung ionic fluoride concentrations were less than plasma ionic fluoride concentrations suggesting that the fluoride in the lung had reached that site via plasma transport rather than by inhalation. A dose-dependent increase in plasma ionic fluoride concentration occurred after upper respiratory tract HF exposure providing strong evidence that fluoride is absorbed systemically from that site. The plasma ionic fluoride concentration after upper respiratory tract exposure was of sufficient magnitude to account for the plasma fluoride concentrations observed in intact nose-only exposed rats. (ERB)« less

Conductivity-Relaxation Relations in Nanocomposite Polymer Electrolytes Containing Ionic Liquid.

PubMed

Shojaatalhosseini, Mansoureh; Elamin, Khalid; Swenson, Jan

2017-10-19

In this study, we have used nanocomposite polymer electrolytes, consisting of poly(ethylene oxide) (PEO), δ-Al 2 O 3 nanoparticles, and lithium bis(trifluoromethanesolfonyl)imide (LiTFSI) salt (with 4 wt % δ-Al 2 O 3 and PEO:Li ratios of 16:1 and 8:1), and added different amounts of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesolfonyl)imide (BMITFSI). The aim was to elucidate whether the ionic liquid is able to dissociate the Li-ions from the ether oxygens and thereby decouple the ionic conductivity from the segmental polymer dynamics. The results from DSC and dielectric spectroscopy show that the ionic liquid speeds up both the segmental polymer dynamics and the motion of the Li + ions. However, a close comparison between the structural (α) relaxation process, given by the segmental polymer dynamics, and the ionic conductivity shows that the motion of the Li + ions decouples from the segmental polymer dynamics at higher concentrations of the ionic liquid (≥20 wt %) and instead becomes more related to the viscosity of the ionic liquid. This decoupling increases with decreasing temperature. In addition to the structural α-relaxation, two more local relaxation processes, denoted β and γ, are observed. The β-relaxation becomes slightly faster at the highest concentration of the ionic liquid (at least for the lower salt concentration), whereas the γ-relaxation is unaffected by the ionic liquid, over the whole concentration range 0-40 wt %.

Computer aided design of nano-structured materials with tailored ionic conductivities.

PubMed

Sayle, Dean C; Doig, James A; Parker, Stephen C; Watson, Graeme W; Sayle, Thi X T

2005-01-07

We show, using simulation techniques, that the high ionic conductivity in BaF2/CaF2 heterolayers is because the interfaces reduce the activation energy barriers to mobility and increase the number of charge carriers.

Cesium migration in saturated silica sand and Hanford sediments as impacted by ionic strength.

PubMed

Flury, Markus; Czigány, Szabolcs; Chen, Gang; Harsh, James B

2004-07-01

Large amounts of 137Cs have been accidentally released to the subsurface from the Hanford nuclear site in the state of Washington, USA. The cesium-containing liquids varied in ionic strengths, and often had high electrolyte contents, mainly in the form of NaNO3 and NaOH, reaching concentrations up to several moles per liter. In this study, we investigated the effect of ionic strengths on Cs migration through two types of porous media: silica sand and Hanford sediments. Cesium sorption and transport was studied in 1, 10, 100, and 1000 mM NaCl electrolyte solutions at pH 10. Sorption isotherms were constructed from batch equilibrium experiments and the batch-derived sorption parameters were compared with column breakthrough curves. Column transport experiments were analyzed with a two-site equilibrium-nonequilibrium model. Cesium sorption to the silica sand in batch experiments showed a linear sorption isotherm for all ionic strengths, which matched well with the results from the column experiments at 100 and 1000 mM ionic strength; however, the column experiments at 1 and 10 mM ionic strength indicated a nonlinear sorption behavior of Cs to the silica sand. Transport through silica sand occurred under one-site sorption and equilibrium conditions. Cesium sorption to Hanford sediments in both batch and column experiments was best described with a nonlinear Freundlich isotherm. The column experiments indicated that Cs transport in Hanford sediments occurred under two-site equilibrium and nonequilibrium sorption. The effect of ionic strength on Cs transport was much more pronounced in Hanford sediments than in silica sands. Effective retardation factors of Cs during transport through Hanford sediments were reduced by a factor of 10 when the ionic strength increased from 100 to 1000 mM; for silica sand, the effective retardation was reduced by a factor of 10 when ionic strength increased from 1 to 1000 mM. A two order of magnitude change in ionic strength was needed in the silica sand to observe the same change in Cs retardation as in Hanford sediments. Copyright 2003 Elsevier B.V.

Ka-band and X-band observations of the solar corona acquired during the Cassini 2001 superior conjunction

NASA Technical Reports Server (NTRS)

Morabito, D. D.

2002-01-01

Simultaneous dual-frequency Ka-band (32 GHz) and X-band (8.4 GHz) carrier signal data have been acquired during the superior conjunction of the Cassini spacecraft June 2001, using the NASA Deep Space Network's facilities located in Goldstone, California. The solar elongation angle of the observations varied from -4.1 degrees (-16 solar radii) to -0.6 degrees (-2.3 solar radii). The observed coronal and solar effects on the signals include spectral broadening, amplitude scintillation, phase scintillation, and increased noise. The measurements were generally consistent with existing solar models, except during solar transient events when the signatures of the measurements were observed to increase significantly above the quiet background levels. This is the second solar conjunction of Cassini for which simultaneous X/Ka data were acquired. Both solar conjunctions, conducted in May 2000 and June 2001, occurred near the peak of the current 11 year solar cycle.

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

Lattice model of ionic liquid confined by metal electrodes

NASA Astrophysics Data System (ADS)

Girotto, Matheus; Malossi, Rodrigo M.; dos Santos, Alexandre P.; Levin, Yan

2018-05-01

We study, using Monte Carlo simulations, the density profiles and differential capacitance of ionic liquids confined by metal electrodes. To compute the electrostatic energy, we use the recently developed approach based on periodic Green's functions. The method also allows us to easily calculate the induced charge on the electrodes permitting an efficient implementation of simulations in a constant electrostatic potential ensemble. To speed up the simulations further, we model the ionic liquid as a lattice Coulomb gas and precalculate the interaction potential between the ions. We show that the lattice model captures the transition between camel-shaped and bell-shaped capacitance curves—the latter characteristic of ionic liquids (strong coupling limit) and the former of electrolytes (weak coupling). We observe the appearance of a second peak in the differential capacitance at ≈0.5 V for 2:1 ionic liquids, as the packing fraction is increased. Finally, we show that ionic size asymmetry decreases substantially the capacitance maximum, when all other parameters are kept fixed.

Gas chromatography on wall-coated open-tubular columns with ionic liquid stationary phases.

PubMed

Poole, Colin F; Lenca, Nicole

2014-08-29

Ionic liquids have moved from novel to practical stationary phases for gas chromatography with an increasing portfolio of applications. Ionic liquids complement conventional stationary phases because of a combination of thermophysical and solvation properties that only exist for ionic solvents. Their high thermal stability and low vapor pressure makes them suitable as polar stationary phases for separations requiring high temperatures. Ionic liquids are good solvents and can be used to expand the chemical space for separations. They are the only stationary phases with significant hydrogen-bond acidity in common use; they extend the hydrogen-bond basicity of conventional stationary phases; they are as dipolar/polarizable as the most polar conventional stationary phases; and some ionic liquids are significantly less cohesive than conventional polar stationary phases. Problems in column coating techniques and related low column performance, column activity, and stationary phase reactivity require further exploration as the reasons for these features are poorly understood at present. Copyright © 2014 Elsevier B.V. All rights reserved.

Impact of water dilution and cation tail length on ionic liquid characteristics: Interplay between polar and non-polar interactions

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

Hegde, Govind A.; Bharadwaj, Vivek S.; Kinsinger, Corey L.

2016-08-14

The recalcitrance of lignocellulosic biomass poses a major challenge that hinders the economical utilization of biomass for the production of biofuel, plastics, and chemicals. Ionic liquids have become a promising solvent that addresses many issues in both the pretreatment process and the hydrolysis of the glycosidic bond for the deconstruction of cellulosic materials. However, to make the use of ionic liquids economically viable, either the cost of ionic liquids must be reduced, or a less expensive solvent (e.g., water) may be added to reduce the overall amount of ionic liquid used in addition to reducing the viscosity of the binarymore » liquid mixture. In this work, we employ atomistic molecular dynamics simulations to investigate the impact of water dilution on the overall liquid structure and properties of three imidazolium based ionic liquids. It is found that ionic liquid-water mixtures exhibit characteristics that can be grouped into two distinct regions, which are a function of the ionic liquid concentration. The trends observed in each region are found to correlate with the ordering in the local structure of the ionic liquid that arises from the dynamic interactions between the ion pairs. Simulation results suggest that there is a high level of local ordering in the molecular structure at high concentrations of ionic liquids that is driven by the aggregation of the cationic tails and the anion-water interactions. It is found that as the concentration of ionic liquids in the binary mixture is decreased, there is a point at which the competing self and cross interaction energies between the ionic liquid and water shifts away from a cation-anion dominated regime, which results in a significant change in the mixture properties. This break point, which occurs around 75% w/w ionic liquids, corresponds to the point at which water molecules percolate into the ionic liquid network disrupting the ionic liquids’ nanostructure. It is observed that as the cationic alkyl tail length increases, the changes in the binary mixtures’ properties become more pronounced.« less

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.

Counterion-induced swelling of ionic microgels

NASA Astrophysics Data System (ADS)

Denton, Alan R.; Tang, Qiyun

2016-10-01

Ionic microgel particles, when dispersed in a solvent, swell to equilibrium sizes that are governed by a balance between electrostatic and elastic forces. Tuning of particle size by varying external stimuli, such as pH, salt concentration, and temperature, has relevance for drug delivery, microfluidics, and filtration. To model swelling of ionic microgels, we derive a statistical mechanical theorem, which proves exact within the cell model, for the electrostatic contribution to the osmotic pressure inside a permeable colloidal macroion. Applying the theorem, we demonstrate how the distribution of counterions within an ionic microgel determines the internal osmotic pressure. By combining the electrostatic pressure, which we compute via both Poisson-Boltzmann theory and molecular dynamics simulation, with the elastic pressure, modeled via the Flory-Rehner theory of swollen polymer networks, we show how deswelling of ionic microgels with increasing concentration of particles can result from a redistribution of counterions that reduces electrostatic pressure. A linearized approximation for the electrostatic pressure, which proves remarkably accurate, provides physical insight and greatly eases numerical calculations for practical applications. Comparing with experiments, we explain why soft particles in deionized suspensions deswell upon increasing concentration and why this effect may be suppressed at higher ionic strength. The failure of the uniform ideal-gas approximation to adequately account for counterion-induced deswelling below close packing of microgels is attributed to neglect of spatial variation of the counterion density profile and the electrostatic pressure of incompletely neutralized macroions.

The presence of functional groups key for biodegradation in ionic liquids: effect on gas solubility.

PubMed

Deng, Yun; Morrissey, Saibh; Gathergood, Nicholas; Delort, Anne-Marie; Husson, Pascale; Costa Gomes, Margarida F

2010-03-22

The effect of the incorporation of either ester or ester and ether functions into the side chain of an 1-alkyl-3-methylimidazolium cation on the physico-chemical properties of ionic liquids containing bis(trifluoromethylsulfonyl)imide or octylsulfate anions is studied. It is believed that the introduction of an ester function into the cation of the ionic liquids greatly increases their biodegradability. The density of three such ionic liquids is measured as a function of temperature, and the solubility of four gases-carbon dioxide, ethane, methane, and hydrogen-is determined between 303 K and 343 K and at pressures close to atmospheric level. Carbon dioxide is the most soluble gas, followed by ethane and methane; the mole fraction solubilities vary from 1.8 x 10(-3) to 3.7 x 10(-2). These solubilities are of the same order of magnitude as those determined for alkylimidazolium-based ionic liquids. The chemical modification of the alkyl side chain does not result in a significant change of the solvation properties of the ionic liquid. All of the solubilities decrease with increasing temperature, corresponding to an exothermal solvation process. From the variation of this property with temperature, the thermodynamic functions of solvation (Gibbs energy, enthalpy, and entropy) are calculated and provide information about the solute-solvent interactions and the molecular structure of the solutions.

Pair distribution function analysis of sulfide glassy electrolytes for all-solid-state batteries: Understanding the improvement of ionic conductivity under annealing condition.

PubMed

Shiotani, Shinya; Ohara, Koji; Tsukasaki, Hirofumi; Mori, Shigeo; Kanno, Ryoji

2017-08-01

In general, the ionic conductivity of sulfide glasses decreases with their crystallization, although it increases for a few sulphide glasses owing to the crystallization of a highly conductive new phase (e.g., Li 7 P 3 S 11 : 70Li 2 S-30P 2 S 5 ). We found that the ionic conductivity of 75Li 2 S-25P 2 S 5 sulfide glass, which consists of glassy and crystalline phases, is improved by optimizing the conditions of the heat treatment, i.e., annealing. A different mechanism of high ionic conductivity from the conventional mechanism is expected in the glassy phase. Here, we report the glassy structure of 75Li 2 S-25P 2 S 5 immediately before the crystallization by using the differential pair distribution function (d-PDF) analysis of high-energy X-ray diffraction. Even though the ionic conductivity increases during the optimum annealing, the d-PDF analysis indicated that the glassy structure undergoes no structural change in the sulfide glass-ceramic electrolyte at a crystallinity of 33.1%. We observed the formation of a nanocrystalline phase in the X-ray and electron diffraction patterns before the crystallization, which means that Bragg peaks were deformed. Thus, the ionic conductivity in the mixture of glassy and crystalline phases is improved by the coexistence of the nanocrystalline phase.

Modeling hardwood crown radii using circular data analysis

Treesearch

Paul F. Doruska; Hal O. Liechty; Douglas J. Marshall

2003-01-01

Cylindrical data are bivariate data composed of a linear and an angular component. One can use uniform, first-order (one maximum and one minimum) or second-order (two maxima and two minima) models to relate the linear component to the angular component. Crown radii can be treated as cylindrical data when the azimuths at which the radii are measured are also recorded....

Understanding and modulating opalescence and viscosity in a monoclonal antibody formulation

PubMed Central

Salinas, Branden A; Sathish, Hasige A; Bishop, Steven M; Harn, Nick; Carpenter, John F; Randolph, Theodore W

2014-01-01

Opalescence and high viscosities can pose challenges for high concentration formulation of antibodies. Both phenomena result from protein-protein intermolecular interactions that can be modulated with solution ionic strength. We studied a therapeutic monoclonal antibody that exhibits high viscosity in solutions at low ionic strength (~20 centipoise (cP) at 90 mg/mL and 23°C) and significant opalescence at isotonic ionic strength (approximately 100 nephelometric turbidity units at 90 mg/mL and 23°C). The intermolecular interactions responsible for these effects were characterized using membrane osmometry, static light scattering and zeta potential measurements. The net protein-protein interactions were repulsive at low ionic strength (~4 mM) and attractive at isotonic ionic strengths. The high viscosities are attributed to electroviscous forces at low ionic strength and the significant opalescence at isotonic ionic strength is correlated with attractive antibody interactions. Furthermore there appears to be a connection to critical phenomena and it is suggested that the extent of opalescence is dependent on the proximity to the critical point. We demonstrate that by balancing the repulsive and attractive forces via intermediate ionic strengths and by increasing the mAb concentration above the apparent critical concentration both opalescence and viscosity can be simultaneously minimized. PMID:19475558

Comparative in vitro study of cholinium-based ionic liquids and deep eutectic solvents toward fish cell line.

PubMed

Radošević, Kristina; Železnjak, Jelena; Cvjetko Bubalo, Marina; Radojčić Redovniković, Ivana; Slivac, Igor; Gaurina Srček, Višnja

2016-09-01

With the advent of ionic liquids, much was expected concerning their applicability as an alternative to organic solvents in the chemical technology and biotechnology fields. However, the most studied and commonly used ionic liquids based on imidazolium and pyridinium were found not to be as environmentally friendly as it was first expected. Therefore, a new generation of alternative solvents named natural ionic liquids and deep eutectic solvents, composed of natural and/or renewable compounds, have come into focus in recent years. Since the number of newly synthesized chemicals increases yearly, simple and reliable methods for their ecotoxicological assessment are necessary. Permanent fish cell lines can serve as a test system for the evaluation of a chemical's cytotoxicity. This paper presents research results on the cytotoxic effects on Channel Catfish Ovary (CCO) cell line induced by fifteen cholinium-based ionic liquids and deep eutectic solvents. Based on the decrease in cell viability, the most obvious toxic effect on CCO cells was caused by ionic liquid choline oxalate, while other solvents tested exhibited low cytotoxicity. Therefore, we can conclude that cholinium-based ionic liquids and deep eutectic solvents are comparatively less toxic to CCO cells than conventional ionic liquids. Copyright © 2016 Elsevier Inc. All rights reserved.

Role of Oxygen in Ionic Liquid Gating on Two-Dimensional Cr2Ge2Te6: A Non-oxide Material.

PubMed

Chen, Yangyang; Xing, Wenyu; Wang, Xirui; Shen, Bowen; Yuan, Wei; Su, Tang; Ma, Yang; Yao, Yunyan; Zhong, Jiangnan; Yun, Yu; Xie, X C; Jia, Shuang; Han, Wei

2018-01-10

Ionic liquid gating can markedly modulate a material's carrier density so as to induce metallization, superconductivity, and quantum phase transitions. One of the main issues is whether the mechanism of ionic liquid gating is an electrostatic field effect or an electrochemical effect, especially for oxide materials. Recent observation of the suppression of the ionic liquid gate-induced metallization in the presence of oxygen for oxide materials suggests the electrochemical effect. However, in more general scenarios, the role of oxygen in the ionic liquid gating effect is still unclear. Here, we perform ionic liquid gating experiments on a non-oxide material: two-dimensional ferromagnetic Cr 2 Ge 2 Te 6 . Our results demonstrate that despite the large increase of the gate leakage current in the presence of oxygen, the oxygen does not affect the ionic liquid gating effect on  the channel resistance of Cr 2 Ge 2 Te 6 devices (<5% difference), which suggests the electrostatic field effect as the mechanism on non-oxide materials. Moreover, our results show that ionic liquid gating is more effective on the modulation of the channel resistances compared to the back gating across the 300 nm thick SiO 2 .

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

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.

Realisation of an all solid state lithium battery using solid high temperature plastic crystal electrolytes exhibiting liquid like conductivity.

PubMed

Shekibi, Youssof; Rüther, Thomas; Huang, Junhua; Hollenkamp, Anthony F

2012-04-07

Replacement of volatile and combustible electrolytes in conventional lithium batteries is desirable for two reasons: safety concerns and increase in specific energy. In this work we consider the use of an ionic organic plastic crystal material (IOPC), N-ethyl-N-methylpyrrolidinium tetrafluoroborate, [C2mpyr][BF(4)], as a solid-state electrolyte for lithium battery applications. The effect of inclusion of 1 to 33 mol% lithium tetrafluoroborate, LiBF(4), into [C2mpyr][BF(4)] has been investigated over a wide temperature range by differential scanning calorimetry (DSC), impedance spectroscopy, cyclic voltammetry and cycling of full Li|LiFePO(4) batteries. The increases in ionic conductivity by orders of magnitude observed at higher temperature are most likely associated with an increase in Li ion mobility in the highest plastic phase. At concentrations >5 mol% LiBF(4) the ionic conductivity of these solid-state composites is comparable to the ionic conductivity of room temperature ionic liquids. Galvanostatic cycling of Li|Li symmetrical cells showed that the reversibility of the lithium metal redox reaction at the interface of this plastic crystal electrolyte is sufficient for lithium battery applications. For the first time we demonstrate an all solid state lithium battery incorporating solid electrolytes based on IOPC as opposed to conventional flammable organic solvents.

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.

Variation in emulsion stabilization behavior of hybrid silicone polymers with change in molecular structure: Phase diagram study.

PubMed

Mehta, Somil C; Somasundaran, P; Kulkarni, Ravi

2009-05-15

Silicone oils are widely used in cosmetics and personal care applications to improve softness and condition skin and hair. Being insoluble in water and most hydrocarbons, a common mode of delivering them is in the form of emulsions. Currently most applications use polyoxyethylene (non-ionic) modified siloxanes as emulsifiers to stabilize silicone oil emulsions. However, ionically grafted silicone polymers have not received much attention. Ionic silicones have significantly different properties than the non-ionic counterpart. Thus considerable potential exists to formulate emulsions of silicones with different water/silicone oil ratios for novel applications. In order to understand the mechanisms underlying the effects of hydrophilic modifications on the ability of hybrid silicone polymers to stabilize various emulsions, this article focuses on the phase diagram studies for silicone emulsions. The emulsifying ability of functional silicones was seen to depend on a number of factors including hydrophilicity of the polymer, nature of the functional groups, the extent of modification, and the method of emulsification. It was observed that the region of stable emulsion in a phase diagram expanded with increase in shear rate. At a given shear rate, the region of stable emulsion and the nature of emulsion (water-in-oil or oil-in-water) was observed to depend on hydrophilic-hydrophobic balance of the hybrid silicone emulsifier. At a fixed amount of modification, the non-ionically modified silicone stabilized an oil-in-water emulsion, whereas the ionic silicones stabilized inverse water-in-oil emulsions. This was attributed to the greater hydrophilicity of the polyoxyethylene modified silicones than the ionic counterparts. In general, it is postulated that with progressive increase in hydrophilicity of hybrid silicone emulsifiers, their tendency to stabilize water-in-oil emulsion decreases with corresponding increase in oil-in-water emulsion. Further, this behavior is hypothesized to depend on the nature of modifying functional groups. Thus a hybrid silicone polymer can be tailored by selecting the nature and degree of hydrophilicity to obtain a desired silicone emulsion.

Curvature dependence of the effect of ionic functionalization on the attraction among nanoparticles in dispersion

NASA Astrophysics Data System (ADS)

Jabes, B. Shadrack; Bratko, Dusan; Luzar, Alenka

2018-06-01

Solubilization of nanoparticles facilitates nanomaterial processing and enables new applications. An effective method to improve dispersibility in water is provided by ionic functionalization. We explore how the necessary extent of functionalization depends on the particle geometry. Using molecular dynamics/umbrella sampling simulations, we determine the effect of the solute curvature on solvent-averaged interactions among ionizing graphitic nanoparticles in aqueous dispersion. We tune the hydrophilicity of molecular-brush coated fullerenes, carbon nanotubes, and graphane platelets by gradually replacing a fraction of the methyl end groups of the alkyl coating by the ionizing -COOK or -NH3Cl groups. To assess the change in nanoparticles' dispersibility in water, we determine the potential-of-mean-force profiles at varied degrees of ionization. When the coating comprises only propyl groups, the attraction between the hydrophobic particles intensifies from spherical to cylindrical to planar geometry. This is explained by the increasing fraction of surface groups that can be brought into contact and the reduced access to water molecules, both following the above sequence. When ionic groups are added, however, the dispersibility increases in the opposite order, with the biggest effect in the planar geometry and the smallest in the spherical geometry. These results highlight the important role of geometry in nanoparticle solubilization by ionic functionalities, with about twice higher threshold surface charge necessary to stabilize a dispersion of spherical than planar particles. At 25%-50% ionization, the potential of mean force reaches a plateau because of the counterion condensation and saturated brush hydration. Moreover, the increase in the fraction of ionic groups can weaken the repulsion through counterion correlations between adjacent nanoparticles. High degrees of ionization and concomitant ionic screening gradually reduce the differences among surface interactions in distinct geometries until an essentially curvature-independent dispersion environment is created. Insights into tuning nanoparticle interactions can guide the synthesis of a broad class of nonpolar nanoparticles, where solubility is achieved by ionic functionalization.

Electron temperature critical gradient and transport stiffness in DIII-D

DOE PAGES

Smith, Sterling P.; Petty, Clinton C.; White, Anne E.; ...

2015-07-06

The electron energy flux has been probed as a function of electron temperature gradient on the DIII-D tokamak, in a continuing effort to validate turbulent transport models. In the scan of gradient, a critical electron temperature gradient has been found in the electron heat fluxes and stiffness at various radii in L-mode plasmas. The TGLF reduced turbulent transport model [G.M. Staebler et al, Phys. Plasmas 14, 055909 (2007)] and full gyrokinetic GYRO model [J. Candy and R.E. Waltz, J. Comput. Phys. 186, 545 (2003)] recover the general trend of increasing electron energy flux with increasing electron temperature gradient scale length,more » but they do not predict the absolute level of transport at all radii and gradients. Comparing the experimental observations of incremental (heat pulse) diffusivity and stiffness to the models’ reveals that TGLF reproduces the trends in increasing diffusivity and stiffness with increasing electron temperature gradient scale length with a critical gradient behavior. Furthermore, the critical gradient of TGLF is found to have a dependence on q 95, contrary to the independence of the experimental critical gradient from q 95.« less

Ionic liquids: dissecting the enthalpies of vaporization.

PubMed

Köddermann, Thorsten; Paschek, Dietmar; Ludwig, Ralf

2008-03-14

We calculate the heats of vaporisation for imidazolium-based ionic liquids [C(n)mim][NTf(2)] with n=1, 2, 4, 6, 8 by means of molecular dynamics (MD) simulations and discuss their behavior with respect to temperature and the alkyl chain length. We use a force field developed recently. The different cohesive energies contributing to the overall heats of vaporisations are discussed in detail. With increasing alkyl chain length, the Coulomb contribution to the heat of vaporisation remains constant at around 80 kJ mol(-1), whereas the van der Waals interaction increases continuously. The calculated increase of about 4.7 kJ mol(-1) per CH(2)-group of the van der Waals contribution in the ionic liquid exactly coincides with the increase in the heats of vaporisation for n-alcohols and n-alkanes, respectively. The results support the importance of van der Waals interactions even in systems completely composed of ions.

A novel conductance glucose biosensor in ultra-low ionic strength solution triggered by the oxidation of Ag nanoparticles.

PubMed

Song, Yonghai; Chen, Jingyi; Liu, Hongyu; Li, Ping; Li, Hongbo; Wang, Li

2015-09-03

A simple, sensitive and effective method to detect glucose in ultra-low ionic strength solution containing citrate-capped silver nanoparticles (CCAgNPs) was developed by monitoring the change of solution conductance. Glucose was catalyzed into gluconic acid firstly by glucose oxidase in an O2-saturated solution accompanied by the reduction of O2 into hydrogen peroxide (H2O2). Then, CCAgNPs was oxidized by H2O2 into Ag(+) and the capping regent of citrate was released at the same time. All these resulted Ag(+), gluconic acid and the released citrate would contribute to the increase of solution ionic strength together, leading to a detectable increase of solution conductance. And a novel conductance glucose biosensor was developed with a routine linear range of 0.06-4.0 mM and a suitable detection limit of 18.0 μM. The novel glucose biosensor was further applied in energy drink sample and proven to be suitable for practical system with low ionic strength. The proposed conductance biosensor achieved a significant breakthrough of glucose detection in ultra-low ionic strength media. Copyright © 2015 Elsevier B.V. All rights reserved.

Electrophoretic mobilities of erythrocytes in various buffers

NASA Technical Reports Server (NTRS)

Plank, L. D.; Kunze, M. E.; Todd, P. W.

1985-01-01

The calibration of space flight equipment depends on a source of standard test particles, this test particle of choice is the fixed erythrocyte. Erythrocytes from different species have different electrophoretic mobilities. Electrophoretic mobility depends upon zeta potential, which, in turn depends upon ionic strength. Zeta potential decreases with increasing ionic strength, so cells have high electrophoretic mobility in space electrophoresis buffers than in typical physiological buffers. The electrophoretic mobilities of fixed human, rat, and rabbit erythrocytes in 0.145 M salt and buffers of varying ionic strength, temperature, and composition, to assess the effects of some of the unique combinations used in space buffers were characterized. Several effects were assessed: glycerol or DMSO (dimethylsulfoxide) were considered for use as cryoprotectants. The effect of these substances on erythrocyte electrophoretic mobility was examined. The choice of buffer depended upon cell mobility. Primary experiments with kidney cells established the choice of buffer and cryoprotectant. A nonstandard temperature of EPM in the suitable buffer was determined. A loss of ionic strength control occurs in the course of preparing columns for flight, the effects of small increases in ionic strength over the expected low values need to be evaluated.

Testing asteroseismic radii of dwarfs and subgiants with Kepler and Gaia

NASA Astrophysics Data System (ADS)

Sahlholdt, C. L.; Silva Aguirre, V.; Casagrande, L.; Mosumgaard, J. R.; Bojsen-Hansen, M.

2018-05-01

We test asteroseismic radii of Kepler main-sequence and subgiant stars by deriving their parallaxes which are compared with those of the first Gaia data release. We compute radii based on the asteroseismic scaling relations as well as by fitting observed oscillation frequencies to stellar models for a subset of the sample, and test the impact of using effective temperatures from either spectroscopy or the infrared flux method. An offset of 3 per cent, showing no dependency on any stellar parameters, is found between seismic parallaxes derived from frequency modelling and those from Gaia. For parallaxes based on radii from the scaling relations, a smaller offset is found on average; however, the offset becomes temperature dependent which we interpret as problems with the scaling relations at high stellar temperatures. Using the hotter infrared flux method temperature scale, there is no indication that radii from the scaling relations are inaccurate by more than about 5 per cent. Taking the radii and masses from the modelling of individual frequencies as reference values, we seek to correct the scaling relations for the observed temperature trend. This analysis indicates that the scaling relations systematically overestimate radii and masses at high temperatures, and that they are accurate to within 5 per cent in radius and 13 per cent in mass for main-sequence stars with temperatures below 6400 K. However, further analysis is required to test the validity of the corrections on a star-by-star basis and for more evolved stars.

Influence of the ionic liquid [C4mpy][Tf2N] on the structure of the miniprotein Trp-cage.

PubMed

Baker, Joseph L; Furbish, Jeffrey; Lindberg, Gerrick E

2015-11-01

We examine the effect of the ionic liquid [C4mpy][Tf2N] on the structure of the miniprotein Trp-cage and contrast these results with the behavior of Trp-cage in water. We find the ionic liquid has a dramatic effect on Trp-cage, though many similarities with aqueous Trp-cage are observed. We assess Trp-cage folding by monitoring root mean square deviation from the crystallographic structure, radius of gyration, proline cis/trans isomerization state, protein secondary structure, amino acid contact formation and distance, and native and non-native contact formation. Starting from an unfolded configuration, Trp-cage folds in water at 298 K in less than 500 ns of simulation, but has very little mobility in the ionic liquid at the same temperature, which can be ascribed to the higher ionic liquid viscosity. At 365 K, the mobility of the ionic liquid is increased and initial stages of Trp-cage folding are observed, however Trp-cage does not reach the native folded state in 2 μs of simulation in the ionic liquid. Therefore, in addition to conventional molecular dynamics, we also employ scaled molecular dynamics to expedite sampling, and we demonstrate that Trp-cage in the ionic liquid does closely approach the aqueous folded state. Interestingly, while the reduced mobility of the ionic liquid is found to restrict Trp-cage motion, the ionic liquid does facilitate proline cis/trans isomerization events that are not seen in our aqueous simulations. Copyright © 2015 Elsevier Inc. All rights reserved.

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

Ionic Liquid Catalyzed Electrolyte for Electrochemical Polyaniline Supercapacitors

NASA Astrophysics Data System (ADS)

Inamdar, A. I.; Im, Hyunsik; Jung, Woong; Kim, Hyungsang; Kim, Byungchul; Yu, Kook-Hyun; Kim, Jin-Sang; Hwang, Sung-Min

2013-05-01

The effect of different wt.% of ionic liquid "1,6-bis (trimethylammonium-1-yl) hexane tetrafluoroborate" in 0.5 M LiClO4+PC electrolyte on the supercapacitor properties of polyaniline (PANI) thin film are investigated. The PANI film is synthesized using electropolymerization of aniline in the presence of sulfuric acid. The electrochemical properties of the PANI thin film are studied by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy (EIS) measurements. The optimum amount of the ionic liquid is found to be 2 wt.% which provides better ionic conductivity of the electrolyte. The highest specific capacitance of 259 F/g is obtained using the 2 wt.% electrolyte. This capacitance remains at up to 208 F/g (80% capacity retention) after 1000 charge-discharge cycles at a current density of 0.5 mA/g. The PANI film in the 2 wt.% ionic liquid catalyzed 0.5 M LiClO4+PC electrolyte shows small electrochemical resistance, better rate performance and higher cyclability. The increased ionic conductivity of the 2 wt.% ionic liquid catalyzed electrolyte causes a reduction in resistance at the electrode/electrolyte interface, which can be useful in electrochemically-preferred power devices for better applicability.

Structure of cyano-anion ionic liquids: X-ray scattering and simulations.

PubMed

Dhungana, Kamal B; Faria, Luiz F O; Wu, Boning; Liang, Min; Ribeiro, Mauro C C; Margulis, Claudio J; Castner, Edward W

2016-07-14

Ionic liquids with cyano anions have long been used because of their unique combination of low-melting temperatures, reduced viscosities, and increased conductivities. Recently we have shown that cyano anions in ionic liquids are particularly interesting for their potential use as electron donors to excited state photo-acceptors [B. Wu et al., J. Phys. Chem. B 119, 14790-14799 (2015)]. Here we report on bulk structural and quantum mechanical results for a series of ionic liquids based on the 1-ethyl-3-methylimidazolium cation, paired with the following five cyano anions: SeCN(-), SCN(-), N(CN)2 (-), C(CN)3 (-), and B(CN)4 (-). By combining molecular dynamics simulations, high-energy X-ray scattering measurements, and periodic boundary condition DFT calculations, we are able to obtain a comprehensive description of the liquid landscape as well as the nature of the HOMO-LUMO states for these ionic liquids in the condensed phase. Features in the structure functions for these ionic liquids are somewhat different than the commonly observed adjacency, charge-charge, and polarity peaks, especially for the bulkiest B(CN)4 (-) anion. While the other four cyano-anion ionic liquids present an anionic HOMO, the one for Im2,1 (+)/B(CN)4 (-) is cationic.

How ionic species structure influences phase structure and transitions from protic ionic liquids to liquid crystals to crystals.

PubMed

Greaves, Tamar L; Broomhall, Hayden; Weerawardena, Asoka; Osborne, Dale A; Canonge, Bastien A; Drummond, Calum J

2017-12-14

The phase behaviour of n-alkylammonium (C6 to C16) nitrates and formates has been characterised using synchrotron small angle and wide angle X-ray scattering (SAXS/WAXS), differential scanning calorimetry (DSC), cross polarised optical microscopy (CPOM) and Fourier transform infrared spectroscopy (FTIR). The protic salts may exist as crystalline, liquid crystalline or ionic liquid materials depending on the alkyl chain length and temperature. n-Alkylammonium nitrates with n ≥ 6 form thermotropic liquid crystalline (LC) lamellar phases, whereas n ≥ 8 was required for the formate series to form this LC phase. The protic ionic liquid phase showed an intermediate length scale nanostructure resulting from the segregation of the polar and nonpolar components of the ionic liquid. This segregation was enhanced for longer n-alkyl chains, with a corresponding increase in the correlation length scale. The crystalline and liquid crystalline phases were both lamellar. Phase transition temperatures, lamellar d-spacings, and liquid correlation lengths for the n-alkylammonium nitrates and formates were compared with those for n-alkylammonium chlorides and n-alkylamines. Plateau regions in the liquid crystalline to liquid phase transition temperatures as a function of n for the n-alkylammonium nitrates and formates are consistent with hydrogen-bonding and cation-anion interactions between the ionic species dominating alkyl chain-chain van der Waals interactions, with the exception of the mid chained hexyl- and heptylammonium formates. The d-spacings of the lamellar phases for both the n-alkylammonium nitrates and formates were consistent with an increase in chain-chain layer interdigitation within the bilayer-based lamellae with increasing alkyl chain length, and they were comparable to the n-alkylammonium chlorides.

Influence of cobalt on structural and magnetic properties of nickel ferrite nanoparticles

NASA Astrophysics Data System (ADS)

Ati, Ali A.; Othaman, Zulkafli; Samavati, Alireza

2013-11-01

Improving the magnetic response of nanocrystalline nickel ferrites is the key issue in high density recording media. A series of cobalt substituted nickel ferrite nanoparticles with composition Ni(1-x)CoxFe2O4, where 0.0 ⩽ x ⩽ 1.0, are synthesized using co-precipitation method. The XRD spectra revealed the single phase spinel structure and the average sizes of nanoparticles are estimated to be 16-19 nm. These sizes are small enough to achieve the suitable signal to noise ratio in the high density recording media. The lattice parameter and coercivity shows monotonic increment with the increase of Co contents ascribed to the larger ionic radii of the cobalt ion. The specific saturation magnetization (Ms), remanent magnetization (Mr) and the coercivity (Hc) of the spinel ferrites are further improved by the substitutions of Co+2 ions. The values of Ms for NiFe2O4 and CoFe2O4 are found to be 43.92 and 78.59 emu/g, respectively and Hc are in the range of 51-778 Oe. The FTIR spectra of the spinel phase calcinated at 600 °C exhibit two prominent fundamental absorption bands in the range of 350-600 cm-1 assigned to the intrinsic stretching vibrations of the metal at the tetrahedral and octahedral sites. The role played by the Co ions in improving the structural and magnetic properties are analyzed and understood. Our simple, economic and environmental friendly preparation method may contribute towards the controlled growth of high quality ferrite nanopowders, potential candidates for recording.

High capacity and stability of Nb-doped Li3VO4 as an anode material for lithium ion batteries

NASA Astrophysics Data System (ADS)

Zhao, Long; Duan, He; Zhao, Yanming; Kuang, Quan; Fan, Qinghua; Chen, Lei; Dong, Youzhong

2018-02-01

To improve the electrochemical performance of Li3VO4, a series of Li3NbxV1-xO4 compounds are prepared via sol-gel method. The similar ionic radii of Nb5+ and V5+ in octahedral coordination make it possible to form single-phased Li3NbxV1-xO4 (0 ≤ x ≤ 0.15). Theoretical calculations show that Li-ions migrate along the c-axis diffusion channel in a curved hopping route. The larger lattice constant caused by the substitution of V with Nb enhances the cross-sectional area, which indirectly provides a higher diffusion coefficient for Li-ion migration. Benefitting from high electronic conductivity (around two orders of magnitude) and good lithium-ion diffusion coefficient, the Li3NbxV1-xO4 (x = 0.02) exhibits the best electrochemical property as an anode of LIBs in comparison to other Li3NbxV1-xO4(x = 0, 0.01, 0.03, 0.04). At the current density of 30 mA g-1, the charge capacity of pure Li3VO4 is around 440 mA h g-1, whereas the Li3NbxV1-xO4 (x = 0.02) shows a higher capacity of 550 mA h g-1. Additionally, the charge/discharge capacities for Nb-doped samples are almost twice to those of the undoped Li3VO4 when the current density increases to1500 mA g-1.

Ceramic Single Phase High-Level Nuclear Waste Forms: Hollandite, Perovskite, and Pyrochlore

NASA Astrophysics Data System (ADS)

Vetter, M.; Wang, J.

2017-12-01

The lack of viable options for the safe, reliable, and long-term storage of nuclear waste is one of the primary roadblocks of nuclear energy's sustainable future. The method being researched is the incorporation and immobilization of harmful radionuclides (Cs, Sr, Actinides, and Lanthanides) into the structure of glasses and ceramics. Borosilicate glasses are the main waste form that is accepted and used by today's nuclear industry, but they aren't the most efficient in terms of waste loading, and durability is still not fully understood. Synroc-phase ceramics (i.e. hollandite, perovskite, pyrochlore, zirconolite) have many attractive qualities that glass waste forms do not: high waste loading, moderate thermal expansion and conductivity, high chemical durability, and high radiation stability. The only downside to ceramics is that they are more complex to process than glass. New compositions can be discovered by using an Artificial Neural Network (ANN) to have more options to optimize the composition, loading for performance by analyzing the non-linear relationships between ionic radii, electronegativity, channel size, and a mineral's ability to incorporate radionuclides into its structure. Cesium can be incorporated into hollandite's A-site, while pyrochlore and perovskite can incorporate actinides and lanthanides into their A-site. The ANN is used to predict new compositions based on hollandite's channel size, as well as the A-O bond distances of pyrochlore and perovskite, and determine which ions can be incorporated. These new compositions will provide more options for more experiments to potentially improve chemical and thermodynamic properties, as well as increased waste loading capabilities.

Novel ascorbic acid based ionic liquids for the in situ synthesis of quasi-spherical and anisotropic gold nanostructures in aqueous medium.

PubMed

Dinda, Enakshi; Si, Satyabrata; Kotal, Atanu; Mandal, Tarun K

2008-01-01

A series of newly designed ascorbic acid based room temperature ionic liquids were successfully used to prepare quasi-spherical and anisotropic gold nanostructures in an aqueous medium at ambient temperature. The synthesis of these room temperature ionic liquids involves, first, the preparation of a 1-alkyl (such as methyl, ethyl, butyl, hexyl, octyl, and decyl) derivative of 3-methylimidazolium hydroxide followed by the neutralization of the derivatised product with ascorbic acid. These ionic liquids show significantly better thermal stability and their glass transition temperature (Tg) decreases with increasing alkyl chain length. The ascorbate counter anion of these ionic liquids acts as a reducing agent for HAuCl4 to produce metallic gold and the alkylated imidazolium counter cation acts as a capping/shape-directing agent. It has been found that the nature of the ionic liquids and the mole ratio of ionic liquid to HAuCl4 has a significant effect on the morphology of the formed gold nanostructures. If an equimolar mixture of ionic liquid and HAuCl4 is used, predominantly anisotropic gold nanostructures are formed and by varying the alkyl chain length attached to imidazolium cation of the ionic liquids, various particle morphologies can formed, such as quasispherical, raspberry-like, flakes or dendritic. A probable formation mechanism for such anisotropic gold nanostructures has been proposed, which is based on the results of some control experiments.

Results of the Apogee-Raising Campaign of the Magnetospheric Multiscale Mission

NASA Technical Reports Server (NTRS)

Williams, Trevor; Ottenstein, Neil; Palmer, Eric J.; Hollister, Jacob

2017-01-01

This paper describes the apogee-raising campaign of the Magnetospheric Multiscale mission, where the spacecraft increased their apogee radii from 12 to 25 Earth radii in a total of 98 maneuvers. These maneuvers included an initial formation resize set to spread the spacecraft apart for safety, 32 apogee-raise delta-v maneuvers, their associated slews, four perigee-raise maneuvers and the associated slews, and finally a set of maneuvers to get back into formation. These activities were all accomplished successfully and on schedule with no anomalies, and at a fuel consumption somewhat less than predicted. As a result, MMS was set up ready to carry out in situ studies of magnetic reconnection in the magnetotail, with sufficient fuel remaining for a significant extended mission.

Development of ATHENA mirror modules

NASA Astrophysics Data System (ADS)

Collon, Maximilien J.; Vacanti, Giuseppe; Barrière, Nicolas M.; Landgraf, Boris; Günther, Ramses; Vervest, Mark; van der Hoeven, Roy; Dekker, Danielle; Chatbi, Abdel; Girou, David; Sforzini, Jessica; Beijersbergen, Marco W.; Bavdaz, Marcos; Wille, Eric; Fransen, Sebastiaan; Shortt, Brian; Haneveld, Jeroen; Koelewijn, Arenda; Booysen, Karin; Wijnperle, Maurice; van Baren, Coen; Eigenraam, Alexander; Müller, Peter; Krumrey, Michael; Burwitz, Vadim; Pareschi, Giovanni; Massahi, Sonny; Christensen, Finn E.; Della Monica Ferreira, Desirée.; Valsecchi, Giuseppe; Oliver, Paul; Checquer, Ian; Ball, Kevin; Zuknik, Karl-Heinz

2017-08-01

Silicon Pore Optics (SPO), developed at cosine with the European Space Agency (ESA) and several academic and industrial partners, provides lightweight, yet stiff, high-resolution x-ray optics. This technology enables ATHENA to reach an unprecedentedly large effective area in the 0.2 - 12 keV band with an angular resolution better than 5''. After developing the technology for 50 m and 20 m focal length, this year has witnessed the first 12 m focal length mirror modules being produced. The technology development is also gaining momentum with three different radii under study: mirror modules for the inner radii (Rmin = 250 mm), outer radii (Rmax = 1500 mm) and middle radii (Rmid = 737 mm) are being developed in parallel.

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

Baines, Ellyn K.; Armstrong, J. Thomas; Schmitt, Henrique R.

Using the Navy Precision Optical Interferometer, we measured the angular diameters of 10 stars that have previously measured solar-like oscillations. Our sample covered a range of evolutionary stages but focused on evolved subgiant and giant stars. We combined our angular diameters with Hipparcos parallaxes to determine the stars' physical radii, and used photometry from the literature to calculate their bolometric fluxes, luminosities, and effective temperatures. We then used our results to test the scaling relations used by asteroseismology groups to calculate radii and found good agreement between the radii measured here and the radii predicted by stellar oscillation studies. Themore » precision of the relations is not as well constrained for giant stars as it is for less evolved stars.« less

The effect of ionic membrane properties on the performance of ionic polymer-metal composite (IPMC) actuator

NASA Astrophysics Data System (ADS)

Jho, Jae Y.; Han, Man J.; Park, Jong H.; Lee, Jang Y.; Wang, Hyuck S.

2005-05-01

On purpose to overcome the limit of conventional ionic polymer-metal composites (IPMC) using the commercial ionic membranes, novel IPMCs with radiation-grafted ion-exchange membranes were prepared. Poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-co-HFP) and poly(ethylene-co-tetrafluoroethylene) (ETFE) were radiation-grafted with styrene, and then sulfonated. The properties of the membranes were modulated by controlling the amount of polystyrene sulfonic acid (PSSA) groups in the membranes. The amount of PSSA groups were tuned by controlling the total absorbed dose of γ-ray. The membranes were characterized by measuring the water-uptake, the ion-exchange capacity, and the ion conductivity. The performance of the IPMCs using these membranes were analyzed with laser displacement meter. They exhibited much larger bending displacement in comparison with Nafion-based IPMC. With increasing the amount of PSSA groups, the maximum displacement and the bending speed were remarkably increased. The results made sure that the property of ion-exchange membrane was the key element affecting the actuation performance of IPMC.

Composite Electrolytes for Lithium Batteries: Ionic Liquids in APTES Crosslinked Polymers

NASA Technical Reports Server (NTRS)

Tigelaar, Dean M.; Meador, Mary Ann B.; Bennett, William R.

2007-01-01

Solvent free polymer electrolytes were made consisting of Li(+) and pyrrolidinium salts of trifluoromethanesulfonimide added to a series of hyperbranched poly(ethylene oxide)s (PEO). The polymers were connected by triazine linkages and crosslinked by a sol-gel process to provide mechanical strength. The connecting PEO groups were varied to help understand the effects of polymer structure on electrolyte conductivity in the presence of ionic liquids. Polymers were also made that contain poly(dimethylsiloxane) groups, which provide increased flexibility without interacting with lithium ions. When large amounts of ionic liquid are added, there is little dependence of conductivity on the polymer structure. However, when smaller amounts of ionic liquid are added, the inherent conductivity of the polymer becomes a factor. These electrolytes are more conductive than those made with high molecular weight PEO imbibed with ionic liquids at ambient temperatures, due to the amorphous nature of the polymer.

The inflated radii of M dwarfs in the Pleiades

NASA Astrophysics Data System (ADS)

Jackson, R. J.; Deliyannis, Constantine P.; Jeffries, R. D.

2018-05-01

Rotation periods obtained with the Kepler satellite have been combined with precise measurements of projected rotation velocity from the WIYN 3.5-m telescope to determine the distribution of projected radii for several hundred low-mass (0.1 ≤ M/M⊙ ≤ 0.8), fast-rotating members of the Pleiades cluster. A maximum likelihood modelling technique, that takes account of observational uncertainties, selection effects and censored data, and considers the effects of differential rotation and unresolved binarity, has been used to find that the average radius of these stars is 14 ± 2 per cent larger at a given luminosity than predicted by current evolutionary models of Dotter et al. and Baraffe et al. The same models are a reasonable match to the interferometric radii of older, magnetically inactive field M dwarfs, suggesting that the over-radius may be associated with the young, magnetically active nature of the Pleiades objects. No evidence is found for any change in this over-radius above and below the boundary marking the transition to full convection. Published evolutionary models that incorporate either the effects of magnetic inhibition of convection or the blocking of flux by dark star-spots do not individually explain the radius inflation, but a combination of the two effects might. The distribution of projected radii is consistent with the adopted hypothesis of a random spatial orientation of spin axes; strong alignments of the spin vectors into cones with an opening semi-angle <30° can be ruled out. Any plausible but weaker alignment would increase the inferred over-radius.

Ionically cross-linked poly(allylamine) as a stimulus-responsive underwater adhesive: ionic strength and pH effects.

PubMed

Lawrence, Patrick G; Lapitsky, Yakov

2015-02-03

Gel-like coacervates that adhere to both hydrophilic and hydrophobic substrates under water have recently been prepared by ionically cross-linking poly(allylamine) (PAH) with pyrophosphate (PPi) and tripolyphosphate (TPP). Among the many advantages of these underwater adhesives (which include their simple preparation and low cost) is their ability to dissolve on demand when exposed to high or low pH. To further analyze their stimulus-responsive properties, we have investigated the pH and ionic strength effects on the formation, rheology and adhesion of PAH/PPi and PAH/TPP complexes. The ionic cross-linker concentrations needed to form these adhesives decreased with increasing pH and ionic strength (although the complexes ceased to form when the parent solution pH exceeded ca. 8.5; i.e., the effective pKa of PAH). Once formed, their ionic cross-links were most stable (as inferred from their relaxation times) at near-neutral or slightly alkaline pH values (of roughly 6.5-9) and at low ionic strengths. The decrease in ionic cross-link stability within complexes prepared at other pH values and at elevated (150-300 mM) NaCl concentrations diminished both the strength and longevity of adhesion (although, under most conditions tested, the short-term tensile adhesion strengths remained above 10(5) Pa). Additionally, the sensitivity of PAH/PPi and PAH/TPP complexes to ionic strength was demonstrated as a potential route to injectable adhesive design (where spontaneous adhesive formation was triggered via injection of low-viscosity, colloidal PAH/TPP dispersions into phosphate buffered saline). Thus, while the sensitivity of ionically cross-linked PAH networks to pH and ionic strength can weaken their adhesion, it can also impart them with additional functionality, such as minimally invasive, injectable delivery, and ability to form and dissolve their bonds on demand.

NafionxAE-based polymer actuators with ionic liquids as solvent incorporated at room temperature

NASA Astrophysics Data System (ADS)

Kikuchi, Kunitomo; Tsuchitani, Shigeki

2009-09-01

Nafion®-based ionic polymer-metal composites (IPMCs), with ionic liquids as solvent, were fabricated by exchanging counterions to ionic liquids at room temperature. Ion exchange is performed by only immersing IPMC in a mixture of de-ionized water and ionic liquids at room temperature for 48 h. The fabricated IPMCs exhibited a bending curvature the same as or larger than that of conventional IPMCs with ionic liquids, formed by ion exchange to ionic liquids at an elevated temperature up to about 100 °C, and also had long-term stability in operation in air, with a fluctuation smaller than 21% in bending curvature during a 180 min operation. The effective ion exchange to ionic liquids in the present method is probably due to an increase in diffusion speed of ionic liquids into IPMC by adsorption of water in a Nafion® membrane. It is a surprise that among IPMCs with ionic liquids 1-ethyl-3-methyl-imidazolium tetrafluoroborate, 1-buthyl-3-methyl-imidazolium tetrafluoroborate (BMIBF4), and 1-buthyl-3-methyl-imidazolium hexafluorophosphate (BMIPF6), IPMC with water-insoluble BMIPF6 exhibited a larger bending curvature than that IPMC with water-miscible BMIBF4. This might be due to effective incorporation of BMIPF6 into IPMC, since BMIPF6 has a higher affinity with IPMC than with water in the mixture of water and BMIPF6. From measurements of complex impedance and step voltage response of the driving current of IPMCs with ionic liquid, they are expressed by an equivalent circuit of a parallel combination of a serial circuit of membrane resistance of Nafion® and electric double layer capacitance at metal electrodes, with membrane capacitance of Nafion®, in a frequency range higher than about 0.1 Hz. The difference in magnitude of bending curvature in three kinds of IPMCs with ionic liquids is mainly due to the difference in bending response speed coming from the difference in the membrane resistance.

The California- Kepler Survey. II. Precise Physical Properties of 2025 Kepler Planets and Their Host Stars

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

Johnson, John Asher; Cargile, Phillip A.; Sinukoff, Evan

We present stellar and planetary properties for 1305 Kepler Objects of Interest hosting 2025 planet candidates observed as part of the California- Kepler Survey. We combine spectroscopic constraints, presented in Paper I, with stellar interior modeling to estimate stellar masses, radii, and ages. Stellar radii are typically constrained to 11%, compared to 40% when only photometric constraints are used. Stellar masses are constrained to 4%, and ages are constrained to 30%. We verify the integrity of the stellar parameters through comparisons with asteroseismic studies and Gaia parallaxes. We also recompute planetary radii for 2025 planet candidates. Because knowledge of planetarymore » radii is often limited by uncertainties in stellar size, we improve the uncertainties in planet radii from typically 42% to 12%. We also leverage improved knowledge of stellar effective temperature to recompute incident stellar fluxes for the planets, now precise to 21%, compared to a factor of two when derived from photometry.« less

Analysis of coronal H I Lyman alpha measurements from a rocket flight on 1979 April 13

NASA Technical Reports Server (NTRS)

Withbroe, G. L.; Kohl, J. L.; Weiser, H.; Noci, G.; Munro, R. H.

1982-01-01

It is noted that measurements of the profiles of resonantly scattered hydrogen Lyman-alpha coronal radiation have been used in determining hydrogen kinetic temperatures from 1.5 to 4 solar radii from sun center in a quiet region of the corona. Proton temperatures derived using the line widths decrease with height from 2.6 x 10 to the 6th K at 1.5 solar radii to 1.2 x 10 to the 6th K at 4 solar radii. These measurements, together with temperatures for lower heights determined from earlier Skylab and eclipse data, suggest that there is a maximum in the quiet coronal proton temperature at about 1.5 solar radii. Comparison of measured Lyman-alpha intensities with those calculated using a representative model for the radial variation of the coronal electron density yields information on the magnitude of the electron temperature gradient and suggests that the solar wind flow was subsonic for distances less than 4 solar radii.

The Large Angle Spectroscopic Coronagraph (LASCO): Visible light coronal imaging and spectroscopy

NASA Technical Reports Server (NTRS)

Brueckner, Guenter E.; Howard, Russell A.; Koomen, Martin J.; Korendyke, C.; Michels, D. J.; Socker, D. G.; Lamy, Philippe; Llebaria, Antoine; Maucherat, J.; Schwenn, Rainer

1992-01-01

The Large Angle Spectroscopic Coronagraph (LASCO) is a triple coronagraph being jointly developed for the Solar and Heliospheric Observatory (SOHO) mission. LASCO comprises three nested coronagraphs (C1, C2, and C3) that image the solar corona for 1.1 to 30 solar radii (C1: 1.1 to 3 solar radii, C2: 1.5 to 6 solar radii, and C3: 3 to 30.0 solar radii). The inner coronagraph (C1) is a newly developed mirror version of the classic Lyot coronagraph without an external occultor, while the middle coronagraph (C2) and the outer coronagraph (C3) are externally occulted instruments. High resolution coronal spectroscopy from 1.1 to 3 R solar radii can be performed by using a Fabry-Perot interferometer, which is part of C1. High volume memories and a high speed microprocessor enable extensive onboard image processing. Image compression by factors of 10 to 20 will result in the transmission of 10 to 20 full images per hour.

Effect of surfactants on sorption of atrazine by soil

NASA Astrophysics Data System (ADS)

Abu-Zreig, Majed; Rudra, R. P.; Dickinson, W. T.; Evans, L. J.

1999-03-01

This study investigates the effect of synthetic wastewater containing surfactants on the sorption of atrazine using an equilibrium batch technique. Laboratory experiments were conducted on three soils with two non-ionic (Rexol and Rexonic) surfactants and one anionic (Sulphonic) surfactant, specifically manufactured for the detergent industry. Four sets of experiments were conducted to examine the influence of surfactants on the equilibrium time of atrazine sorption, to explore the effect of surfactant concentration, pH and type of surfactant on the amount of atrazine sorbed and to determine sorption isotherms of atrazine in the presence of surfactants. The results indicate that the application of Sulphonic results in dramatic increase in the adsorption of atrazine on to soils, the increase being directly proportional to the concentration of the surfactant. Application of the Sulphonic surfactants with a concentration of 3000 mg/l can result in a significant increase in Kd values of atrazine for loam and sandy loam soils. On the other hand, the effect of non-ionic surfactants depends on their concentration. Generally, non-ionic surfactants can result in a slight increase in atrazine sorption at high concentration, an exception being Rexol on sandy loam soil. At low concentrations, non-ionic surfactants have shown a tendency to decrease atrazine sorption.

Effects of alkyl chain length and solvents on thermodynamic dissociation constants of the ionic liquids with one carboxyl group in the alkyl chain of imidazolium cations.

PubMed

Chen, Yuehua; Wang, Huiyong; Wang, Jianji

2014-05-01

Thermodynamic dissociation constants of the Brønsted acidic ionic liquids (ILs) are important for their catalytic and separation applications. In this work, a series of imidazolium bromides with one carboxylic acid substitute group in their alkyl chain ([{(CH2)nCOOH}mim]Br, n = 1,3,5,7) have been synthesized, and their dissociation constants (pKa) at different ionic strengths have been determined in aqueous and aqueous organic solvents at 0.1 mole fraction (x) of ethanol, glycol, iso-propanol, and dimethyl sulfoxide by potentiometric titrations at 298.2 K. The standard thermodynamic dissociation constants (pKa(T)) of the ILs in these solvents were calculated from the extended Debye-Hückel equation. It was found that the pKa values increased with the increase of ionic strength of the media and of the addition of organic solvent in water. The pKa(T) values also increased with the increase of the alkyl chain length of cations of the ILs. In addition, the effect of solvent nature on pKa(T) values is interpreted from solvation of the dissociation components and their Gibbs energy of transfer from water to aqueous organic solutions.

Toxicity evaluation of selected ammonium-based ionic liquid forms with MCPP and dicamba moieties on Pseudomonas putida.

PubMed

Piotrowska, Aleksandra; Syguda, Anna; Wyrwas, Bogdan; Chrzanowski, Łukasz; Heipieper, Hermann J

2017-01-01

Combination of the hydrophilic herbicidal anion with hydrophobic, antimicrobial ammonium cation allows to obtain compounds in ionic liquid form with better properties then conventional herbicides. Both cation and anion can be modified by selection of herbicide and the length of alkyl chains in cation structure. However the knowledge of their potential toxic effects are still limited. Furthermore, the relation between hydrophobicity associated with the length of alkyl chains and toxicity for ionic liquids has not been thoroughly studied. Therefore we investigated toxic effects of herbicidal ionic liquid forms on growth inhibition, given as EC 50, of the common soil bacterium Pseudomonas putida. We thereby concentrated on quaternary ammonium salts. Analyzed compounds were composed of dicamba or MCPP moieties and cation with various alkyl chain lengths (n = 6,8,10) We compared them with commercial herbicides, and ammonium-based ionic liquids with neutral anion (Br - ). In addition, cis-trans isomerisation of unsaturated membrane fatty acids in Pseudomonas putida was applied as the proxy for toxicity and membrane activity. We showed that toxicity increased with the length of alkyl chains. However, this correlation is only valid for six and eight carbon atom in alkyl chains, where for n = 10 the EC 50 values rise by one order of magnitude. In our studies, the herbicidal ionic liquids [C 10 ,C 10 ,C 1 ,C 1 N][MCPP] and [C 10 ,C 10 ,C 1 ,C 1 N][dicamba] showed the lowest toxicity among analyzed quaternary ammonium salts and comparable toxicity with corresponding herbicides. No clear increase in toxicity could be followed by changing the anion moieties for ammonium-based ionic liquid forms. Copyright © 2016 Elsevier Ltd. All rights reserved.

Temperature- and pressure-dependent infrared spectroscopy of 1-butyl-3-methylimidazolium trifluoromethanesulfonate: A dipolar coupling theory analysis

NASA Astrophysics Data System (ADS)

Burba, Christopher M.; Chang, Hai-Chou

2018-03-01

Continued growth and development of ionic liquids requires a thorough understanding of how cation and anion molecular structure defines the liquid structure of the materials as well as the various properties that make them technologically useful. Infrared spectroscopy is frequently used to assess molecular-level interactions among the cations and anions of ionic liquids because the intramolecular vibrational modes of the ions are sensitive to the local potential energy environments in which they reside. Thus, different interaction modes among the ions may lead to different spectroscopic signatures in the vibrational spectra. Charge organization present in ionic liquids, such as 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([C4mim]CF3SO3), is frequently modeled in terms of a quasicrystalline structure. Highly structured quasilattices enable the dynamic coupling of vibrationally-induced dipole moments to produce optical dispersion and transverse optical-longitudinal optical (TO-LO) splitting of vibrational modes of the ionic liquid. According to dipolar coupling theory, the degree of TO-LO splitting is predicted to have a linear dependence on the number density of the ionic liquid. Both temperature and pressure will affect the number density of the ionic liquid and, therefore, the amount of TO-LO splitting for this mode. Therefore, we test these relationships through temperature- and pressure-dependent FT-IR spectroscopic studies of [C4mim]CF3SO3, focusing on the totally symmetric Ssbnd O stretching mode for the anion, νs(SO3). Increased temperature decreases the amount of TO-LO splitting for νs(SO3), whereas elevated pressure is found to increase the amount of band splitting. In both cases, the experimental observations follow the general predictions of dipolar coupling theory, thereby supporting the quasilattice model for this ionic liquid.

Metal Cations in G-Quadruplex Folding and Stability

NASA Astrophysics Data System (ADS)

Bhattacharyya, Debmalya; Mirihana Arachchilage, Gayan; Basu, Soumitra

2016-09-01

This review is focused on the structural and physico-chemical aspects of metal cation coordination to G-Quadruplexes (GQ) and their effects on GQ stability and conformation. G-Quadruplex structures are non-canonical secondary structures formed by both DNA and RNA. G-quadruplexes regulate a wide range of important biochemical processes. Besides the sequence requirements, the coordination of monovalent cations in the GQ is essential for its formation and determines the stability and polymorphism of GQ structures. The nature, location and dynamics of the cation coordination and their impact on the overall GQ stability are dependent on several factors such as the ionic radii, hydration energy and the bonding strength to the O6 of guanines. The intracellular monovalent cation concentration and the localized ion concentrations determine the formation of GQs and can potentially dictate their regulatory roles. A wide range of biochemical and biophysical studies on an array of GQ enabling sequences have generated at a minimum the knowledge base that allows us to often predict the stability of GQs in presence of the physiologically relevant metal ions, however, prediction of conformation of such GQs is still out of the realm.

Using 15N-Ammonium to Characterise and Map Potassium Binding Sites in Proteins by NMR Spectroscopy

PubMed Central

Werbeck, Nicolas D; Kirkpatrick, John; Reinstein, Jochen; Hansen, D Flemming

2014-01-01

A variety of enzymes are activated by the binding of potassium ions. The potassium binding sites of these enzymes are very specific, but ammonium ions can often replace potassium ions in vitro because of their similar ionic radii. In these cases, ammonium can be used as a proxy for potassium to characterise potassium binding sites in enzymes: the 1H,15N spin-pair of enzyme-bound 15NH4+ can be probed by 15N-edited heteronuclear NMR experiments. Here, we demonstrate the use of NMR spectroscopy to characterise binding of ammonium ions to two different enzymes: human histone deacetylase 8 (HDAC8), which is activated allosterically by potassium, and the bacterial Hsp70 homologue DnaK, for which potassium is an integral part of the active site. Ammonium activates both enzymes in a similar way to potassium, thus supporting this non-invasive approach. Furthermore, we present an approach to map the observed binding site onto the structure of HDAC8. Our method for mapping the binding site is general and does not require chemical shift assignment of the enzyme resonances. PMID:24520048

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

Sorption of triclosan onto activated carbon, kaolinite and montmorillonite: effects of pH, ionic strength, and humic acid.

PubMed

Behera, Shishir Kumar; Oh, Seok-Young; Park, Hung-Suck

2010-07-15

Sorption of triclosan on three sorbents, viz., activated carbon, kaolinite and montmorillonite was studied as a function of pH, ionic strength and humic acid (HA) concentration through controlled batch experiments. Triclosan sorption was found to be higher in the acidic pH range, as varying pH showed significant influence on the surface charge of the sorbents and degree of ionization of the sorbate. Sorption capacity of the sorbents increased with an increase in the ionic strength of solution. At low pH (pH 3), the overall increase in triclosan sorption was 1.2, approximately 4 and 3.5 times, respectively for activated carbon, kaolinite and montmorillonite when ionic strength was increased from 1x10(-3) to 5x10(-1) M. Triclosan sorption onto activated carbon decreased from 31.4 to 10.6 mg g(-1) by increasing the HA concentration to 200 mg C L(-1). However, during sorption onto kaolinite and montmorillonite, the effect of HA was very complex probably due to (i) hydrophobicity (log K(ow)=4.76) of triclosan; and (ii) complexation of HA with triclosan. Though triclosan sorption onto activated carbon is higher, the potential of kaolinite and montmorillonite in controlling the transport of triclosan in subsurface environment can still be appreciable. 2010 Elsevier B.V. All rights reserved.

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.

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

Salting out of proteins using ammonium sulfate precipitation.

PubMed

Duong-Ly, Krisna C; Gabelli, Sandra B

2014-01-01

Protein solubility is affected by ions. At low ion concentrations (<0.5 M), protein solubility increases along with ionic strength. Ions in the solution shield protein molecules from the charge of other protein molecules in what is known as 'salting-in'. At a very high ionic strength, protein solubility decreases as ionic strength increases in the process known as 'salting-out'. Thus, salting out can be used to separate proteins based on their solubility in the presence of a high concentration of salt. In this protocol, ammonium sulfate will be added incrementally to an E. coli cell lysate to isolate a recombinantly over-expressed protein of 20 kDa containing no cysteine residues or tags. © 2014 Elsevier Inc. All rights reserved.

Mobilization of natural colloids from an iron oxide-coated sand aquifer--Effect of pH and ionic strength

USGS Publications Warehouse

Bunn, Rebecca A.; Magelky, Robin D.; Ryan, Joseph N.; Elimelech, Menachem

2002-01-01

Field and laboratory column experiments were performed to assess the effect of elevated pH and reduced ionic strength on the mobilization of natural colloids in a ferric oxyhydroxide-coated aquifer sediment. The field experiments were conducted as natural gradient injections of groundwater amended by sodium hydroxide additions. The laboratory experiments were conducted in columns of undisturbed, oriented sediments and disturbed, disoriented sediments. In the field, the breakthrough of released colloids coincided with the pH pulse breakthrough and lagged the bromide tracer breakthrough. The breakthrough behavior suggested that the progress of the elevated pH front controlled the transport of the mobilized colloids. In the laboratory, about twice as much colloid release occurred in the disturbed sediments as in the undisturbed sediments. The field and laboratory experiments both showed that the total mass of colloid release increased with increasing pH until the concurrent increase in ionic strength limited release. A decrease in ionic strength did not mobilize significant amounts of colloids in the field. The amount of colloids released normalized to the mass of the sediments was similar for the field and the undisturbed laboratory experiments.

The effect of humidity on ionic wind velocity in ambient air

NASA Astrophysics Data System (ADS)

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

2016-09-01

Due to the evolution of portable electronics and LED lightning system, advances in air cooling technologies must also keep pace. Active cooling by ionic wind, which is usually generated by corona discharge, can greatly reduce the noise and lifetime issues compared to the mechanical fans. The wind is induced when a gas discharge is formed, and neutral molecules gain their energy by the momentum transfer of ion-neutral collisions. However, there is few discussion about the effect of gas composition such as humidity on the wind generation and the physical mechanism is not clear. In the experiment, a positive 5-20 kV DC voltage is applied to the needle-cylinder electrodes with separation of 20 mm. The ionic wind velocity is measured by hot wire anemometry. As the relative humidity (RH) in the ambient air increases, the velocity is found to be severely inhibited. The current is also measured between the cylinder electrode and earth. The results show that the DC component of corona current decreases when RH increases. Since both the discharge current and the ion mobility are reduced when RH increases, their combined effects determine the ionic wind velocity. This work is supported by STW project 13651.

Low-lying Photoexcited States of a One-Dimensional Ionic Extended Hubbard Model

NASA Astrophysics Data System (ADS)

Yokoi, Kota; Maeshima, Nobuya; Hino, Ken-ichi

2017-10-01

We investigate the properties of low-lying photoexcited states of a one-dimensional (1D) ionic extended Hubbard model at half-filling. Numerical analysis by using the full and Lanczos diagonalization methods shows that, in the ionic phase, there exist low-lying photoexcited states below the charge transfer gap. As a result of comparison with numerical data for the 1D antiferromagnetic (AF) Heisenberg model, it was found that, for a small alternating potential Δ, these low-lying photoexcited states are spin excitations, which is consistent with a previous analytical study [Katsura et al., Phys. Rev. Lett. 103, 177402 (2009)]. As Δ increases, the spectral intensity of the 1D ionic extended Hubbard model rapidly deviates from that of the 1D AF Heisenberg model and it is clarified that this deviation is due to the neutral-ionic domain wall, an elementary excitation near the neutral-ionic transition point.

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

Solvation structures of water in trihexyltetradecylphosphonium-orthoborate ionic liquids

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

Wang, Yong-Lei, E-mail: wangyonl@gmail.com; System and Component Design, Department of Machine Design, KTH Royal Institute of Technology, SE-100 44 Stockholm; Sarman, Sten

2016-08-14

Atomistic molecular dynamics simulations have been performed to investigate effective interactions of isolated water molecules dispersed in trihexyltetradecylphosphonium-orthoborate ionic liquids (ILs). The intrinsic free energy changes in solvating one water molecule from gas phase into bulk IL matrices were estimated as a function of temperature, and thereafter, the calculations of potential of mean force between two dispersed water molecules within different IL matrices were performed using umbrella sampling simulations. The systematic analyses of local ionic microstructures, orientational preferences, probability and spatial distributions of dispersed water molecules around neighboring ionic species indicate their preferential coordinations to central polar segments in orthoboratemore » anions. The effective interactions between two dispersed water molecules are partially or totally screened as their separation distance increases due to interference of ionic species in between. These computational results connect microscopic anionic structures with macroscopically and experimentally observed difficulty in completely removing water from synthesized IL samples and suggest that the introduction of hydrophobic groups to central polar segments and the formation of conjugated ionic structures in orthoborate anions can effectively reduce residual water content in the corresponding IL samples.« less

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.

Global transcriptome response to ionic liquid by a tropical rain forest soil bacterium, Enterobacter lignolyticus.

PubMed

Khudyakov, Jane I; D'haeseleer, Patrik; Borglin, Sharon E; Deangelis, Kristen M; Woo, Hannah; Lindquist, Erika A; Hazen, Terry C; Simmons, Blake A; Thelen, Michael P

2012-08-07

To process plant-based renewable biofuels, pretreatment of plant feedstock with ionic liquids has significant advantages over current methods for deconstruction of lignocellulosic feedstocks. However, ionic liquids are often toxic to the microorganisms used subsequently for biomass saccharification and fermentation. We previously isolated Enterobacter lignolyticus strain SCF1, a lignocellulolytic bacterium from tropical rain forest soil, and report here that it can grow in the presence of 0.5 M 1-ethyl-3-methylimidazolium chloride, a commonly used ionic liquid. We investigated molecular mechanisms of SCF1 ionic liquid tolerance using a combination of phenotypic growth assays, phospholipid fatty acid analysis, and RNA sequencing technologies. Potential modes of resistance to 1-ethyl-3-methylimidazolium chloride include an increase in cyclopropane fatty acids in the cell membrane, scavenging of compatible solutes, up-regulation of osmoprotectant transporters and drug efflux pumps, and down-regulation of membrane porins. These findings represent an important first step in understanding mechanisms of ionic liquid resistance in bacteria and provide a basis for engineering microbial tolerance.

HAT-P-65b and HAT-P-66b: Two Transiting Inflated Hot Jupiters and Observational Evidence for the Reinflation of Close-in Giant Planets

NASA Astrophysics Data System (ADS)

Hartman, J. D.; Bakos, G. Á.; Bhatti, W.; Penev, K.; Bieryla, A.; Latham, D. W.; Kovács, G.; Torres, G.; Csubry, Z.; de Val-Borro, M.; Buchhave, L.; Kovács, T.; Quinn, S.; Howard, A. W.; Isaacson, H.; Fulton, B. J.; Everett, M. E.; Esquerdo, G.; Béky, B.; Szklenar, T.; Falco, E.; Santerne, A.; Boisse, I.; Hébrard, G.; Burrows, A.; Lázár, J.; Papp, I.; Sári, P.

2016-12-01

We present the discovery of the transiting exoplanets HAT-P-65b and HAT-P-66b, with orbital periods of 2.6055 and 2.9721 days, masses of 0.527+/- 0.083 {M}{{J}} and 0.783+/- 0.057 {M}{{J}}, and inflated radii of 1.89+/- 0.13 {R}{{J}} and {1.59}-0.10+0.16 {R}{{J}}, respectively. They orbit moderately bright (V=13.145+/- 0.029 and V=12.993+/- 0.052) stars of mass 1.212+/- 0.050 {M}⊙ and {1.255}-0.054+0.107 {M}⊙ . The stars are at the main-sequence turnoff. While it is well known that the radii of close-in giant planets are correlated with their equilibrium temperatures, whether or not the radii of planets increase in time as their hosts evolve and become more luminous is an open question. Looking at the broader sample of well-characterized close-in transiting giant planets, we find that there is a statistically significant correlation between planetary radii and the fractional ages of their host stars, with a false-alarm probability of only 0.0041%. We find that the correlation between the radii of planets and the fractional ages of their hosts is fully explained by the known correlation between planetary radii and their present-day equilibrium temperatures; however, if the zero-age main-sequence equilibrium temperature is used in place of the present-day equilibrium temperature, then a correlation with age must also be included to explain the planetary radii. This suggests that, after contracting during the pre-main-sequence, close-in giant planets are reinflated over time due to the increasing level of irradiation received from their host stars. Prior theoretical work indicates that such a dynamic response to irradiation requires a significant fraction of the incident energy to be deposited deep within the planetary interiors. Based on observations obtained with the Hungarian-made Automated Telescope Network. Based on observations obtained at the W. M. Keck Observatory, which is operated by the University of California and the California Institute of Technology. Keck time has been granted by NOAO (A289Hr, A245Hr) and NASA (N029Hr, N154Hr, N130Hr, N133Hr, N169Hr, N186Hr). Based on observations obtained with the Tillinghast Reflector 1.5 m telescope and the 1.2 m telescope, both operated by the Smithsonian Astrophysical Observatory at the Fred Lawrence Whipple Observatory in Arizona. Based on observations made with the Nordic Optical Telescope, operated by the Nordic Optical Telescope Scientific Association at the Observatorio del Roque de los Muchachos, La Palma, Spain, of the Intituto de Astrofísica de Canarias. Based on observations made with the SOPHIE spectrograph on the 1.93 m telescope at Observatoire de Haute-Provence (OHP, CNRS/AMU), France (programs 15A.PNP.HEBR and 15B.PNP.HEBR). Data presented herein were obtained at the WIYN Observatory from telescope time allocated to NN-EXPLORE through the scientific partnership of the National Aeronautics and Space Administration, the National Science Foundation, and the National Optical Astronomy Observatory. This work was supported by a NASA WIYN PI Data Award, administered by the NASA Exoplanet Science Institute.

Regional nonuniformity of normal adult human left ventricle.

PubMed

Bogaert, J; Rademakers, F E

2001-02-01

Regional nonuniformity is a feature of both diseased and normal left ventricles (LV). With the use of magnetic resonance (MR) myocardial tagging, we performed three-dimensional strain analysis on 87 healthy adults in local cardiac and fiber coordinate systems (radial, circumferential, longitudinal, and fiber strains) to characterize normal nonuniformities and to test the validity of wall thickening as a parameter of regional function. Regional morphology included wall thickness and radii of curvature measurements. With respect to transmural nonuniformity, subendocardial strains exceeded subepicardial strains. Going from base to apex, wall thickness and circumferential radii of curvature decreased, whereas longitudinal radii of curvature increased. All of the strains increased from LV base to apex, resulting in a higher ejection fraction (EF) at the apex than at the base (70.9 +/- 0.4 vs. 62.4 +/- 0.4%; means +/- SE, P < 0.0001). When we looked around the circumference of the ventricle, the anterior part of the LV was the flattest and thinnest and showed the largest wall thickening (46.6 +/- 1.2%) but the lowest EF (64.7 +/- 0.5%). The posterior LV wall was thicker, more curved, and showed a lower wall thickening (32.8 +/- 1.0%) but a higher EF (71.3 +/- 0.5%). The regional contribution of the LV wall to the ejection of blood is thus highly variable and is not fully characterized by wall thickening alone. Differences in regional LV architecture and probably local stress are possible explanations for this marked functional nonuniformity.

Simulations of the gyroid phase in diblock copolymers with the Gaussian disphere model

NASA Astrophysics Data System (ADS)

Karatchentsev, A.; Sommer, J.-U.

2010-12-01

Pure melts of asymmetric diblock copolymers are studied by means of the off-lattice Gaussian disphere model with Monte-Carlo kinetics. In this model, a diblock copolymer chain is mapped onto two soft repulsive spheres with fluctuating radii of gyration and distance between centers of mass of the spheres. Microscopic input quantities of the model such as the combined probability distribution for the radii of gyration and the distance between the spheres as well as conditional monomer number densities assigned to each block were derived in the previous work of F. Eurich and P. Maass [J. Chem. Phys. 114, 7655 (2001)] within an underlying Gaussian chain model. The polymerization degree of the whole chain as well as those of the individual blocks are freely tunable parameters thus enabling a precise determination of the regions of stability of various phases. The model neglects entanglement effects which are irrelevant for the formation of ordered structures in diblock copolymers and which would otherwise unnecessarily increase the equilibration time of the system. The gyroid phase was reproduced in between the cylindrical and lamellar phases in systems with box sizes being commensurate with the size of the unit cell of the gyroid morphology. The region of stability of the gyroid phase was studied in detail and found to be consistent with the prediction of the mean-field theory. Packing frustration was observed in the form of increased radii of gyration of both blocks of the chains located close to the gyroid nodes.

Effects of phosphonium-based ionic liquids on phospholipid membranes studied by small-angle X-ray scattering.

PubMed

Kontro, Inkeri; Svedström, Kirsi; Duša, Filip; Ahvenainen, Patrik; Ruokonen, Suvi-Katriina; Witos, Joanna; Wiedmer, Susanne K

2016-12-01

The effects of ionic liquids on model phospholipid membranes were studied by small-angle X-ray scattering, dynamic light scattering (DLS) and zeta potential measurements. Multilamellar 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine liposomes and large unilamellar vesicles composed of l-α-phosphatidylcholine (eggPC) and l-α-phosphatidylglycerol (eggPG) (80:20mol%) or eggPC, eggPG, and cholesterol (60:20:20mol%) were used as biomimicking membrane models. The effects of the phosphonium-based ionic liquids: tributylmethylphosphonium acetate, trioctylmethylphosphonium acetate, tributyl(tetradecyl)-phosphonium acetate, and tributyl(tetradecyl)-phosphonium chloride, were compared to those of 1-ethyl-3-methyl-imidazolium acetate. With multilamellar vesicles, the ionic liquids that did not disrupt liposomes decreased the lamellar spacing as a function of concentration. The magnitude of the effect depended on concentration for all studied ionic liquids. Using large unilamellar vesicles, first a slight decrease in the vesicle size, then aggregation of vesicles was observed by DLS for increasing ionic liquid concentrations. At concentrations just below those that caused aggregation of liposomes, large unilamellar vesicles were coated by ionic liquid cations, evidenced by a change in their zeta potential. The ability of phosphonium-based ionic liquids to affect liposomes is related to the length of the hydrocarbon chains in the cation. Generally, the ability of ionic liquids to disrupt liposomes goes hand in hand with inducing disorder in the phospholipid membrane. However, trioctylmethylphosphonium acetate selectively extracted and induced a well-ordered lamellar structure in phospholipids from disrupted cholesterol-containing large unilamellar vesicles. This kind of effect was not seen with any other combination of ionic liquids and liposomes. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Study on the temperature-dependent coupling among viscosity, conductivity and structural relaxation of ionic liquids.

PubMed

Yamaguchi, Tsuyoshi; Yonezawa, Takuya; Koda, Shinobu

2015-07-15

The frequency-dependent viscosity and conductivity of three imidazolium-based ionic liquids were measured at several temperatures in the MHz region, and the results are compared with the intermediate scattering functions determined by neutron spin echo spectroscopy. The relaxations of both the conductivity and the viscosity agree with that of the intermediate scattering function at the ionic correlation when the relaxation time is short. As the relaxation time increases, the relaxations of the two transport properties deviate to lower frequencies than that of the ionic structure. The deviation begins at a shorter relaxation time for viscosity than for conductivity, which explains the fractional Walden rule between the zero-frequency values of the shear viscosity and the molar conductivity.

Interaction between 2',4-dihydroxychalcone and the N, f, e conformers of bovine serum albumin: influence of temperature and ionic strength.

PubMed

Curvale, Rolando A; Debattista, Nora B; Pappano, Nora B

2012-04-01

UV-Vis spectroscopy was used to study the interaction between the 2',4- dihydroxychalcone, flavonoid which is known to have anti-tumor activity in vitro, and others biological properties, and the N, F and E conformers of bovine serum albumin at different ionic strengths and temperatures. The Klotz model was found to be adequate to determine the constants and number of binding sites. The reaction was found to be exothermic and spontaneous. The number of binding sites decreases and the reaction is more exergonic along with the increase in ionic strength and the conformational change of N to E. The reactions were necessarily hydrophobic and followed by a process of ionic character.

Non-haloaluminate room-temperature ionic liquids in electrochemistry--a review.

PubMed

Buzzeo, Marisa C; Evans, Russell G; Compton, Richard G

2004-08-20

Some twenty-five years after they first came to prominence as alternative electrochemical solvents, room temperature ionic liquids (RTILs) are currently being employed across an increasingly wide range of chemical fields. This review examines the current state of ionic liquid-based electrochemistry, with particular focus on the work of the last decade. Being composed entirely of ions and possesing wide electrochemical windows (often in excess of 5 volts), it is not difficult to see why these compounds are seen by electrochemists as attractive potential solvents. Accordingly, an examination of the pertinent properties of ionic liquids is presented, followed by an assessment of their application to date across the various electrochemical disciplines, concluding with an outlook viewing current problems and directions.

Mirror Charge Radii and the Neutron Equation of State

NASA Astrophysics Data System (ADS)

Brown, B. Alex

2017-09-01

The differences in the charge radii of mirror nuclei are shown to be proportional to the derivative of the neutron equation of state and the symmetry energy at nuclear matter saturation density. This derivative is important for constraining the neutron equation of state for use in astrophysics. The charge radii of several neutron-rich nuclei are already measured to the accuracy of about 0.005 fm. Experiments at isotope-separator and radioactive-beam facilities are needed to measure the charge radii of the corresponding proton-rich mirror nuclei to a similar accuracy. It is also shown that neutron skins of nuclei with N =Z depend upon the value of the symmetry energy at a density of 0.10 nucleons /fm3 .

Theoretical derivation of anodizing current and comparison between fitted curves and measured curves under different conditions.

PubMed

Chong, Bin; Yu, Dongliang; Jin, Rong; Wang, Yang; Li, Dongdong; Song, Ye; Gao, Mingqi; Zhu, Xufei

2015-04-10

Anodic TiO2 nanotubes have been studied extensively for many years. However, the growth kinetics still remains unclear. The systematic study of the current transient under constant anodizing voltage has not been mentioned in the original literature. Here, a derivation and its corresponding theoretical formula are proposed to overcome this challenge. In this paper, the theoretical expressions for the time dependent ionic current and electronic current are derived to explore the anodizing process of Ti. The anodizing current-time curves under different anodizing voltages and different temperatures are experimentally investigated in the anodization of Ti. Furthermore, the quantitative relationship between the thickness of the barrier layer and anodizing time, and the relationships between the ionic/electronic current and temperatures are proposed in this paper. All of the current-transient plots can be fitted consistently by the proposed theoretical expressions. Additionally, it is the first time that the coefficient A of the exponential relationship (ionic current j(ion) = A exp(BE)) has been determined under various temperatures and voltages. And the results indicate that as temperature and voltage increase, ionic current and electronic current both increase. The temperature has a larger effect on electronic current than ionic current. These results can promote the research of kinetics from a qualitative to quantitative level.

Theoretical derivation of anodizing current and comparison between fitted curves and measured curves under different conditions

NASA Astrophysics Data System (ADS)

Chong, Bin; Yu, Dongliang; Jin, Rong; Wang, Yang; Li, Dongdong; Song, Ye; Gao, Mingqi; Zhu, Xufei

2015-04-01

Anodic TiO2 nanotubes have been studied extensively for many years. However, the growth kinetics still remains unclear. The systematic study of the current transient under constant anodizing voltage has not been mentioned in the original literature. Here, a derivation and its corresponding theoretical formula are proposed to overcome this challenge. In this paper, the theoretical expressions for the time dependent ionic current and electronic current are derived to explore the anodizing process of Ti. The anodizing current-time curves under different anodizing voltages and different temperatures are experimentally investigated in the anodization of Ti. Furthermore, the quantitative relationship between the thickness of the barrier layer and anodizing time, and the relationships between the ionic/electronic current and temperatures are proposed in this paper. All of the current-transient plots can be fitted consistently by the proposed theoretical expressions. Additionally, it is the first time that the coefficient A of the exponential relationship (ionic current jion = A exp(BE)) has been determined under various temperatures and voltages. And the results indicate that as temperature and voltage increase, ionic current and electronic current both increase. The temperature has a larger effect on electronic current than ionic current. These results can promote the research of kinetics from a qualitative to quantitative level.

Influence of Ionic Liquids on Thermodynamics of Small Molecule-DNA Interaction: The Binding of Ethidium Bromide to Calf Thymus DNA.

PubMed

Mishra, Arpit; Ekka, Mary Krishna; Maiti, Souvik

2016-03-17

Ionic liquids (ILs) are salts with poor ionic coordination, resultantly remaining in liquid state below 100 °C and some may retain liquid state even at room temperature. ILs are known to provide a conducive environment for many biological enzymatic reactions, but their interaction with biomacromolecules are poorly understood. In the present study, we investigate the effect of various ionic liquids on DNA-small molecule interaction using calf thymus DNA (ctDNA)-ethidium bromide (EB) as a model system. The effect of various ionic liquids on these interactions is studied by an array of techniques such as circular dichroism (CD), UV melting, fluorescence exclusion and isothermal titration calorimetry. Interestingly, we observed that presence of IL increased the stability of ctDNA without altering its structure. The binding affinities Kbs for EB binding to ctDNA in the presence of 300 mM ILs are about half order of magnitude smaller than the Kbs in absence of ILs and correspond to a less favorable free energy. We noted that, when adjusted to corresponding buffer condition, the unfavorable shift in ΔG of ctDNA-EB interaction is attributed to decreased entropy in the case of ILs, whereas the same effect by NaCl was due to increased enthalpy.

Effect of nitrate and sulfate relative abundance in PM2.5 on liquid water content explored through half-hourly observations of inorganic soluble aerosols at a polluted receptor site

NASA Astrophysics Data System (ADS)

Xue, Jian; Griffith, Stephen M.; Yu, Xin; Lau, Alexis K. H.; Yu, Jian Zhen

2014-12-01

Liquid water content (LWC) is the amount of liquid water on aerosols. It contributes to visibility degradation, provides a surface for gas condensation, and acts as a medium for heterogeneous gas/particle reactions. In this study, 520 half-hourly measurements of ionic chemical composition in PM2.5 at a receptor site in Hong Kong are used to investigate the dependence of LWC on ionic chemical composition, particularly on the relative abundance of sulfate and nitrate. LWC was estimated using a thermodynamic model (AIM-III). Within this data set of PM2.5 ionic compositions, LWC was highly correlated with the multivariate combination of sulfate and nitrate concentrations and RH (R2 = 0.90). The empirical linear regression result indicates that LWC is more sensitive to nitrate mass than sulfate. During a nitrate episode, the highest LWC (80.6 ± 17.9 μg m-3) was observed and the level was 70% higher than that during a sulfate episode despite a similar ionic PM2.5 mass concentration. A series of sensitivity tests were conducted to study LWC change as a function of the relative nitrate and sulfate abundance, the trend of which is expected to shift to more nitrate in China as a result of SO2 reduction and increase in NOx emission. Starting from a base case that uses the average of measured PM2.5 ionic chemical composition (63% SO42-, 11% NO3-, 19% NH4+, and 7% other ions) and an ionic equivalence ratio, [NH4+]/(2[SO42-] + [NO3-]), set constant to 0.72, the results show LWC would increase by 204% at RH = 40% when 50% of the SO42- is replaced by NO3- mass concentration. This is largely due to inhibition of (NH4)3H(SO4)2 crystallization while PM2.5 ionic species persist in the aqueous phase. At RH = 90%, LWC would increase by 12% when 50% of the SO42- is replaced by NO3- mass concentration. The results of this study highlight the important implications to aerosol chemistry and visibility degradation associated with LWC as a result of a shift in PM2.5 ionic chemical composition to more nitrate in atmospheric environments as is expected in many Chinese cities.

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

Centrifugally driven winds from protostellar accretion discs - I. Formulation and initial results

NASA Astrophysics Data System (ADS)

Nolan, C. A.; Salmeron, R.; Federrath, C.; Bicknell, G. V.; Sutherland, R. S.

2017-10-01

Protostellar discs play an important role in star formation, acting as the primary mass reservoir for accretion on to young stars and regulating the extent to which angular momentum and gas is released back into stellar nurseries through the launching of powerful disc winds. In this study, we explore how disc structure relates to the properties of the wind-launching region, mapping out the regions of protostellar discs where wind launching could be viable. We combine a series of 1.5D semi-analytic, steady-state, vertical disc-wind solutions into a radially extended 1+1.5D model, incorporating all three diffusion mechanisms (Ohm, Hall and ambipolar). We observe that the majority of mass outflow via disc winds occurs over a radial width of a fraction of an astronomical unit, with outflow rates attenuating rapidly on either side. We also find that the mass accretion rate, magnetic field strength and surface density profile each have significant effects on both the location of the wind-launching region and the ejection/accretion ratio \\dot{M}_out/\\dot{M}_in. Increasing either the accretion rate or the magnetic field strength corresponds to a shift of the wind-launching region to smaller radii and a decrease in \\dot{M}_out/\\dot{M}_in, while increasing the surface density corresponds to launching regions at larger radii with increased \\dot{M}_out/\\dot{M}_in. Finally, we discover a class of disc winds containing an ineffective launching configuration at intermediate radii, leading to two radially separated regions of wind launching and diminished \\dot{M}_out/\\dot{M}_in. We find that the wind locations and ejection/accretion ratio are consistent with current observational and theoretical estimates.

Effects of ionic strength on passive and iontophoretic transport of cationic permeant across human nail.

PubMed

Smith, Kelly A; Hao, Jinsong; Li, S Kevin

2009-06-01

Transport across the human nail under hydration can be modeled as hindered transport across aqueous pore pathways. As such, nail permselectivity to charged species can be manipulated by changing the ionic strength of the system in transungual delivery to treat nail diseases. The present study investigated the effects of ionic strength upon transungual passive and iontophoretic transport. Transungual passive and anodal iontophoretic transport experiments of tetraethylammonium ion (TEA) were conducted under symmetric conditions in which the donor and receiver had the same ionic strength in vitro. Experiments under asymmetric conditions were performed to mimic the in vivo conditions. Prior to the transport studies, TEA uptake studies were performed to assess the partitioning of TEA into the nail. Permselectivity towards TEA was inversely related to ionic strength in both passive and iontophoretic transport. The permeability and transference number of TEA were higher at lower ionic strengths under the symmetric conditions due to increased partitioning of TEA into the nail. Transference numbers were smaller under the asymmetric conditions compared with their symmetric counterparts. The results demonstrate significant ionic strength effects upon the partitioning and transport of a cationic permeant in transungual transport, which may be instrumental in the development of transungual delivery systems.

Effect of the alkyl chain length on the rotational dynamics of nonpolar and dipolar solutes in a series of N-alkyl-N-methylmorpholinium ionic liquids.

PubMed

Khara, Dinesh Chandra; Kumar, Jaini Praveen; Mondal, Navendu; Samanta, Anunay

2013-05-02

Rotational dynamics of two dipolar solutes, 4-aminophthalimide (AP) and 6-propionyl-2-dimethylaminonaphthalene (PRODAN), and a nonpolar solute, anthracene, have been studied in N-alkyl-N-methylmorpholinium (alkyl = ethyl, butyl, hexyl, and octyl) bis(trifluoromethansulfonyl)imide (Tf2N) ionic liquids as a function of temperature and excitation wavelength to probe the microheterogeneous nature of these ionic liquids, which are recently reported to be more structured than the imidazolium ionic liquids (Khara and Samanta, J. Phys. Chem. B2012, 116, 13430-13438). Analysis of the measured rotational time constants of the solutes in terms of the Stokes-Einstein-Debye (SED) hydrodynamic theory reveals that with increase in the alkyl chain length attached to the cationic component of the ionic liquids, AP shows stick to superstick behavior, PRODAN rotation lies between stick and slip boundary conditions, whereas anthracene exhibits slip to sub slip behavior. The contrasting rotational dynamics of these probe molecules is a reflection of their location in distinct environments of the ionic liquids thus demonstrating the heterogeneity of these ionic liquids. The microheterogeneity of these media, in particular, those with the long alkyl chain, is further evidence from the excitation wavelength dependence study of the rotational diffusion of the dipolar probe molecules.

Quasielastic neutron scattering studies on glass-forming ionic liquids with imidazolium cations

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

Kofu, Maiko; Inamura, Yasuhiro; Miyazaki, Kyoko

2015-12-21

Relaxation processes for imidazolium-based ionic liquids (ILs) were investigated by means of an incoherent quasielastic neutron scattering technique. In order to clarify the cation and anion effects on the relaxation processes, ten samples were measured. For all of the samples, we found three relaxations at around 1 ps, 10 ps, and 100 ps-10 ns, each corresponding to the alkyl reorientation, the relaxation related to the imidazolium ring, and the ionic diffusion. The activation energy (E{sub a}) for the alkyl relaxation is insensitive to both anion and alkyl chain lengths. On the other hand, for the imidazolium relaxation and the ionicmore » diffusion processes, E{sub a} increases as the anion size decreases but is almost independent of the alkyl chain length. This indicates that the ionic diffusion and imidazolium relaxation are governed by the Coulombic interaction between the core parts of the cations (imidazolium ring) and the anions. This is consistent with the fact that the imidazolium-based ILs have nanometer scale structures consisting of ionic and neutral (alkyl chain) domains. It is also found that there is a clear correlation between the ionic diffusion and viscosity, indicating that the ionic diffusion is mainly associated with the glass transition which is one of the characteristics of imidazolium-based ILs.« less

A Study of the Hydration of the Alkali Metal Ions in Aqueous Solution

PubMed Central

2011-01-01

The hydration of the alkali metal ions in aqueous solution has been studied by large angle X-ray scattering (LAXS) and double difference infrared spectroscopy (DDIR). The structures of the dimethyl sulfoxide solvated alkali metal ions in solution have been determined to support the studies in aqueous solution. The results of the LAXS and DDIR measurements show that the sodium, potassium, rubidium and cesium ions all are weakly hydrated with only a single shell of water molecules. The smaller lithium ion is more strongly hydrated, most probably with a second hydration shell present. The influence of the rubidium and cesium ions on the water structure was found to be very weak, and it was not possible to quantify this effect in a reliable way due to insufficient separation of the O–D stretching bands of partially deuterated water bound to these metal ions and the O–D stretching bands of the bulk water. Aqueous solutions of sodium, potassium and cesium iodide and cesium and lithium hydroxide have been studied by LAXS and M–O bond distances have been determined fairly accurately except for lithium. However, the number of water molecules binding to the alkali metal ions is very difficult to determine from the LAXS measurements as the number of distances and the temperature factor are strongly correlated. A thorough analysis of M–O bond distances in solid alkali metal compounds with ligands binding through oxygen has been made from available structure databases. There is relatively strong correlation between M–O bond distances and coordination numbers also for the alkali metal ions even though the M–O interactions are weak and the number of complexes of potassium, rubidium and cesium with well-defined coordination geometry is very small. The mean M–O bond distance in the hydrated sodium, potassium, rubidium and cesium ions in aqueous solution have been determined to be 2.43(2), 2.81(1), 2.98(1) and 3.07(1) Å, which corresponds to six-, seven-, eight- and eight-coordination. These coordination numbers are supported by the linear relationship of the hydration enthalpies and the M–O bond distances. This correlation indicates that the hydrated lithium ion is four-coordinate in aqueous solution. New ionic radii are proposed for four- and six-coordinate lithium(I), 0.60 and 0.79 Å, respectively, as well as for five- and six-coordinate sodium(I), 1.02 and 1.07 Å, respectively. The ionic radii for six- and seven-coordinate K+, 1.38 and 1.46 Å, respectively, and eight-coordinate Rb+ and Cs+, 1.64 and 1.73 Å, respectively, are confirmed from previous studies. The M–O bond distances in dimethyl sulfoxide solvated sodium, potassium, rubidium and cesium ions in solution are very similar to those observed in aqueous solution. PMID:22168370

The Electrostatic Screening Length in Concentrated Electrolytes Increases with Concentration.

PubMed

Smith, Alexander M; Lee, Alpha A; Perkin, Susan

2016-06-16

According to classical electrolyte theories interactions in dilute (low ion density) electrolytes decay exponentially with distance, with the Debye screening length the characteristic length scale. This decay length decreases monotonically with increasing ion concentration due to effective screening of charges over short distances. Thus, within the Debye model no long-range forces are expected in concentrated electrolytes. Here we reveal, using experimental detection of the interaction between two planar charged surfaces across a wide range of electrolytes, that beyond the dilute (Debye-Hückel) regime the screening length increases with increasing concentration. The screening lengths for all electrolytes studied-including aqueous NaCl solutions, ionic liquids diluted with propylene carbonate, and pure ionic liquids-collapse onto a single curve when scaled by the dielectric constant. This nonmonotonic variation of the screening length with concentration, and its generality across ionic liquids and aqueous salt solutions, demonstrates an important characteristic of concentrated electrolytes of substantial relevance from biology to energy storage.

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.

Nanomechanics of layer-by-layer polyelectrolyte complexes: a manifestation of ionic cross-links and fixed charges.

PubMed

Han, Biao; Chery, Daphney R; Yin, Jie; Lu, X Lucas; Lee, Daeyeon; Han, Lin

2016-01-28

This study investigates the roles of two distinct features of ionically cross-linked polyelectrolyte networks - ionic cross-links and fixed charges - in determining their nanomechanical properties. The layer-by-layer assembled poly(allylamine hydrochloride)/poly(acrylic acid) (PAH/PAA) network is used as the model material. The densities of ionic cross-links and fixed charges are modulated through solution pH and ionic strength (IS), and the swelling ratio, elastic and viscoelastic properties are quantified via an array of atomic force microscopy (AFM)-based nanomechanical tools. The roles of ionic cross-links are underscored by the distinctive elastic and viscoelastic nanomechanical characters observed here. First, as ionic cross-links are highly sensitive to solution conditions, the instantaneous modulus, E0, exhibits orders-of-magnitude changes upon pH- and IS-governed swelling, distinctive from the rubber elasticity prediction based on permanent covalent cross-links. Second, ionic cross-links can break and self-re-form, and this mechanism dominates force relaxation of PAH/PAA under a constant indentation depth. In most states, the degree of relaxation is >90%, independent of ionic cross-link density. The importance of fixed charges is highlighted by the unexpectedly more elastic nature of the network despite low ionic cross-link density at pH 2.0, IS 0.01 M. Here, the complex is a net charged, loosely cross-linked, where the degree of relaxation is attenuated to ≈50% due to increased elastic contribution arising from fixed charge-induced Donnan osmotic pressure. In addition, this study develops a new method for quantifying the thickness of highly swollen polymer hydrogel films. It also underscores important technical considerations when performing nanomechanical tests on highly rate-dependent polymer hydrogel networks. These results provide new insights into the nanomechanical characters of ionic polyelectrolyte complexes, and lay the ground for further investigation of their unique time-dependent properties.

The effect of starspots on the radii of low-mass pre-main-sequence stars

NASA Astrophysics Data System (ADS)

Jackson, R. J.; Jeffries, R. D.

2014-07-01

A polytropic model is used to investigate the effects of dark photospheric spots on the evolution and radii of magnetically active, low-mass (M < 0.5 M⊙), pre-main-sequence (PMS) stars. Spots slow the contraction along Hayashi tracks and inflate the radii of PMS stars by a factor of (1 - β)-N compared to unspotted stars of the same luminosity, where β is the equivalent covering fraction of dark starspots and N ≃ 0.45 ± 0.05. This is a much stronger inflation than predicted by Spruit & Weiss for main-sequence stars with the same β, where N ˜ 0.2-0.3. These models have been compared to radii determined for very magnetically active K- and M-dwarfs in the young Pleiades and NGC 2516 clusters, and the radii of tidally locked, low-mass eclipsing binary components. The binary components and zero-age main-sequence K-dwarfs have radii inflated by ˜10 per cent compared to an empirical radius-luminosity relation that is defined by magnetically inactive field dwarfs with interferometrically measured radii; low-mass M-type PMS stars, that are still on their Hayashi tracks, are inflated by up to ˜40 per cent. If this were attributable to starspots alone, we estimate that an effective spot coverage of 0.35 < β < 0.51 is required. Alternatively, global inhibition of convective flux transport by dynamo-generated fields may play a role. However, we find greater consistency with the starspot models when comparing the loci of active young stars and inactive field stars in colour-magnitude diagrams, particularly for the highly inflated PMS stars, where the large, uniform temperature reduction required in globally inhibited convection models would cause the stars to be much redder than observed.

Use of the Posterior/Anterior Corneal Curvature Radii Ratio to Improve the Accuracy of Intraocular Lens Power Calculation: Eom's Adjustment Method.

PubMed

Kim, Mingue; Eom, Youngsub; Lee, Hwa; Suh, Young-Woo; Song, Jong Suk; Kim, Hyo Myung

2018-02-01

To evaluate the accuracy of IOL power calculation using adjusted corneal power according to the posterior/anterior corneal curvature radii ratio. Nine hundred twenty-eight eyes from 928 reference subjects and 158 eyes from 158 cataract patients who underwent phacoemulsification surgery were enrolled. Adjusted corneal power of cataract patients was calculated using the fictitious refractive index that was obtained from the geometric mean posterior/anterior corneal curvature radii ratio of reference subjects and adjusted anterior and predicted posterior corneal curvature radii from conventional keratometry (K) using the posterior/anterior corneal curvature radii ratio. The median absolute error (MedAE) based on the adjusted corneal power was compared with that based on conventional K in the Haigis and SRK/T formulae. The geometric mean posterior/anterior corneal curvature radii ratio was 0.808, and the fictitious refractive index of the cornea for a single Scheimpflug camera was 1.3275. The mean difference between adjusted corneal power and conventional K was 0.05 diopter (D). The MedAE based on adjusted corneal power (0.31 D in the Haigis formula and 0.32 D in the SRK/T formula) was significantly smaller than that based on conventional K (0.41 D and 0.40 D, respectively; P < 0.001 and P < 0.001, respectively). The percentage of eyes with refractive prediction error within ± 0.50 D calculated using adjusted corneal power (74.7%) was significantly greater than that obtained using conventional K (62.7%) in the Haigis formula (P = 0.029). IOL power calculation using adjusted corneal power according to the posterior/anterior corneal curvature radii ratio provided more accurate refractive outcomes than calculation using conventional K.

Computational and Experimental Investigation of Li-doped Ionic Liquid Electrolytes: [pyr14][tfsi], [pyr13][fsi], and [EMIM][BF4

NASA Technical Reports Server (NTRS)

Haskins, Justin B.; Bennett, William R.; Wu, James J.; Hernandez, Dionne M.; Borodin, Oleg; Monk, Joshua D.; Bauschlicher, Charles W.; Lawson, John W.

2014-01-01

We employ molecular dynamics (MD) simulation and experiment to investigate the structure, thermodynamics, and transport of N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N -methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li-salt mole fraction (0.05 xLi+ 0.33) and temperature (298 K T 393 K). Structurally, Li+ is shown to be solvated by three anion neigh- bors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi+ we find the presence of lithium aggregates. Pulsed field gradient spin-echo NMR measurements of diffusion and electrochemical impedance spectroscopy measurements of ionic conductivity are made for the neat ionic liquids as well as 0.5 molal solutions of Li-salt in the ionic liquids. Bulk ionic liquid properties (density, diffusion, viscosity, and ionic conductivity) are obtained with MD and show excellent agreement with experiment. While the diffusion exhibits a systematic decrease with increasing xLi+, the contribution of Li+ to ionic conductivity increases until reach- ing a saturation doping level of xLi+ 0.10. Comparatively, the Li+ conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1-0.3 mScm. Our transport results also demonstrate the necessity of long MD simulation runs ( 200 ns) required to converge transport properties at room T. The differences in Li+ transport are reflected in the residence times of Li+ with the anions (Li), which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, to comment on the relative kinetics of Li+ transport in each liquid, we find that while the net motion of Li+ with its solvation shell (vehicular) significantly contributes to net diffusion in all liquids, the importance of transport through anion exchange (hopping) increases at high xLi+ and in liquids with large anions.

Nuclear States with Abnormally Large Radii (size Isomers)

NASA Astrophysics Data System (ADS)

Ogloblin, A. A.; Demyanova, A. S.; Danilov, A. N.; Belyaeva, T. L.; Goncharov, S. A.

2015-06-01

Application of the methods of measuring the radii of the short-lived excited states (Modified diffraction model MDM, Inelastic nuclear rainbow scattering method INRS, Asymptotic normalization coefficients method ANC) to the analysis of some nuclear reactions provide evidence of existing in 9Be, 11B, 12C, 13C the excited states whose radii exceed those of the corresponding ground states by ~ 30%. Two types of structure of these "size isomers" were identified: neutron halo an α-clusters.

Global Geodesy Using GPS Without Fiducial Sites

NASA Technical Reports Server (NTRS)

Heflin, Michael B.; Blewitt, Geoffrey

1994-01-01

Global Positioning System, GPS, used to make global geodetic measurements without use of fiducial site coordinates. Baseline lengths and geocentric radii for each site determined without having to fix any site coordinates. Given n globally distributed sites, n baseline lengths and n geocentric radii form polyhedron with each site at vertex and with geocenter at intersection of all radii. Geodetic information derived from structure of polyhedron and its change with time. Approach applied to any global geodetic technique.

Radii of neutron drops probed via the neutron skin thickness of nuclei

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

Zhao, P. W.; Gandolfi, S.

Multineutron systems are crucial to understanding the physics of neutron-rich nuclei and neutron stars. Neutron drops, neutrons confined in an external field, are investigated systematically in both nonrelativistic and relativistic density functional theories and with ab initio calculations. Here, we demonstrate a new strong linear correlation, which is universal in the realm of mean-field models, between the rms radii of neutron drops and the neutron skin thickness of 208 Pb and 48 Ca , i.e., the difference between the neutron and proton rms radii of a nucleus. This correlation can be used to deduce the radii of neutron drops frommore » the measured neutron skin thickness in a model-independent way, and the radii obtained for neutron drops can provide a useful constraint for realistic three-neutron forces, due to its high quality. Furthermore, we present a new correlation between the slope L of the symmetry energy and the radii of neutron drops, and provide the first validation of such a correlation by using density-functional models and ab initio calculations. These newly established correlations, together with more precise measurements of the neutron skin thicknesses of 208 Pb and 48 Ca and/or accurate determinations of L , will have an enduring impact on the understanding of multineutron interactions, neutron-rich nuclei, neutron stars, etc.« less

Radii of neutron drops probed via the neutron skin thickness of nuclei

DOE PAGES

Zhao, P. W.; Gandolfi, S.

2016-10-10

Multineutron systems are crucial to understanding the physics of neutron-rich nuclei and neutron stars. Neutron drops, neutrons confined in an external field, are investigated systematically in both nonrelativistic and relativistic density functional theories and with ab initio calculations. Here, we demonstrate a new strong linear correlation, which is universal in the realm of mean-field models, between the rms radii of neutron drops and the neutron skin thickness of 208 Pb and 48 Ca , i.e., the difference between the neutron and proton rms radii of a nucleus. This correlation can be used to deduce the radii of neutron drops frommore » the measured neutron skin thickness in a model-independent way, and the radii obtained for neutron drops can provide a useful constraint for realistic three-neutron forces, due to its high quality. Furthermore, we present a new correlation between the slope L of the symmetry energy and the radii of neutron drops, and provide the first validation of such a correlation by using density-functional models and ab initio calculations. These newly established correlations, together with more precise measurements of the neutron skin thicknesses of 208 Pb and 48 Ca and/or accurate determinations of L , will have an enduring impact on the understanding of multineutron interactions, neutron-rich nuclei, neutron stars, etc.« less

The equivalent depth of burst for impact cratering

NASA Technical Reports Server (NTRS)

Holsapple, K. A.

1980-01-01

The concept of modeling an impact cratering event with an explosive event with the explosive buried at some equivalent depth of burst (d.o.b.) is discussed. Various and different ways to define this equivalent d.o.b. are identified. Recent experimental results for a dense quartz sand are used to determine the equivalent d.o.b. for various conditions of charge type, event size, and impact conditions. The results show a decrease in equivalent d.o.b. with increasing energy for fixed impact velocity and a decrease in equivalent d.o.b. with increasing velocity for fixed energy. The values for an iron projectile are on the order of 2-3 projectile radii for energy equal to one ton of TNT, decreasing to about 1.5 radii at a megaton of TNT. The dependence on projectile and target mass density matches that included in common jet-penetration formulas for projectile densities greater than target densities and for the higher energies.

Sensitivity of Stratospheric Geoengineering with Black Carbon to Aerosol Size and Altitude of Injection

NASA Technical Reports Server (NTRS)

Kravitz, Ben; Robock, Alan; Shindell, Drew T.; Miller, Mark A.

2012-01-01

Simulations of stratospheric geoengineering with black carbon (BC) aerosols using a general circulation model with fixed sea surface temperatures show that the climate effects strongly depend on aerosol size and altitude of injection. 1 Tg BC/a injected into the lower stratosphere would cause little surface cooling for large radii but a large amount of surface cooling for small radii and stratospheric warming of over 60 C. With the exception of small particles, increasing the altitude of injection increases surface cooling and stratospheric warming. Stratospheric warming causes global ozone loss by up to 50% in the small radius case. The Antarctic shows less ozone loss due to reduction of polar stratospheric clouds, but strong circumpolar winds would enhance the Arctic ozone hole. Using diesel fuel to produce the aerosols is likely prohibitively expensive and infeasible. Although studying an absorbing aerosol is a useful counterpart to previous studies involving sulfate aerosols, black carbon geoengineering likely carries too many risks to make it a viable option for deployment.

Magnetic field and particle pressure in the plasma sheet of Jupiter

NASA Technical Reports Server (NTRS)

Lanzerotti, L. J.; Maclennan, C. G.; Broughton, J. N.; Venkatesan, D.; Lepping, R. P.

1987-01-01

The results of an analysis of the energetic particle and magnetic field data acquired by the Voyager 2 spacecraft at distances of about 40-70 Jupiter radii on the nightside of the planet are reported. As in a previous study of similar data at distances of greater than about 80 Jupiter radii, the energy densities of ions (primarily protons) is found to be sufficient to provide the diamagnetic depressions measured in the magnetic field intensity as the spacecraft made successive encounters with the nightside plasma sheet. There is some evidence that the percent contribution of the protons to the energy balance decreases with increasing distance from the planet over this radial interval, although this conclusion is dependent upon the assumption that the proton and heavier ion (oxygen) energy spectra are similar.

The magnetic field of the equatorial magnetotail from 10 to 40 earth radii

NASA Technical Reports Server (NTRS)

Fairfield, D. H.

1986-01-01

A statistical study of IMP 6, 7, and 8 magnetotail magnetic field measurements near the equatorial plane reveals new information about various aspects of magnetospheric structure. More magnetic flux crosses the equatorial plane on the dawn and dusk flanks of the tail than near midnight, but no evidence is found for a dependence on the interplanetary magnetic field sector polarity. Field magnitudes within 3 earth radii of the equatorial plane near dawn are more than twice as large as those near dusk for Xsm = -20 to -10 earth radii. The frequency of occurrence of southward fields is greatest near midnight, and such fields are seen almost twice as often for Xsm = -20 to -10 earth radii as for Xsm beyond -20 earth radii. This latter result supports the idea that the midnight region of the tail between 10 and 20 is a special location where neutral lines are particularly apt to form. Such a neutral line will approach nearest the earth in the midnight and premidnight region, where substorms are thought to have their onset.

Oxidative desulfurization of dibenzothiophene from model oil using ionic liquids as extracting agent

NASA Astrophysics Data System (ADS)

Taha, Mohd F.; Atikah, N.; Chong, F. K.; Shaharun, Maizatul S.

2012-09-01

The oxidative desulfurization of dibenzothiophene (DBT) from model oil (in n-dodecane) was carried out using ionic liquid as the extractant and catalyst, and hydrogen peroxide (H2O2) in combination with acetic acid (CH3COOH) and sulphuric acid (H2SO4) as the oxidant. The ionic liquids used were 1-butyl-3-methylimidazolium octyl sulphate ([Bmim][OcSO4]) and 1-butyl-3-methylimidazolium acetate ([Bmim][Ac]). The effect of the amounts of H2O2 on oxidative desulphurization of model oil was first investigated without the usage of ionic liquids at room temperature. The results indicate that greater amount of H2O2 give higher desulfurization and the maximum desulfurization in this study, i.e. 34 %, was occurred when the molar ratio of H2O2 to sulfur was 5:1. With the usage of ionic liquid and the molar ratio of 5:1 (H2O2:sulfur), the efficiency of DBT removal from model oil was increased significantly in terms of percent removal and removal time. Ionic liquid of [Bmim][OcSO4] performed better than [Bmim][Ac] with 72 % DBT removal. When molar ratio of H2O2 to sulphur was 5:1, volume ratio of ionic liquid to model oil was 1:1 and mixing time was 60 min at room temperature. The results indicate the potential of ionic liquids as the extractant and catalyst for oxidative desulfurization of hydrocarbon fuels.

Using the β-glucosidase catalyzed reaction product glucose to improve the ionic liquid tolerance of β-glucosidases.

PubMed

Goswami, Shubhasish; Gupta, Neha; Datta, Supratim

2016-01-01

Pretreating biomass with ionic liquids (IL) increases enzyme accessibility and cellulose is typically recovered through precipitation with an anti-solvent. An industrially feasible pretreatment and hydrolysis process requires robust cellulases that are stable and active in the presence of either small amounts of ILs co-precipitated with recovered cellulose or for saccharifications in the presence of IL. β-glucosidase (BG) hydrolyzes cellobiose into two molecules of glucose (Glc) and is the last step of biomass hydrolysis. These enzymes are prone not only to product inhibition by glucose but also to inactivation by ILs. With increasing interest in IL-based pretreatment methods, there is increasing focus toward a search for Glc-tolerant and IL-tolerant BG. We identified a BG belonging to the GH1 family, H0HC94, encoded in Agrobacterium tumefaciens 5A, and cloned and overexpressed the protein in Escherichia coli. H0HC94 exhibited high enzymatic activity with β-glycosidic substrates (248 µmol/min/mg on pNPGlc and 262 µmol/min/mg on cellobiose) and tolerant to Glc (apparent K i = 686 mM). Further evidence of Glc-based stabilization came from the increase in melting temperature of H0HC94, with increasing Glc concentrations. The half-life of H0HC94 also increased between 2- and 20-fold in the presence of increasing concentrations of Glc. In the presence of 0.9 M of different [C2mim]-based ionic liquids, the specific activity of H0HC94 decreased by around 20-30 %. However, the addition of 100 mM glucose to the IL-enzyme mix resulted in a more stable enzyme as evidenced by the slight recovery of H0HC94 melting temperature and up to tenfold increase in half-life. This higher stability came at a cost of 2-10 % decrease in specific activity. The steady-state kinetic analyses for a subset of the ionic liquids tested indicate that the enzyme undergoes uncompetitive inhibition by glucose and ionic liquid, indicating the possibility of binding of the ionic liquid and glucose to the enzyme-substrate complex. H0HC94 is a Glc-stabilized BG that is also tolerant up to 0.9 M concentrations of different IL's and indicates the possibilities of using an IL-Glc-based cellulose solvent that displays enzyme-compatibility.

Gray and multigroup radiation transport through 3D binary stochastic media with different sphere radii distributions

DOE PAGES

Olson, Gordon Lee

2016-12-06

Here, gray and multigroup radiation is transported through 3D media consisting of spheres randomly placed in a uniform background. Comparisons are made between using constant radii spheres and three different distributions of sphere radii. Because of the computational cost of 3D calculations, only the lowest angle order, n=1, is tested. If the mean chord length is held constant, using different radii distributions makes little difference. This is true for both gray and multigroup solutions. 3D transport solutions are compared to 2D and 1D solutions with the same mean chord lengths. 2D disk and 3D sphere media give solutions that aremore » nearly identical while 1D slab solutions are fundamentally different.« less

Gray and multigroup radiation transport through 3D binary stochastic media with different sphere radii distributions

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

Olson, Gordon Lee

Here, gray and multigroup radiation is transported through 3D media consisting of spheres randomly placed in a uniform background. Comparisons are made between using constant radii spheres and three different distributions of sphere radii. Because of the computational cost of 3D calculations, only the lowest angle order, n=1, is tested. If the mean chord length is held constant, using different radii distributions makes little difference. This is true for both gray and multigroup solutions. 3D transport solutions are compared to 2D and 1D solutions with the same mean chord lengths. 2D disk and 3D sphere media give solutions that aremore » nearly identical while 1D slab solutions are fundamentally different.« less

Influence of microstructure and AlPO4 secondary-phase on the ionic conductivity of Li1.3Al0.3Ti1.7(PO4)3 solid-state electrolyte

NASA Astrophysics Data System (ADS)

Yu, Shicheng; Mertens, Andreas; Gao, Xin; Gunduz, Deniz Cihan; Schierholz, Roland; Benning, Svenja; Hausen, Florian; Mertens, Josef; Kungl, Hans; Tempel, Hermann; Eichel, Rüdiger-A.

2016-09-01

A ceramic solid-state electrolyte of lithium aluminum titanium phosphate with the composition of Li1.3Al0.3Ti1.7(PO4)3 (LATP) was synthesized by a sol-gel method using a pre-dissolved Ti-source. The annealed LATP powders were subsequently processed in a binder-free dry forming method and sintered under air for the pellet preparation. Phase purity, density, microstructure as well as ionic conductivity of the specimen were characterized. The highest density (2.77gṡcm-3) with an ionic conductivity of 1.88×10-4 Sṡcm-1 (at 30∘C) was reached at a sintering temperature of 1100∘C. Conductivity of LATP ceramic electrolyte is believed to be significantly affected by both, the AlPO4 secondary phase content and the ceramic electrolyte microstructure. It has been found that with increasing sintering temperature, the secondary-phase content of AlPO4 increased. For sintering temperatures above 1000∘C, the secondary phase has only a minor impact, and the ionic conductivity is predominantly determined by the microstructure of the pellet, i.e. the correlation between density, porosity and particle size. In that respect, it has been demonstrated, that the conductivity increases with increasing particle size in this temperature range and density.

Modelling sound propagation in the Southern Ocean to estimate the acoustic impact of seismic research surveys on marine mammals

NASA Astrophysics Data System (ADS)

Breitzke, Monika; Bohlen, Thomas

2010-05-01

Modelling sound propagation in the ocean is an essential tool to assess the potential risk of air-gun shots on marine mammals. Based on a 2.5-D finite-difference code a full waveform modelling approach is presented, which determines both sound exposure levels of single shots and cumulative sound exposure levels of multiple shots fired along a seismic line. Band-limited point source approximations of compact air-gun clusters deployed by R/V Polarstern in polar regions are used as sound sources. Marine mammals are simulated as static receivers. Applications to deep and shallow water models including constant and depth-dependent sound velocity profiles of the Southern Ocean show dipole-like directivities in case of single shots and tubular cumulative sound exposure level fields beneath the seismic line in case of multiple shots. Compared to a semi-infinite model an incorporation of seafloor reflections enhances the seismically induced noise levels close to the sea surface. Refraction due to sound velocity gradients and sound channelling in near-surface ducts are evident, but affect only low to moderate levels. Hence, exposure zone radii derived for different hearing thresholds are almost independent of the sound velocity structure. With decreasing thresholds radii increase according to a spherical 20 log10 r law in case of single shots and according to a cylindrical 10 log10 r law in case of multiple shots. A doubling of the shot interval diminishes the cumulative sound exposure levels by -3 dB and halves the radii. The ocean bottom properties only slightly affect the radii in shallow waters, if the normal incidence reflection coefficient exceeds 0.2.

Spread of the dust temperature distribution in circumstellar disks

NASA Astrophysics Data System (ADS)

Heese, S.; Wolf, S.; Dutrey, A.; Guilloteau, S.

2017-07-01

Context. Accurate temperature calculations for circumstellar disks are particularly important for their chemical evolution. Their temperature distribution is determined by the optical properties of the dust grains, which, among other parameters, depend on their radius. However, in most disk studies, only average optical properties and thus an average temperature is assumed to account for an ensemble of grains with different radii. Aims: We investigate the impact of subdividing the grain radius distribution into multiple sub-intervals on the resulting dust temperature distribution and spectral energy distribution (SED). Methods: The temperature distribution, the relative grain surface below a certain temperature, the freeze-out radius, and the SED were computed for two different scenarios: (1) Radius distribution represented by 16 logarithmically distributed radius intervals, and (2) radius distribution represented by a single grain species with averaged optical properties (reference). Results: Within the considered parameter range, I.e., of grain radii between 5 nm and 1 mm and an optically thin and thick disk with a parameterized density distribution, we obtain the following results: in optically thin disk regions, the temperature spread can be as large as 63% and the relative grain surface below a certain temperature is lower than in the reference disk. With increasing optical depth, the difference in the midplane temperature and the relative grain surface below a certain temperature decreases. Furthermore, below 20 K, this fraction is higher for the reference disk than for the case of multiple grain radii, while it shows the opposite behavior for temperatures above this threshold. The thermal emission in the case of multiple grain radii at short wavelengths is stronger than for the reference disk. The freeze-out radius (snowline) is a function of grain radius, spanning a radial range between the coldest and warmest grain species of 30 AU.

Mechanisms of the Diffusion of Nonpolar Substances in a Hydrophilic Ionic Liquid

NASA Astrophysics Data System (ADS)

Atamas', N. A.

2018-01-01

The structural-dynamic features of ionic liquid-nonpolar substance systems are studied by means of molecular dynamics using Frenkel's fundamental theory of a liquid and the phonon theory of the thermodynamics of a liquid, in combination with the DL_POLY_4.05 software package. Argon, methane, and benzene molecules serve as the dissolved substances. Model concepts are proposed and analyzed to describe the diffusion of molecules of a dissolved substance in an ionic liquid. It is shown that an increase in the mass of the molecules of a dissolved nonpolar substance correlates with their mobility in a hydrophilic ionic liquid (IL). This determines the diffusion of the components of dmim+/Cl- IL solutions and is responsible for the anomalous behavior of the solubility of nonpolar substances in them.

Capacitance of Nanoporous Carbon-Based Supercapacitors Is a Trade-Off between the Concentration and the Separability of the Ions.

PubMed

Burt, Ryan; Breitsprecher, Konrad; Daffos, Barbara; Taberna, Pierre-Louis; Simon, Patrice; Birkett, Greg; Zhao, X S; Holm, Christian; Salanne, Mathieu

2016-10-06

Nanoporous carbon-based supercapacitors store electricity through adsorption of ions from the electrolyte at the surface of the electrodes. Room temperature ionic liquids, which show the largest ion concentrations among organic liquid electrolytes, should in principle yield larger capacitances. Here, we show by using electrochemical measurements that the capacitance is not significantly affected when switching from a pure ionic liquid to a conventional organic electrolyte using the same ionic species. By performing additional molecular dynamics simulations, we interpret this result as an increasing difficulty of separating ions of opposite charges when they are more concentrated, that is, in the absence of a solvent that screens the Coulombic interactions. The charging mechanism consistently changes with ion concentration, switching from counterion adsorption in the diluted organic electrolyte to ion exchange in the pure ionic liquid. Contrarily to the capacitance, in-pore diffusion coefficients largely depend on the composition, with a noticeable slowing of the dynamics in the pure ionic liquid.

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

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.

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.

Influence of cellulose nanocrystals concentration and ionic strength on the elaboration of cellulose nanocrystals-xyloglucan multilayered thin films.

PubMed

Dammak, Abir; Moreau, Céline; Azzam, Firas; Jean, Bruno; Cousin, Fabrice; Cathala, Bernard

2015-12-15

The effect of the variation of CNC concentration on the growth pattern of CNC-XG films is investigated. We found that a transition in the growth slope occurs at a CNC concentration of roughly 3-4gL(-1). A close effect can be obtained by the increase of the ionic strength of the CNC suspensions, suggesting that electrostatic interactions are involved. Static light scattering investigation of CNC dispersions at increasing concentrations demonstrated that the particle-particle interactions change as the CNC concentration increases. Neutron Reflectivity (NR) was used to probe the internal structure of the films. The increase of the CNC concentration as well as the increase of the ionic strength in the CNC suspension were found to induce a densification of the adsorbed CNC layers, even though the mechanisms are not strictly identical in both cases. Small changes in these parameters provide a straightforward way of controlling the architecture of CNC-based multilayered thin films and, as a result, their functional properties. Copyright © 2015 Elsevier Inc. All rights reserved.

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

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Polyelectrolyte brushes in mixed ionic medium studied via intermolecular forces

NASA Astrophysics Data System (ADS)

Farina, Robert; Laugel, Nicolas; Pincus, Philip; Tirrell, Matthew

2011-03-01

The vast uses and applications of polyelectrolyte brushes make them an attractive field of research especially with the growing interest in responsive materials. Polymers which respond via changes in temperature, pH, and ionic strength are increasingly being used for applications in drug delivery, chemical gating, etc. When polyelectrolyte brushes are found in either nature (e.g., surfaces of cartilage and mammalian lung interiors) or commercially (e.g., skin care products, shampoo, and surfaces of medical devices) they are always surrounded by mixed ionic medium. This makes the study of these brushes in varying ionic environments extremely relevant for both current and future potential applications. The polyelectrolyte brushes in this work are diblock co-polymers of poly-styrene sulfonate (N=420) and poly-t-butyl styrene (N=20) which tethers to a hydrophobic surface allowing for a purely thermodynamic study of the polyelectrolyte chains. Intermolecular forces between two brushes are measured using the SFA. As multi-valent concentrations are increased, the brushes collapse internally and form strong adhesion between one another after contact (properties not seen in a purely mono-valent environment).

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

Effects of glycine and current density on the mechanism of electrodeposition, composition and properties of Ni-Mn films prepared in ionic liquid

NASA Astrophysics Data System (ADS)

Guo, Jiacheng; Guo, Xingwu; Wang, Shaohua; Zhang, Zhicheng; Dong, Jie; Peng, Liming; Ding, Wenjiang

2016-03-01

The effects of glycine on the mechanism of electrodeposition of Ni-Mn alloy film prepared in ChCl-urea ionic liquid were studied in order to control the composition, microstructure and properties of the film. The cyclic voltammograms revealed that the presence of glycine in the ionic liquid can inhibit the reduction of Ni2+ ions but promote the reduction of Mn2+ ions in the cathodic scan. However, it promoted the dissolution of both Ni and Mn deposits in the ChCl-urea ionic liquids during the reverse scan. Glycine changed the mode of Ni-Mn film growth from Volmer-Weber mode into Stranski-Krastanov mode. The Mn content in the Ni-Mn film increased with the increase of concentration of glycine and current density. The Ni-Mn alloy film with 3.1 at.% Mn exhibited the lowest corrosion current density of 3 × 10-7 A/cm2 compared with other films prepared and exhibited better corrosion resistance than pure Ni film in 3.5 wt.% NaCl solution.

Visualization and Quantification of Rotor Tip Vortices in Helicopter Flows

NASA Technical Reports Server (NTRS)

Kao, David L.; Ahmad, Jasim U.; Holst, Terry L.

2015-01-01

This paper presents an automated approach for effective extraction, visualization, and quantification of vortex core radii from the Navier-Stokes simulations of a UH-60A rotor in forward flight. We adopt a scaled Q-criterion to determine vortex regions and then perform vortex core profiling in these regions to calculate vortex core radii. This method provides an efficient way of visualizing and quantifying the blade tip vortices. Moreover, the vortices radii are displayed graphically in a plane.

Proton Distribution Radii of 12-19C Illuminate Features of Neutron Halos

DOE PAGES

Kanungo, R.; Horiuchi, W.; Hagen, Gaute; ...

2016-09-02

We report proton radii of 12-19C densities derived from first accurate charge changing cross section measurements at 900A MeV with a carbon target. A thick neutron surface evolves from ~0.5 fm in 15C to ~1 fm in 19C. Also, the halo radius in 19C is found to be 6.4±0.7 fm as large as 11Li. Ab initio calculations based on chiral nucleon-nucleon and three-nucleon forces reproduce the radii well.

Calculation of Protein Heat Capacity from Replica-Exchange Molecular Dynamics Simulations with Different Implicit Solvent Models

DTIC Science & Technology

2008-10-30

rigorous Poisson-based methods generally apply a Lee-Richards mo- lecular surface.9 This surface is considered the de facto description for continuum...definition and calculation of the Born radii. To evaluate the Born radii, two approximations are invoked. The first is the Coulomb field approximation (CFA...energy term, and depending on the particular GB formulation, higher-order non- Coulomb correction terms may be added to the Born radii to account for the

Synthesis of flower-like Boehmite (γ-AlOOH) via a one-step ionic liquid-assisted hydrothermal route

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

Tang, Zhe, E-mail: tangzhe1983@163.com; Liang, Jilei, E-mail: liangjilei_httplan@126.com; Li, Xuehui, E-mail: lxhhmx@163.com

A simple and novel synthesis process, one-step ionic liquid-assisted hydrothermal synthesis route, has been developed in the work to synthesize Bohemithe (γ-AlOOH) with flower-like structure. The samples were characterized by X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR) and Scanning Electron Microscope (SEM). Ionic liquid [Omim]{sup +}Cl{sup −}, as a template, plays an important role in the morphology and pore structure of the products due to its strong interactions with reaction particles. With the increase in the dosage of ionic liquid [Omim]{sup +}Cl{sup −}, the morphology of the γ-AlOOH was changed from initial bundles of nanosheets (without ionic liquid) intomore » final well-developed monodispersed 3D flower-like architectures ([Omim]{sup +}Cl{sup −}=72 mmol). The pore structure was also altered gradually from initial disordered slit-like pore into final relatively ordered ink-bottle pore. Furthermore, the proposed formation mechanism and other influencing factors such as reaction temperature and urea on formation and morphology of the γ-AlOOH have also been investigated. - Graphical abstract: The flower-like γ-AlOOH architectures composed by nanosheets with narrow size distribution (1.6–2.2 μm) and uniform pore size (6.92 nm) have been synthesized via a one-step ionic liquid-assisted hydrothermal route. - Highlights: • The γ-AlOOH microflowers were synthesized via an ionic liquid-assisted hydrothermal route. • Ionic liquid plays an important role on the morphology and porous structure of the products. • Ionic liquid can be easily removed from the products and reused in recycling experiments. • A “aggregation–recrystallization–Ostwald Ripening“formation mechanism may occur.« less

Globular, Sponge-like to Layer-like Morphological Transition in 1-n-Alkyl-3-methylimidazolium Octylsulfate Ionic Liquid Homologous Series.

PubMed

Kapoor, Utkarsh; Shah, Jindal K

2018-01-11

Segregation of polar and nonpolar domains in ionic liquids for which either the cation or anion is responsible for inducing nonpolar domains is well understood. On the other hand, information regarding the nanoscale heterogeneities originating due to the presence of nonpolar content on both the ions is rudimentary at this point. The present contribution is aimed at addressing this question and focuses on a molecular dynamics simulation study to probe nanoscale structural and aggregation features of the 1-n-alkyl-3-methylimidazolium [C n mim] octylsulfate [C 8 SO 4 ] ionic liquid homologous series (n = 2, 4, 6, 8, 10, and 12). The objective of this work is to determine the effect of increasing alkyl chain length in the cation on nonpolar domain formation, especially when the alkyl chain lengths from both the ions participate in defining such domains. The results indicate that all the ionic liquids form nonpolar domains, morphology of which gradually changes from globular, sponge-like to layer-like structure with increase in the cationic alkyl chain length. The length of the nonpolar domains calculated from the total structure factor for [C 10 mim][C 8 SO 4 ] is considerably higher than that reported for other imidazolium-based ionic liquid containing smaller anions. The structure factor for [C 12 mim][C 8 SO 4 ] ionic liquid contains multiple intermediate peaks separating the charge alternation peak and pre-peak, which points to nonpolar domains of varying lengths, an observation that remains to be validated. Analysis of the heterogeneous order parameters and orientational correlation functions of the alkyl chains further suggests an increase in the spatial heterogeneity and long-range order along the homologous series. The origin of rich diversity of structures obtained by introducing nonpolar content on both the ions is discussed.

Spring thaw ionic pulses boost nutrient availability and microbial growth in entombed Antarctic Dry Valley cryoconite holes

PubMed Central

Telling, Jon; Anesio, Alexandre M.; Tranter, Martyn; Fountain, Andrew G.; Nylen, Thomas; Hawkings, Jon; Singh, Virendra B.; Kaur, Preeti; Musilova, Michaela; Wadham, Jemma L.

2014-01-01

The seasonal melting of ice entombed cryoconite holes on McMurdo Dry Valley glaciers provides oases for life in the harsh environmental conditions of the polar desert where surface air temperatures only occasionally exceed 0°C during the Austral summer. Here we follow temporal changes in cryoconite hole biogeochemistry on Canada Glacier from fully frozen conditions through the initial stages of spring thaw toward fully melted holes. The cryoconite holes had a mean isolation age from the glacial drainage system of 3.4 years, with an increasing mass of aqueous nutrients (dissolved organic carbon, total nitrogen, total phosphorus) with longer isolation age. During the initial melt there was a mean nine times enrichment in dissolved chloride relative to mean concentrations of the initial frozen holes indicative of an ionic pulse, with similar mean nine times enrichments in nitrite, ammonium, and dissolved organic matter. Nitrate was enriched twelve times and dissolved organic nitrogen six times, suggesting net nitrification, while lower enrichments for dissolved organic phosphorus and phosphate were consistent with net microbial phosphorus uptake. Rates of bacterial production were significantly elevated during the ionic pulse, likely due to the increased nutrient availability. There was no concomitant increase in photosynthesis rates, with a net depletion of dissolved inorganic carbon suggesting inorganic carbon limitation. Potential nitrogen fixation was detected in fully melted holes where it could be an important source of nitrogen to support microbial growth, but not during the ionic pulse where nitrogen availability was higher. This study demonstrates that ionic pulses significantly alter the timing and magnitude of microbial activity within entombed cryoconite holes, and adds credence to hypotheses that ionic enrichments during freeze-thaw can elevate rates of microbial growth and activity in other icy habitats, such as ice veins and subglacial regelation zones. PMID:25566210

Spring thaw ionic pulses boost nutrient availability and microbial growth in entombed Antarctic Dry Valley cryoconite holes.

PubMed

Telling, Jon; Anesio, Alexandre M; Tranter, Martyn; Fountain, Andrew G; Nylen, Thomas; Hawkings, Jon; Singh, Virendra B; Kaur, Preeti; Musilova, Michaela; Wadham, Jemma L

2014-01-01

The seasonal melting of ice entombed cryoconite holes on McMurdo Dry Valley glaciers provides oases for life in the harsh environmental conditions of the polar desert where surface air temperatures only occasionally exceed 0°C during the Austral summer. Here we follow temporal changes in cryoconite hole biogeochemistry on Canada Glacier from fully frozen conditions through the initial stages of spring thaw toward fully melted holes. The cryoconite holes had a mean isolation age from the glacial drainage system of 3.4 years, with an increasing mass of aqueous nutrients (dissolved organic carbon, total nitrogen, total phosphorus) with longer isolation age. During the initial melt there was a mean nine times enrichment in dissolved chloride relative to mean concentrations of the initial frozen holes indicative of an ionic pulse, with similar mean nine times enrichments in nitrite, ammonium, and dissolved organic matter. Nitrate was enriched twelve times and dissolved organic nitrogen six times, suggesting net nitrification, while lower enrichments for dissolved organic phosphorus and phosphate were consistent with net microbial phosphorus uptake. Rates of bacterial production were significantly elevated during the ionic pulse, likely due to the increased nutrient availability. There was no concomitant increase in photosynthesis rates, with a net depletion of dissolved inorganic carbon suggesting inorganic carbon limitation. Potential nitrogen fixation was detected in fully melted holes where it could be an important source of nitrogen to support microbial growth, but not during the ionic pulse where nitrogen availability was higher. This study demonstrates that ionic pulses significantly alter the timing and magnitude of microbial activity within entombed cryoconite holes, and adds credence to hypotheses that ionic enrichments during freeze-thaw can elevate rates of microbial growth and activity in other icy habitats, such as ice veins and subglacial regelation zones.

Effects of humic acid and solution chemistry on the aggregation and dispersion of carboxyl-functionalized carbon black nanoparticles

NASA Astrophysics Data System (ADS)

Hwang, G.; Gomez-Flores, A.; Choi, S.; Han, Y., , Dr; Kim, H.

2017-12-01

The influence of humic acid, ionic strength and ionic species on the aggregation and dispersion of carboxyl-functionalized carbon black nanoparticles (CB-NPs) was systemically investigated in aqueous media. The experimental conditions of stability tests were selected to the changes in the solution chemistry (0.1-10 mM NaCl and 0.01-1 mM CaCl2) and in the presence/absence of humic acid (1 and 5 mg L-1) in an aquatic environment. The CB-NPs suspension was more rapidly settled in NaCl solution than in CaCl2. Specifically, in the case of NaCl, the aggregation rate of CB-NPs increased with ionic strength. Contrary, CB-NPs dispersed in CaCl2 were insensitive to the aggregation as the ionic strength increased; that was because specific adsorption of the divalent cation Ca2+ occurred since the zeta potential of the CB-NPs is reversed to a positive charge with increasing of the ionic strength. It was confirmed that humic acid greatly influences the stability of the CB-NPs. In particular, the dispersion of CB-NPs was improved in the whole range of ionic strengths of NaCl as well as of CaCl2. To support the results, the interaction energy between CB-NPs was calculated for each condition by using the classical Derjaguin-Landau-Verwey-Overbeek (DLVO) and modified-DLVO theories. In the presence of humic acid, the improved stability of CB-NPs is attributed to the steric repulsive force.This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2015R1D1A3A01020766), the Ministry of Education (MOE) and National Research Foundation of Korea (NRF) through the Human Resource Training Project for Regional Innovation (2015H1C1A1035930) and Korea Energy and Mineral Resources Engineering Program (KEMREP).

Effect of Micellization on the Adsorption Kinetics of Polymeric Surfactants to the Solid/Water Interface

NASA Astrophysics Data System (ADS)

Toomey, Ryan; Tirrell, Matthew

2002-03-01

We have studied the adsorption kinetics of two classes of hydrophobic/ionic diblock copolymer surfactants in aqueous environments to understand the role that micellization plays in the adsorption process. The two systems studied were poly(t-butyl styrene)-block-poly(styrene sulfonate) (PtBS-b-PSS) and polystyrene-block-poly(acrylic acid) (PS-b-PAA). It is found that by changing the hydrophobicity of the adsorbing surface, micelle adsorption can be turned on or off. When micelle adsorption occurs, the initial adsorption rate is always slower than the supply rate of micelles to the surface, indicating “reaction-limited” adsorption. Since these micelles have essentially frozen cores, the adsorption cannot be explained by the release of unimers from the micelles. Rather, micelles directly adsorb, and they have to overcome the potential barrier imposed by their corona. Due to micellization, the adsorption rate can also be a complex function of ionic strength. A regime was found where the initial adsorption rate decreased with increasing ionic strength. This anomaly can be explained by the onset of micellization. As the salt concentration is increased, more micelles are formed. However micelles adsorb roughly an order of magnitude slower than free chains. Therefore, if increasing the ionic strength produces more micelles, the adsorption rate will simultaneously decrease.

Adsorption of sulfamethoxazole by magnetic biochar: Effects of pH, ionic strength, natural organic matter and 17α-ethinylestradiol.

PubMed

Reguyal, Febelyn; Sarmah, Ajit K

2018-07-01

Recent studies have shown the widespread occurrence of pharmaceuticals in the aquatic environment leading to increasing global concern on their potential adverse effects in the environment and public health. In this study, we evaluated the use of magnetic biochar derived from pine sawdust, one of New Zealand's major wood wastes, to remove an emerging contaminant, sulfamethoxazole (SMX), at different pH, ionic strength, natural organic matter (NOM) and a competing compound, 17α-ethinylestradiol (EE2). In single-solute system, the sorption of SMX onto magnetic biochar was found to be highly pH-dependent and slightly increased with increase in ionic strength. However, the effects of pH, ionic strength and NOM were relatively insignificant compared to the sorption inhibition caused by EE2 in binary-solute system. Both SMX and EE2 sorption onto the highly carbonised biochar in magnetic biochar were postulated to be due to the π-π electron donor acceptor and hydrophobic interaction. EE2 is more hydrophobic than SMX. Hence, strong competition between these compounds was identified where EE2 markedly inhibited the sorption of SMX onto magnetic biochar in all artificial environmental conditions studied. Copyright © 2018 Elsevier B.V. All rights reserved.

On the structural and impedance characteristics of Li- doped PEO, using n-butyl lithium in hexane as dopant

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

Anand, P. B., E-mail: anandputhirath@gmail.com, E-mail: jayalekshmi@cusat.ac.in; Jayalekshmi, S., E-mail: anandputhirath@gmail.com, E-mail: jayalekshmi@cusat.ac.in

2014-01-28

Nowadays polymer based solid state electrolytes for applications in rechargeable battery systems are highly sought after materials, pursued extensively by various research groups worldwide. Numerous methods are discussed in literature to improve the fundamental properties like electrical conductivity, mechanical stability and interfacial stability of polymer based electrolytes. The application of these electrolytes in Li-ion cells is still in the amateur state, due to low ionic conductivity, low lithium transport number and the processing difficulties. The present work is an attempt to study the effects of Li doping on the structural and transport properties of the polymer electrolyte, poly-ethelene oxide (PEO)more » (Molecular weight: 200,000). Li doped PEO was obtained by treating PEO with n-Butyllithium in hexane for different doping concentrations. Structural characterization of the samples was done by XRD and FTIR techniques. Impedance measurements were carried out to estimate the ionic conductivity of Li doped PEO samples. It is seen that, the crystallinity of the doped PEO decreases on increasing the doping concentration. XRD and FTIR studies support this observation. It is inferred that, ionic conductivity of the sample is increasing on increasing the doping concentration since less crystallinity permits more ionic transport. Impedance measurements confirm the results quantitatively.« less

Highly efficient micellar extraction of toxic picric acid into novel ionic liquid: Effect of parameters, solubilization isotherm, evaluation of thermodynamics and design parameters.

PubMed

Bhatt, Darshak R; Maheria, Kalpana C; Parikh, Jigisha K

2015-12-30

A simple and new approach in cloud point extraction (CPE) method was developed for removal of picric acid (PA) by the addition of N,N,N,N',N',N'-hexaethyl-ethane-1,2-diammonium dibromide ionic liquid (IL) in non-ionic surfactant Triton X-114 (TX-114). A significant increase in extraction efficiency was found upon the addition of dicationic ionic liquid (DIL) at both nearly neutral and high acidic pH. The effects of different operating parameters such as pH, temperature, time, concentration of surfactant, PA and DIL on extraction of PA were investigated and optimum conditions were established. The extraction mechanism was also proposed. A developed Langmuir isotherm was used to compute the feed surfactant concentration required for the removal of PA up to an extraction efficiency of 90%. The effects of temperature and concentration of surfactant on various thermodynamic parameters were examined. It was found that the values of ΔG° increased with temperature and decreased with surfactant concentration. The values of ΔH° and ΔS° increased with surfactant concentration. The developed approach for DIL mediated CPE has proved to be an efficient and green route for extraction of PA from water sample. Copyright © 2015 Elsevier B.V. All rights reserved.

Characteristics of ionic polymer-metal composite with chemically doped TiO2 particles

NASA Astrophysics Data System (ADS)

Jung, Youngsoo; Kim, Seong Jun; Kim, Kwang J.; Lee, Deuk Yong

2011-12-01

Many studies have investigated techniques to improve the bending performance of ionic polymer-metal composite (IPMC) actuators, including 'doping' of metal particles in the polymer membrane usually by means of physical processes. This study is mainly focused on the characterization of the physical, electrochemical and electromechanical properties of TiO2-doped ionic polymer membranes and IPMCs prepared by the sol-gel method, which results in a uniform distribution of the particles inside the polymer membrane. X-ray and UV-visible spectra indicate the presence of anatase-TiO2 in the modified membranes. TiO2-doped membranes (0.16 wt%) exhibit the highest level of water uptake. The glass transition temperature of these membranes, measured using differential scanning calorimetry (DSC), increases with the increase of the amount of TiO2 in the membrane. Dynamic mechanical analysis (DMA) demonstrated that the storage modulus of dried TiO2-doped ionic polymer membranes increases as the amount of TiO2 in the membrane increases, whereas the storage modulus of hydrated samples is closely related to the level of water uptake. Electrochemical impedance spectroscopy (EIS) shows that the conductivity of TiO2-doped membranes decreases with increasing TiO2 content in spite of an internal resistance drop in the samples. Above all, bending deflection of TiO2-doped IPMC decreased with higher TiO2 content in the membrane while the blocking force of each sample increased with the higher TiO2 content. Additionally, it was determined that the lifetime of IPMC is strongly dependent on the level of water uptake.

Charge carrier dynamics and relaxation in (polyethylene oxide-lithium-salt)-based polymer electrolyte containing 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide as ionic liquid

NASA Astrophysics Data System (ADS)

Karmakar, A.; Ghosh, A.

2011-11-01

In this paper we report the dynamics of charge carriers and relaxation in polymer electrolytes based on polyethylene oxide (PEO), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMPTFSI) ionic liquid prepared by solution cast technique. It has been observed that the incorporation of BMPTFSI into PEO-LiTFSI electrolyte is an effective way for increasing the amorphous phase to a large extent. It has also been observed that both the glass transition and melting temperatures decrease with the increase of BMPTFSI concentration. The ionic conductivity of these polymer electrolytes increases with the increase of BMPTFSI concentration. The highest ionic conductivity obtained at 25 °C is ˜3×10-4 S cm-1 for the electrolyte containing 60 wt % BMPTFSI and ethylene oxide (EO)/Li ratio of 20. The temperature dependence of the dc conductivity and the hopping frequency show Vogel-Tamman-Fulcher type behavior indicating a strong coupling between the ionic and the polymer chain segmental motions. The frequency dependence of the ac conductivity exhibits a power law with an exponent n which decreases with the increase of temperature. The scaling of the ac conductivity indicates that relaxation dynamics of charge carriers follows a common mechanism for all temperatures and BMPTFSI concentrations. We have also presented the electric modulus data which have been analyzed in the framework of a Havriliak-Negami equation and the shape parameters obtained by the analysis show slight temperature dependence, but change sharply with BMPTFSI concentration. The stretched exponent β obtained from Kohlrausch-Williams-Watts fit to the modulus data is much lower than unity signifying that the relaxation is highly nonexponential. The decay function obtained from analysis of experimental modulus data is highly asymmetric with time.

Ionic liquid and deep eutectic solvent-activated CelA2 variants generated by directed evolution.

PubMed

Lehmann, Christian; Bocola, Marco; Streit, Wolfgang R; Martinez, Ronny; Schwaneberg, Ulrich

2014-06-01

Chemoenzymatic cellulose degradation is one of the key steps for the production of biomass-based fuels under mild conditions. An effective cellulose degradation process requires diverse physico-chemical dissolution of the biomass prior to enzymatic degradation. In recent years, "green" solvents, such as ionic liquids and, more recently, deep eutectic liquids, have been proposed as suitable alternatives for biomass dissolution by homogenous catalysis. In this manuscript, a directed evolution campaign of an ionic liquid tolerant β-1,4-endoglucanase (CelA2) was performed in order to increase its performance in the presence of choline chloride/glycerol (ChCl:Gly) or 1-butyl-3-methylimidazolium chloride ([BMIM]Cl), as a first step to identify residues which govern ionic strength resistance and obtaining insights for employing cellulases on the long run in homogenous catalysis of lignocellulose degradation. After mutant library screening, variant M4 (His288Phe, Ser300Arg) was identified, showing a dramatically reduced activity in potassium phosphate buffer and an increased activity in the presence of ChCl:Gly or [BMIM]Cl. Further characterization showed that the CelA2 variant M4 is activated in the presence of these solvents, representing a first report of an engineered enzyme with an ionic strength activity switch. Structural analysis revealed that Arg300 could be a key residue for the ionic strength activation through a salt bridge with the neighboring Asp287. Experimental and computational results suggest that the salt bridge Asp287-Arg300 generates a nearly inactive CelA2 variant and activity is regained when ChCl:Gly or [BMIM]Cl are supplemented (~5-fold increase from 0.64 to 3.37 μM 4-MU/h with the addition ChCl:Gly and ~23-fold increase from 3.84 to 89.21 μM 4-pNP/h with the addition of [BMIM]Cl). Molecular dynamic simulations further suggest that the salt bridge between Asp287 and Arg300 in variant M4 (His288Phe, Ser300Arg) modulates the observed salt activation.

Reinflating Giant Planets

NASA Astrophysics Data System (ADS)

Kohler, Susanna

2017-01-01

Two new, large gas-giant exoplanets have been discovered orbiting close to their host stars. A recent study examining these planets and others like them may help us to better understand what happens to close-in hot Jupiters as their host stars reach the end of their main-sequence lives.OversizedGiantsUnbinned transit light curves for HAT-P-65b. [Adapted from Hartman et al. 2016]The discovery of HAT-P-65b and HAT-P-66b, two new transiting hot Jupiters, is intriguing. These planets have periods of just under 3 days and masses of roughly 0.5 and 0.8 times that of Jupiter, but their sizes are whats really interesting: they have inflated radii of 1.89 and 1.59 times that of Jupiter.These two planets, discovered using the Hungarian-made Automated Telescope Network (HATNet) in Arizona and Hawaii, mark the latest in an ever-growing sample of gas-giant exoplanets with radii larger than expected based on theoretical planetary structure models.What causes this discrepancy? Did the planets just fail to contract to the expected size when they were initially formed, or were they reinflated later in their lifetimes? If the latter, how? These are questions that scientists are only now starting to be able to address using statistics of the sample of close-in, transiting planets.Unbinned transit light curves for HAT-P-66b. [Hartman et al. 2016]Exploring Other PlanetsLed by Joel Hartman (Princeton University), the team that discovered HAT-P-65b and HAT-P-66b has examined these planets observed parameters and those of dozens of other known close-in, transiting exoplanets discovered with a variety of transiting exoplanet missions: HAT, WASP, Kepler, TrES, and KELT. Hartman and collaborators used this sample to draw conclusions about what causes some of these planets to have such large radii.The team found that there is a statistically significant correlation between the radii of close-in giant planets and the fractional ages of their host stars (i.e., the stars age divided by its full expected lifetime). The two newly discovered hot Jupiters with inflated radii, for instance, are orbiting stars that are roughly 84% and 83% through their life spans and are approaching the main-sequence turnoff point.Late-Life ReinflationFractional age of the host stars of close-in transiting exoplanets vs. the planets radius. There is a statistically significant correlation between age and planet radius. [Adapted from Hartman et al. 2016]Hartman and collaborators propose that the data support the following scenario: as host stars evolve and become more luminous toward the ends of their main-sequence lifetimes, they deposit more energy deep into the interiors of the planets closely orbiting them. These close-in planets then increase their equilibrium temperatures and their radii reinflate as a result.Based on these results, we would expect to continue to find hot Jupiters with inflated radii primarily orbiting closely around older stars. Conversely, close-in giant planets around younger stars should primarily have non-inflated radii. As we continue to build our observational sample of transiting hot Jupiters in the future, we will be able to see how this model holds up.CitationJ. D. Hartman et al 2016 AJ 152 182. doi:10.3847/0004-6256/152/6/182

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.

Interaction of indole-papaverine with DNA in solutions of various ionic strength

NASA Astrophysics Data System (ADS)

Travkina, V. I.; Moroshkina, E. B.; Osinnikova, D. N.

2017-11-01

Interaction of synthetic alkaloid of isoquinoline series, which is an analogue of the biologically active compound papaverine, was studied by spectral, microcalorimetric, optical and hydrodynamic methods at different ionic strengths of medium. It was found that the investigated compound may interact with DNA in various ways depending on the ratio of ligand - DNA concentrations and ionic strength of solution (μ). When μ = 0.001, indole-papaverine intercalates into the double helix of DNA. The increase of μ resulted in a decrease of the affinity of the compound to DNA and a change its binding method.

Biodegradation of diesel fuel by a microbial consortium in the presence of 1-alkoxymethyl-2-methyl-5-hydroxypyridinium chloride homologues.

PubMed

Chrzanowski, Lukasz; Stasiewicz, Monika; Owsianiak, Mikołaj; Szulc, Alicja; Piotrowska-Cyplik, Agnieszka; Olejnik-Schmidt, Agnieszka K; Wyrwas, Bogdan

2009-09-01

Fast development of ionic liquids as gaining more and more attention valuable chemicals will undoubtedly lead to environmental pollution. New formulations and application of ionic liquids may result in contamination in the presence of hydrophobic compounds, such as petroleum mixtures. We hypothesize that in the presence of diesel fuel low-water-soluble ionic liquids may become more toxic to hydrocarbon-degrading microorganisms. In this study the influence of 1-alkoxymethyl-2-methyl-5-hydroxypyridinium chloride homologues (side-chain length from C(3) to C(18)) on biodegradation of diesel fuel by a bacterial consortium was investigated. Whereas test performed for the consortium cultivated on disodium succinate showed that toxicity of the investigated ionic liquids decreased with increase in side-chain length, only higher homologues (C(8)-C(18)) caused a decrease in diesel fuel biodegradation. As a result of exposure to toxic compounds also modification in cell surface hydrophobicity was observed (MATH). Disulphine blue active substances method was employed to determine partitioning index of ionic liquids between water and diesel fuel phase, which varied from 1.1 to 51% for C(3) and C(18) homologues, respectively. We conclude that in the presence of hydrocarbons acting as a solvent, the increased bioavailability of hydrophobic homologues is responsible for the decrease in biodegradation efficiency of diesel fuel.

Phase Transitions of Triflate-Based Ionic Liquids under High Pressure.

PubMed

Faria, Luiz F O; Ribeiro, Mauro C C

2015-11-05

Raman spectroscopy has been used to study phase transitions of ionic liquids based on the triflate anion, [TfO](-), as a function of pressure or temperature. Raman spectra of ionic liquids containing the cations 1-butyl-3-methylimidazolium, [C4C1Im](+), 1-octyl-3-methylimidazolium, [C8C1Im](+), 1-butyl-2,3-dimethylimidazolium, [C4C1C1Im](+), and 1-butyl-1-methylpyrrolidinium, [C4C1Pyr](+), were compared. Vibrational frequencies and binding energy of ionic pairs were calculated by quantum chemistry methods. The ionic liquids [C4C1Im][TfO] and [C4C1Pyr][TfO] crystallize at 1.0 GPa when the pressure is increased in steps of ∼ 0.2 GPa from the atmospheric pressure, whereas [C8C1Im][TfO] and [C4C1C1Im][TfO] do not crystallize up to 2.3 GPa of applied pressure. The low-frequency range of the Raman spectrum of [C4C1Im][TfO] indicates that the system undergoes glass transition, rather than crystallization, when the pressure applied on the liquid has been increased above 2.0 GPa in a single step. Strong hysteresis of spectral features (frequency shift and bandwidth) of the high-pressure crystalline phase when the pressure was released stepwise back to the atmospheric pressure has been found .

Structure and thermal properties of salicylate-based-protic ionic liquids as new heat storage media. COSMO-RS structure characterization and modeling of heat capacities.

PubMed

Jacquemin, Johan; Feder-Kubis, Joanna; Zorębski, Michał; Grzybowska, Katarzyna; Chorążewski, Mirosław; Hensel-Bielówka, Stella; Zorębski, Edward; Paluch, Marian; Dzida, Marzena

2014-02-28

During this research, we present a study on the thermal properties, such as the melting, cold crystallization, and glass transition temperatures as well as heat capacities from 293.15 K to 323.15 K of nine in-house synthesized protic ionic liquids based on the 3-(alkoxymethyl)-1H-imidazol-3-ium salicylate ([H-Im-C1OC(n)][Sal]) with n = 3-11. The 3D structures, surface charge distributions and COSMO volumes of all investigated ions are obtained by combining DFT calculations and the COSMO-RS methodology. The heat capacity data sets as a function of temperature of the 3-(alkoxymethyl)-1H-imidazol-3-ium salicylate are then predicted using the methodology originally proposed in the case of ionic liquids by Ge et al. 3-(Alkoxymethyl)-1H-imidazol-3-ium salicylate based ionic liquids present specific heat capacities higher in many cases than other ionic liquids that make them suitable as heat storage media and in heat transfer processes. It was found experimentally that the heat capacity increases linearly with increasing alkyl chain length of the alkoxymethyl group of 3-(alkoxymethyl)-1H-imidazol-3-ium salicylate as was expected and predicted using the Ge et al. method with an overall relative absolute deviation close to 3.2% for temperatures up to 323.15 K.

Structure of cyano-anion ionic liquids: X-ray scattering and simulations

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

Dhungana, Kamal B.; Faria, Luiz F. O.; Wu, Boning

2016-07-14

Ionic liquids with cyano anions have long been used because of their unique combination of low-melting temperatures, reduced viscosities, and increased conductivities. Recently we have shown that cyano anions in ionic liquids are particularly interesting for their potential use as electron donors to excited state photo-acceptors [B. Wu et al., J. Phys. Chem. B 119, 14790–14799 (2015)]. Here we report on bulk structural and quantum mechanical results for a series of ionic liquids based on the 1-ethyl-3-methylimidazolium cation, paired with the following five cyano anions: SeCN-, SCN-, N(CN)-2N(CN)2-, C(CN)-3C(CN)3-, and B(CN)-4B(CN)4-. By combining molecular dynamics simulations, high-energy X-ray scattering measurements,more » and periodic boundary condition DFT calculations, we are able to obtain a comprehensive description of the liquid landscape as well as the nature of the HOMO-LUMO states for these ionic liquids in the condensed phase. Features in the structure functions for these ionic liquids are somewhat different than the commonly observed adjacency, charge-charge, and polarity peaks, especially for the bulkiest B(CN)-4B(CN)4- anion. While the other four cyano-anion ionic liquids present an anionic HOMO, the one for Im+2,1Im2,1+/B(CN)-4B(CN)4- is cationic.« less

Architecture and migration of an epithelium on a cylindrical wire.

PubMed

Yevick, Hannah G; Duclos, Guillaume; Bonnet, Isabelle; Silberzan, Pascal

2015-05-12

In a wide range of epithelial tissues such as kidney tubules or breast acini, cells organize into bidimensional monolayers experiencing an out-of-plane curvature. Cancer cells can also migrate collectively from epithelial tumors by wrapping around vessels or muscle fibers. However, in vitro experiments dealing with epithelia are mostly performed on flat substrates, neglecting this out-of-plane component. In this paper, we study the development and migration of epithelial tissues on glass wires of well-defined radii varying from less than 1 µm up to 85 µm. To uncouple the effect of out-of-plane curvature from the lateral confinement experienced by the cells in these geometries, we compare our results to experiments performed on narrow adhesive tracks. Because of lateral confinement, the velocity of collective migration increases for radii smaller than typically 20 µm. The monolayer dynamics is then controlled by front-edge protrusions. Conversely, high curvature is identified as the inducer of frequent cell detachments at the front edge, a phenotype reminiscent of the Epithelial-Mesenchymal Transition. High curvature also induces a circumferential alignment of the actin cytoskeleton, stabilized by multiple focal adhesions. This organization of the cytoskeleton is reminiscent of in vivo situations such as the development of the trachea of the Drosophila embryo. Finally, submicron radii halt the monolayer, which then reconfigures into hollow cysts.

A white-light /Fe X/H-alpha coronal transient observation to 10 solar radii

NASA Technical Reports Server (NTRS)

Wagner, W. J.; Illing, R. M. E.; Sawyer, C. B.; House, L. L.; Sheeley, N. R., Jr.; Howard, R. A.; Koomen, M. J.; Michels, D. J.; Smartt, R. N.; Dryer, M.

1983-01-01

Multitelescope observations of the coronal transient of April 15-16, 1980 provide simultaneous data from the Solar Maximum Mission Coronagraph/Polarimeter, the Solwind Coronagraph, and the new Emission line Coronagraph of the Sacramento Peak Observatory. An eruptive prominence-associated white light transient is for the first time seen as an unusual wave or brightening in Fe X 6374 A (but not in Fe XIV 5303 A). Several interpretations of this fleeting enhancement are offered. The prominence shows a slowly increasing acceleration which peaks at the time of the Fe event. The white light loop transient surrounding the prominence expands at a well-documented constant speed to solar radii, with an extrapolated start time at zero height coincident with the surface activity. This loop transient exemplifies those seen above 1.7 solar radii, in that leading the disturbance is a bright N(e)-enhanced) loop rather than a dark one. This is consistent with a report of the behavior of another eruptive event observed by Fisher and Poland (1981) which began as a density depletion in the lower corona, with a bright loop forming at greater altitudes. The top of the bright loop ultimately fades in the outer corona while slow radial growth continues in the legs.

Theoretical assessment of the disparity in the electrostatic forces between two point charges and two conductive spheres of equal radii

NASA Astrophysics Data System (ADS)

Kolikov, Kiril

2016-11-01

The Coulomb's formula for the force FC of electrostatic interaction between two point charges is well known. In reality, however, interactions occur not between point charges, but between charged bodies of certain geometric form, size and physical structure. This leads to deviation of the estimated force FC from the real force F of electrostatic interaction, thus imposing the task to evaluate the disparity. In the present paper the problem is being solved theoretically for two charged conductive spheres of equal radii and arbitrary electric charges. Assessment of the deviation is given as a function of the ratio of the distance R between the spheres centers to the sum of their radii. For the purpose, relations between FC and F derived in a preceding work of ours, are employed to generalize the Coulomb's interactions. At relatively short distances between the spheres, the Coulomb force FC, as estimated to be induced by charges situated at the centers of the spheres, differ significantly from the real force F of interaction between the spheres. In the case of zero and non-zero charge we prove that with increasing the distance between the two spheres, the force F decrease rapidly, virtually to zero values, i.e. it appears to be short-acting force.

Effect of salts on the kinetic parameters and thermal stability of bovine brain acid phosphatase.

PubMed

Bittencourt, H M; Chaimovich, H

1976-08-01

Bovine brain acid phosphatase is inhibited, at any pH, by an increase in ionic strength. The rate decrease is associated at pH 5, with a marked decrease in Km and, at pH 8, with a noticeable decrease in Vm. The rate of thermal inactivation of the enzyme is unaffected by increasing ionic strength up to 300 mM. These results are discussed in terms of interactions at the active site of the enzyme.

Spectro-Timing Study of GX 339-4 in a Hard Intermediate State

NASA Technical Reports Server (NTRS)

Furst, F.; Grinberg, V.; Tomsick, J. A.; Bachetti, M.; Boggs, S. E.; Brightman, M.; Christensen, F. E.; Craig, W. W.; Ghandi, P.; Zhang, William W.

2016-01-01

We present an analysis of Nuclear Spectroscopic Telescope Array observations of a hard intermediate state of the transient black hole GX 339-4 taken in 2015 January. With the source softening significantly over the course of the 1.3 day long observation we split the data into 21 sub-sets and find that the spectrum of all of them can be well described by a power-law continuum with an additional relativistically blurred reflection component. The photon index increases from approx. 1.69 to approx. 1.77 over the course of the observation. The accretion disk is truncated at around nine gravitational radii in all spectra. We also perform timing analysis on the same 21 individual data sets, and find a strong type-C quasi-periodic oscillation (QPO), which increases in frequency from approx. 0.68 to approx. 1.05 Hz with time. The frequency change is well correlated with the softening of the spectrum. We discuss possible scenarios for the production of the QPO and calculate predicted inner radii in the relativistic precession model as well as the global disk mode oscillations model. We find discrepancies with respect to the observed values in both models unless we allow for a black hole mass of approx. 100 Mass compared to the Sun, which is highly unlikely. We discuss possible systematic uncertainties, in particular with the measurement of the inner accretion disk radius in the relativistic reflection model. We conclude that the combination of observed QPO frequencies and inner accretion disk radii, as obtained from spectral fitting, is difficult to reconcile with current models.

Parameterization of aerosol scavenging due to atmospheric ionization under varying relative humidity

NASA Astrophysics Data System (ADS)

Zhang, Liang; Tinsley, Brian A.

2017-05-01

Simulations and parameterizations of the modulation of aerosol scavenging by electric charges on particles and droplets for different relative humidities have been made for 3 μm radii droplets and a wide range of particle radii. For droplets and particles with opposite-sign charges, the attractive Coulomb force increases the collision rate coefficients above values due to other forces. With same-sign charges, the repulsive Coulomb force decreases the rate coefficients, and the short-range attractive image forces become important. The phoretic forces are attractive for relative humidity less than 100% and repulsive for relative humidity greater than 100% and have increasing overall effect for particle radii up to about 1 μm. There is an analytic solution for rate coefficients if only inverse square forces are present, but due to the presence of image forces, and for larger particles the intercept, weight, and the flow around the particle affecting the droplet trajectory, the simulated results usually depart far from the analytic solution. We give simple empirical parameterization formulas for some cases and more complex parameterizations for more exact fits to the simulated results. The results can be used in cloud models with growing droplets, as in updrafts, as well as with evaporating droplets in downdrafts. There is considered to be little scavenging of uncharged ice-forming nuclei in updrafts, but with charged ice-forming nuclei it is possible for scavenging in updrafts in cold clouds to produce contact ice nucleation. Scavenging in updrafts below the freezing level produces immersion nuclei that promote enhanced freezing as droplets rise above it.

Precise Masses & Radii of the Planets Orbiting K2-3 and GJ3470

NASA Astrophysics Data System (ADS)

Kosiarek, Molly; Crossfield, Ian; Hardegree-Ullman, Kevin; Livingston, John; Howard, Andrew; Fulton, Benjamin; Hirsch, Lea; Isaacson, Howard; Petigura, Erik; Sinukoff, Evan; Weiss, Lauren; Knutson, Heather; Bonfils, Xavier; Benneke, Björn; Beichman, Charles; Dressing, Courtney

2018-01-01

We report improved masses, radii, and densities for two planetary systems, K2-3 and GJ3470, derived from a combination of new radial velocity and transit observations. Both stars are nearby, early M dwarfs. K2-3 hosts three super-Earth planets between 1.5 and 2 Earth-radii at orbital periods between 10 and 45 days, while GJ 3470 hosts one 4 Earth-radii planet with a period of 3.3 days. Furthermore, we confirmed GJ3470's rotation period through multi-year ground-based photometry; RV analysis must account for this rotation signature. Due to the planets' low densities (all < 4.2 g/cm3) and bright host stars, they are among the best candidates for transmission spectroscopy with JWST and HST in order to characterize their atmospheric compositions.

Evaluation of ionic liquids supported on silica as a sorbent for fully automated online solid-phase extraction with LC-MS determination of sulfonamides in bovine milk samples.

PubMed

da Silva, Meire Ribeiro; Mauro Lanças, Fernando

2018-03-10

Sulfonamides are antibiotics widely used in the treatment of diseases in dairy cattle. However, their indiscriminate use for disease control may lead to their presence in tissues and milk and their determination requires a sample preparation step as part of an analytical approach. Among the several sample preparation techniques available, those based upon the use of sorptive materials have been widely employed. Recently, the application of ionic liquids immobilized on silica surfaces or polymeric materials has been evaluated for such an application. This manuscript addresses the evaluation of silica-based ionic liquid obtained by a sol-gel synthesis process by basic catalysis as sorbent for online solid-phase extraction with liquid chromatography and electrospray ionization time-of-flight mass spectrometry for sulfonamides determination. Infrared vibrational spectroscopy confirmed the presence of the ionic liquid on the silica surface, suggesting that the ionic liquid was anchored on to the silica surface. Other sorbents varying the ionic liquid alkyl chain were also synthesized and evaluated by off-line solid-phase extraction in the sulfonamide extraction. As the length of the alkyl chain increased, the amount of extracted sulfonamides decreased, possibly due to a decrease in the electrostatic interaction caused by the reduction in the polarity, as well as the presence of a hexafluorophosphate anion that increases the hydrophobic character of the material. The use of 1-butyl-3-methylimidazolium hexafluorophosphate as a selective ionic liquid sorbent enabled the isolation and sulfonamide preconcentration in bovine milk by online solid-phase extraction with liquid chromatography and electrospray ionization time-of-flight mass spectrometry. The limit of quantification for the method developed was 5-7, 5 μg/mL, with extraction recoveries ranging between 74 and 93% and intra- and interassay between 1.5-12.5 and 2.3-13.1, respectively. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Time-dependent density functional theory for the charging kinetics of electric double layer containing room-temperature ionic liquids

DOE PAGES

Lian, Cheng; Univ. of California, Riverside, CA; Zhao, Shuangliang; ...

2016-11-29

Understanding the charging kinetics of electric double layers is of fundamental importance for the design and development of novel electrochemical devices such as supercapacitors and field-effect transistors. In this paper, we study the dynamic behavior of room-temperature ionic liquids using a classical time-dependent density functional theory that accounts for the molecular excluded volume effects, the electrostatic correlations, and the dispersion forces. While the conventional models predict a monotonic increase of the surface charge with time upon application of an electrode voltage, our results show that dispersion between ions results in a non-monotonic increase of the surface charge with the durationmore » of charging. Finally and furthermore, we investigate the effects of van der Waals attraction between electrode/ionic-liquid interactions on the charging processes.« less

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.

Ionic liquids behave as dilute electrolyte solutions

PubMed Central

Gebbie, Matthew A.; Valtiner, Markus; Banquy, Xavier; Fox, Eric T.; Henderson, Wesley A.; Israelachvili, Jacob N.

2013-01-01

We combine direct surface force measurements with thermodynamic arguments to demonstrate that pure ionic liquids are expected to behave as dilute weak electrolyte solutions, with typical effective dissociated ion concentrations of less than 0.1% at room temperature. We performed equilibrium force–distance measurements across the common ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][NTf2]) using a surface forces apparatus with in situ electrochemical control and quantitatively modeled these measurements using the van der Waals and electrostatic double-layer forces of the Derjaguin–Landau–Verwey–Overbeek theory with an additive repulsive steric (entropic) ion–surface binding force. Our results indicate that ionic liquids screen charged surfaces through the formation of both bound (Stern) and diffuse electric double layers, where the diffuse double layer is comprised of effectively dissociated ionic liquid ions. Additionally, we used the energetics of thermally dissociating ions in a dielectric medium to quantitatively predict the equilibrium for the effective dissociation reaction of [C4mim][NTf2] ions, in excellent agreement with the measured Debye length. Our results clearly demonstrate that, outside of the bound double layer, most of the ions in [C4mim][NTf2] are not effectively dissociated and thus do not contribute to electrostatic screening. We also provide a general, molecular-scale framework for designing ionic liquids with significantly increased dissociated charge densities via judiciously balancing ion pair interactions with bulk dielectric properties. Our results clear up several inconsistencies that have hampered scientific progress in this important area and guide the rational design of unique, high–free-ion density ionic liquids and ionic liquid blends. PMID:23716690

Challenges in Determining Intrinsic Viscosity Under Low Ionic Strength Solution Conditions.

PubMed

Pindrus, Mariya A; Shire, Steven J; Yadav, Sandeep; Kalonia, Devendra S

2017-04-01

To determine the intrinsic viscosity of several monoclonal antibodies (mAbs) under varying pH and ionic strength solution conditions. An online viscosity detector attached to HPLC (Viscotek®) was used to determine the intrinsic viscosity of mAbs. The Ross and Minton equation was used for viscosity prediction at high protein concentrations. Bulk viscosity was determined by a Cambridge viscometer. At 15 mM ionic strength, intrinsic viscosity of the mAbs determined by the single-point approach varied from 5.6 to 6.4 mL/g with changes in pH. High ionic strength did not significantly alter intrinsic viscosity, while a significant increase (up to 24.0 mL/g) was observed near zero mM. No difference in bulk viscosity of mAb3 was observed around pH 6 as a function of ionic strength. Data analysis revealed that near zero mM ionic strength limitations of the single-point technique result in erroneously high intrinsic viscosity. Intrinsic viscosity is a valuable tool that can be used to model baseline viscosity at higher protein concentrations. However, it is not predictive of solution non-ideality at higher protein concentrations. Furthermore, breakdown of numerous assumptions limits the applicability of experimental techniques near zero mM ionic strength conditions. For molecules and conditions studied, the single-point approach produced reliable intrinsic viscosity results at 15 mM. However, this approach must be used with caution near zero mM ionic strength. Data analysis can be used to reveal whether determined intrinsic viscosity is reliable or erroneously high.

Study the effect of Gd3+ incorporation into nanocrystalline (Ni-Ti) substituted Mn-Zn ferrites on its structure and functional properties

NASA Astrophysics Data System (ADS)

Rady, K. E.; Shams, M. S.

2017-03-01

Ferrite samples with general chemical formula Mn0.9Zn0.1Ni0.05Ti0.05GdtFe1.9-tO4; (0.0≤ t≤0.05; step 0.01) were prepared using solid state reaction technique and the effect of Gd3+ ions incorporation on its physical properties has been studied. From the obtained results, XRD analysis reveals that the samples have a cubic spinel single phase structure for 0.0≤ t≤0.02; while for t≥0.03 a small peak of secondary phase (Gd3Fe5O12) appears and becomes more noticeable with increasing Gd content. The lattice parameter (a) of the prepared samples was found to be initially increases and then decreases with increasing Gd content which may be attributed to the difference in the ionic radii of the cations involved and the solubility limit of Gd3+ ions. The crystallite size of the samples was estimated using Scherrer's equation and ranged from 96 nm to 107 nm. A vibrating sample magnetometer (VSM) was used at room temperature in order to study the effect of Gd content on the magnetic hysteresis parameters of the prepared ferrites such as saturation magnetization and coercivity. DC molar magnetic susceptibility (χM) for the prepared samples was measured using Faraday's method as a function of temperature and the Curie temperature was calculated from the magnetic susceptibility measurements. Also the DC resistivity of the samples was measured at room temperature. The obtained results show that, the substitution by Gd3+ ions improves the electrical properties of the samples by increasing it DC electrical resistivity by 118% and consequently decreases it eddy current loss while the saturation magnetization slightly decreased by 14% only. The sample of t=0.01 shows a high dc magnetic susceptibility, high saturation magnetization (43.1 emu/g), high electric resistivity 12×103 Ω.m and high Curie temperature (496 K), which is useful in some technological applications such as transformer and inductor cores.

Thermoelectricity in Heterogeneous Nanofluidic Channels.

PubMed

Li, Long; Wang, Qinggong

2018-05-01

Ionic fluids are essential to energy conversion, water desalination, drug delivery, and lab-on-a-chip devices. Ionic transport in nanoscale confinements and complex physical fields still remain elusive. Here, a nanofluidic system is developed using nanochannels of heterogeneous surface properties to investigate transport properties of ions under different temperatures. Steady ionic currents are observed under symmetric temperature gradients, which is equivalent to generating electricity using waste heat (e.g., electronic chips and solar panels). The currents increase linearly with temperature gradient and nonlinearly with channel size. Contributions to ion motion from temperatures and channel properties are evaluated for this phenomenon. The findings provide insights into the study of confined ionic fluids in multiphysical fields, and suggest applications in thermal energy conversion, temperature sensors, and chip-level thermal management. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Carbon nanotube-graphene composite for ionic polymer actuators

NASA Astrophysics Data System (ADS)

Yang, Woosung; Choi, Hyonkwang; Choi, Suho; Jeon, Minhyon; Lee, Seung-Yop

2012-05-01

In this paper, we develop a new ionic polymer-metal composite (IPMC) by replacing a typical platinum or gold electrode with a multi-walled carbon nanotube (MWNT)-graphene based electrode. A solvent of MWNT and graphene is formed on both sides of the ionic polymer membranes as electrodes by means of spray coating and baking. Then, the ionic liquid process is performed for actuating in air. The four kinds of IPMC samples with different MWNT-graphene ratios are fabricated with the same solid Nafion film. Experimental results show that the IPMC with a pure MWNT based electrode exhibits higher displacement compared to the conventional IPMC with a platinum electrode. Also, the increment of the ratio of graphene to the MWNT-graphene electrode decreases the resultant displacement but increases the fundamental natural frequency of the polymer actuator.

Hall Determination of Atomic Radii of Alkali Metals

ERIC Educational Resources Information Center

Houari, Ahmed

2008-01-01

I will propose here an alternative method for determining atomic radii of alkali metals based on the Hall measurements of their free electron densities and the knowledge of their crystal structure. (Contains 2 figures.)

Toward ambient temperature operation with all-solid-state lithium metal batteries with a sp3 boron-based solid single ion conducting polymer electrolyte

NASA Astrophysics Data System (ADS)

Zhang, Yunfeng; Cai, Weiwei; Rohan, Rupesh; Pan, Meize; Liu, Yuan; Liu, Xupo; Li, Cuicui; Sun, Yubao; Cheng, Hansong

2016-02-01

The ionic conductivity decay problem of poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) when increase the lithium salt of the SPEs up to high concentration is here functionally overcome by the incorporation of a charge delocalized sp3 boron based single ion conducting polymer electrolyte (SIPE) with poly(ethylene oxide) to fabricate solid-state sp3 boron based SIPE membranes (S-BSMs). By characterizations, particularly differential scanning calorimeter (DSC) and ionic conductivity studies, the fabricated S-BSMs showed decreased melting points and increased ionic conductivity as steadily increase the content of sp3 boron based SIPE, which significantly improved the low temperature performance of the all-solid-state lithium batteries. The fabricated Li | S-BSMs | LiFePO4 cells exhibit highly electrochemical stability and excellent cycling at temperature below melting point of PEO, which has never been reported so far for SIPEs based all-solid-state lithium batteries.

Immobilization of yeast cells with ionic hydrogel carriers by adhesion-multiplication.

PubMed

Zhaoxin, L; Fujimura, T

2000-12-01

The mixture of an ionic monomer, 2-acrylamido 2-methylpropanesulfonic acid (TBAS), and a series of poly(ethylene glycol) dimethacrylate (nG) monomers were copolymerized with 60Co gamma-rays, and the produced ionic hydrogel polymers were used for immobilization of yeast cells. The cells were adhered onto the surface of the hydrogel polymers and intruded into the interior of the polymers with growing. The immobilized yeast cells with these hydrogel polymers had higher ethanol productivity than that of free cells. The yield of ethanol with poly(TBAS-14G) carrier was the highest and increased by 3.5 times compared to the free cells. It was found that the ethanol yield increased with the increase of glycol number in poly(ethylene glycol) dimethacrylate. The state of the immobilized cells was observed with microscope, and it was also found that the difference in the ethanol productivity is mainly due to the difference in the internal structure and properties of polymer carrier, such as surface charge, hydrophilicity, and swelling ability of polymer carrier.

Glued Langmuir-Blodgett bilayers from calix[ n]arenes: Influence of calix[ n]arene size on ionic cross-linking, film thickness, and permeation selectivity

DOE PAGES

Wang, Minghui; Janout, Vaclav; Regen, Steven L.

2010-07-12

A homologous series of calix[4]arene-, calix[5]arene- and calix[6]arene-based surfactants, containing pendant trimethylammonium and n-hexadecyl groups, have been compared with respect to their ability (i) to undergo ionic crosslinking at the air/water interface, (ii) to incorporate poly(4-styrenesulfonate) (PSS) in Langmuir-Blodgett (LB) bilayers, and (iii) to act as barriers towards He, N 2 and CO 2 when assembled into crosslinked LB bilayers. As these calix[n]arenes increase in size, their ability to undergo ionic crosslinking has been found to increase, the thickness of corresponding glued LB bilayers has been found to decrease, and their barrier properties and permeation selectivities have been found tomore » increase. In conclusion, the likely origin for these effects and the probable mechanism by which He, N 2 and CO 2 cross these ultrathin films are discussed.« less

Effect of rare-earth ion size on local electron structure in RBa 2Cu 3O 7- δ (R = Tm, Dy, Gd, Eu, Nd and Y) superconductors: A positron study

NASA Astrophysics Data System (ADS)

Chen, Zhenping; Zhang, Jincang; Su, Yuling; Xue, Yuncai; Cao, Shixun

2006-02-01

The effects of rare-earth ionic size on the local electron structure, lattice parameters and superconductivity have been investigated by positron annihilation technique (PAT) and related experiments for RBa 2Cu 3O 7- δ (R = Tm, Dy, Gd, Eu, Nd and Y) superconductors. The local electron density ne is evaluated as a function of the rare-earth radius. The results show that both the bulk-lifetime τB and the defect lifetime τ2 increase with increasing rare-earth ionic radius, while the local electron density ne decrease with increasing rare-earth ionic radius. These results prove that the changes of ne, the degree of orthorhombic distortion and the coupling between the Cu-O chains and the CuO 2 planes all have an effect on the superconductivity of RBa 2Cu 3O 7- δ systems.

Influence of ionic strength and OH(-) ion concentration on the Cu(II) complex formation with EDTA in alkaline solutions.

PubMed

Norkus, E; Vaskelis, A; Zakaite, I

1996-03-01

D.c. polarographic data show that the complex formation of copper ions with EDTA depends markedly on the ionic strength of the solution at pH 8-10. This is primarily associated with the dependence of the fourth deprotonization constant of EDTA on the solution ionic strength: when it increases from 0.4 to 3.4, the pK(a4) value decreases from 9.5 to 8.2. According to polarographic and spectrophotometric data the degree of Cu(II) complexation increases at pH>10 due to transformation of the complex CuY(2-) to the more stable CuY(OH)(3-) (Y(4-), a fully deprotonized anion of EDTA), but it decreases with increase in alkalinity in a highly alkaline solution (pH>13.5). The latter result could be explained by the decrease in the EDTA anion activity. The calculated values of the activity coefficient are lower than 0.05 at pH>14.

Amino acid ionic liquids.

PubMed

Ohno, Hiroyuki; Fukumoto, Kenta

2007-11-01

The preparation of ionic liquids derived from amino acids, and their properties, are outlined. Since amino acids have both a carboxylic acid residue and an amino group in a single molecule, they can be used as either anions or cations. These groups are also useful in their ability to introduce functional group(s). Twenty different natural amino acids were used as anions, to couple with the 1-ethyl-3-methylimidazolium cation. The salts obtained were all liquid at room temperature. The properties of the resulting ionic liquids (AAILs) depend on the side groups of the amino acids involved. These AAILs, composed of an amino acid with some functional groups such as a hydrogen bonding group, a charged group, or an aromatic ring, had an increased glass transition (or melting) temperature and/or higher viscosity as a result of additional interactions among the ions. Viscosity is reduced and the decomposition temperature of imidazolium-type salts is improved by using the tetrabutylphosphonium cation. The chirality of AAILs was maintained even upon heating to 150 degrees C after acetylation of the free amino group. The amino group was also modified to introduce a strong acid group so as to form hydrophobic and chiral ionic liquids. Unique phase behavior of the resulting hydrophobic ionic liquids and water mixture is found; the mixture is clearly phase separated at room temperature, but the solubility of water in this IL increases upon cooling, to give a homogeneous solution. This phase change is reversible, and separation occurs again by raising the temperature a few degrees. It is extraordinary for an IL/water mixture to display such behavior with a lower critical solution temperature. Some likely applications are proposed for these amino acid derived ionic liquids.

Diffusion of ionic and non-ionic contrast agents in articular cartilage with increased cross-linking--contribution of steric and electrostatic effects.

PubMed

Kulmala, K A M; Karjalainen, H M; Kokkonen, H T; Tiitu, V; Kovanen, V; Lammi, M J; Jurvelin, J S; Korhonen, R K; Töyräs, J

2013-10-01

To investigate the effect of threose-induced collagen cross-linking on diffusion of ionic and non-ionic contrast agents in articular cartilage. Osteochondral plugs (Ø=6mm) were prepared from bovine patellae and divided into two groups according to the contrast agent to be used in contrast enhanced computed tomography (CECT) imaging: (I) anionic ioxaglate and (II) non-ionic iodixanol. The groups I and II contained 7 and 6 sample pairs, respectively. One of the paired samples served as a reference while the other was treated with threose to induce collagen cross-linking. The equilibrium partitioning of the contrast agents was imaged after 24h of immersion. Fixed charge density (FCD), water content, contents of proteoglycans, total collagen, hydroxylysyl pyridinoline (HP), lysyl pyridinoline (LP) and pentosidine (Pent) cross-links were determined as a reference. The equilibrium partitioning of ioxaglate (group I) was significantly (p=0.018) lower (-23.4%) in threose-treated than control samples while the equilibrium partitioning of iodixanol (group II) was unaffected by the threose-treatment. FCD in the middle and deep zones of the cartilage (p<0.05) and contents of Pent and LP (p=0.001) increased significantly due to the treatment. However, the proteoglycan concentration was not systematically altered after the treatment. Water content was significantly (-3.5%, p=0.007) lower after the treatment. Since non-ionic iodixanol showed no changes in partition after cross-linking, in contrast to anionic ioxaglate, we conclude that the cross-linking induced changes in charge distribution have greater effect on diffusion compared to the cross-linking induced changes in steric hindrance. Copyright © 2013 IPEM. Published by Elsevier Ltd. All rights reserved.

Evaluation of ionic air purifiers for reducing aerosol exposure in confined indoor spaces.

PubMed

Grinshpun, S A; Mainelis, G; Trunov, M; Adhikari, A; Reponen, T; Willeke, K

2005-08-01

Numerous techniques have been developed over the years for reducing aerosol exposure in indoor air environments. Among indoor air purifiers of different types, ionic emitters have gained increasing attention and are presently used for removing dust particles, aeroallergens and airborne microorganisms from indoor air. In this study, five ionic air purifiers (two wearable and three stationary) that produce unipolar air ions were evaluated with respect to their ability to reduce aerosol exposure in confined indoor spaces. The concentration decay of respirable particles of different properties was monitored in real time inside the breathing zone of a human manikin, which was placed in a relatively small (2.6 m3) walk-in chamber during the operation of an ionic air purifier in calm air and under mixing air condition. The particle removal efficiency as a function of particle size was determined using the data collected with a size-selective optical particle counter. The removal efficiency of the more powerful of the two wearable ionic purifiers reached about 50% after 15 min and almost 100% after 1.5 h of continuous operation in the chamber under calm air conditions. In the absence of external ventilation, air mixing, especially vigorous one (900 CFM), enhanced the air cleaning effect. Similar results were obtained when the manikin was placed inside a partial enclosure that simulated an aircraft seating configuration. All three stationary ionic air purifiers tested in this study were found capable of reducing the aerosol concentration in a confined indoor space. The most powerful stationary unit demonstrated an extremely high particle removal efficiency that increased sharply to almost 90% within 5-6 min, reaching about 100% within 10-12 min for all particle sizes (0.3-3 microm) tested in the chamber. For the units of the same emission rate, the data suggest that the ion polarity per se (negative vs. positive) does not affect the performance but the ion emission rate does. The effects of particle size (within the tested range) and properties (NaCl, PSL, Pseudomonas fluorescens bacteria) as well as the effects of the manikin's body temperature and its breathing on the ionic purifier performance were either small or insignificant. The data suggest that the unipolar ionic air purifiers are particularly efficient in reducing aerosol exposure in the breathing zone when used inside confined spaces with a relatively high surface-to-volume ratio. Ionic air purifiers have become increasingly popular for removing dust particles, aeroallergens and airborne microorganisms from indoor air in various settings. While the indoor air cleaning effect, resulting from unipolar and bipolar ion emission, has been tested by several investigators, there are still controversial claims (favorable and unfavorable) about the performance of commercially available ionic air purifiers. Among the five tested ionic air purifiers (two wearable and three stationary) producing unipolar air ions, the units with a higher ion emission rate provided higher particle removal efficiency. The ion polarity (negative vs. positive), the particle size (0.3-3 microm) and properties (NaCl, PSL, Pseudomonas fluorescens bacteria), as well as the body temperature and breathing did not considerable affected the ionization-driven particle removal. The data suggest that the unipolar ionic air purifiers are particularly efficient in reducing aerosol exposure in the breathing zone when they are used inside confined spaces with a relatively high surface-to-volume ratio (such as automobile cabins, aircraft seating areas, bathrooms, cellular offices, small residential rooms, and animal confinements). Based on our experiments, we proposed that purifiers with a very high ion emission rate be operated in an intermittent mode if used indoors for extended time periods. As the particles migrate to and deposit on indoor surfaces during the operation of ionic air purifiers, some excessive surface contamination may occur, which introduces the need of periodic cleaning these surfaces.

Solubility and dissolution improvement of ketoprofen by emulsification ionic gelation

NASA Astrophysics Data System (ADS)

Rachmaniar, Revika; Tristiyanti, Deby; Hamdani, Syarif; Afifah

2018-02-01

Ketoprofen or [2-(3-benzoylphenyl) propionic acid] is non-steroidal anti-inflammatory (NSAID) and an analgesic which has high permeability and low solubility. The purpose of this work was to improve the solubility and dissolution of poorly water-soluble ketoprofen prepared by emulsification ionic gelation method and utilizing polymer (chitosan) and cross linker (tripolyphosphate, TPP) for particles formulation. The results show that increasing pH value of TPP, higher solubility and dissolution of as-prepared ketoprofen-chitosan was obtained. The solubility in water of ketoprofen-chitosan with pH 6 for TPP increased 2.71-fold compared to untreated ketoprofen. While the dissolution of ketoprofen-chitosan with pH 6 of TPP in simulated gastric fluid without enzyme (0.1 N HCl), pH 4.5 buffer and simulated intestinal fluid without enzyme (phosphate buffer pH 6.8) was increased 1.9-fold, 1.6-fold and 1.2-fold compared to untreated ketoprofen for dissolution time of 30 minutes, respectively. It could be concluded that chitosan and TPP in the emulsification ionic gelation method for ketoprofen preparation effectively increases solubility and dissolution of poorly water-soluble ketoprofen.

Monoclinic to cubic phase transformation and photoluminescence properties in Hf1-xSmxO2 (x = 0-0.12) nanoparticles

NASA Astrophysics Data System (ADS)

Kumar, Sandeep; Rai, S. B.; Rath, Chandana

2018-02-01

Bulk hafnium oxide (HfO2) exhibits the monoclinic phase at room temperature which transforms to tetragonal and cubic phases at 1700 and 2600 °C, respectively, under ambient conditions. For the first time, we observe a monoclinic to stable cubic phase transformation at room temperature in nanoparticles of HfO2 by incorporating Sm3+ ions up to 12 at. %. Although the monoclinic structure is retained at 1 at. % of Sm, a mixed phase of monoclinic and cubic is observed at intermediate Sm concentration (5-11 at. %). Le-Bail profile refinement of X-ray diffraction patterns confirms the monoclinic to cubic phase transformation with increasing Sm3+ ion concentration. While the significant difference in ionic radii of Sm3+ and Hf4+ ion induces strain in the lattice above 9 at. %, a lower valency of Sm produces oxygen vacancy leading to 8-fold coordination with Sm3+ ion and stabilizes the cubic phase at room temperature. Not only the particle size obtained from transmission electron micrograph (TEM) matches well with the size calculated from the Williamson-Hall plot, the lattice spacing estimated from high resolution TEM also confirms the monoclinic and cubic phases in HfO2 and Hf0.88Sm0.12O2, respectively. Apart from phase transformation induced by Sm3+ ions, photoluminescence studies demonstrate an excellent emission in near green and red regions in Hf1-xSmxO2 nanoparticles. A schematic energy band diagram has been proposed based on the excitation and emission processes involved in HfO2 and Hf0.99Sm0.01O2 nanoparticles.

Anisotropic magnetic field observed at 300 K in citrate-coated iron oxide nanoparticles: effect of counterions

NASA Astrophysics Data System (ADS)

Misra, Sushil K.; Li, Lin; Mukherjee, Sudip; Ghosh, Goutam

2015-12-01

Iron oxide nanoparticles (IONPs) have been synthesized by chemical co-precipitation method and coated with three citrates, namely, tri-lithium citrate (TLC), tri-sodium citrate (TSC), or tri-potassium citrate (TKC). In these `core-shell' structures, the `core' is a cluster of average 3 IONPs which is enveloped by a `shell' of citrate molecules and counterions, and thus called `core-shell' nano-clusters (CS-NCs), of average size 20 to 22 nm. The counterions in the three CS-NCs differ in ionic radii (r_{{ion}}), in the order of Li+ < Na+ < K+. Our aim was to investigate the effect of counterions on magnetic interactions between CS-NCs in different powder samples at 300 K, using vibrating sample magnetometer and electron magnetic resonance (EMR) techniques. The hysteresis loops showed negligible coercivity field ( H c) in all samples. The saturation magnetization ( M S) was the highest for TLC-coated CS-NCs. The blocking temperature ( T B), obtained from zero-field-cooled measurements, was >300 K for TLC-coated CS-NCs and <300 K for TSC- and TKC-coated CS-NCs. The EMR linewidth (∆ B PP), measured at 300 K, was also the broadest for TLC-coated CS-NCs. At low temperatures, Δ B PP was found to increase more significantly for TSC- and TKC-coated CS-NCs than for TLC-coated CS-NCs. These results indicate a significant anisotropic field effect; arising due to thermal motion of counterions at 300 K, on the magnetic interactions in TLC-coated CS-NCs. To our knowledge, this is the first report on the effect of counterions on magnetic interactions between CS-NCs.

Isomorphous Substitution of Rare-Earth Elements in Lacunary Apatite Pb8Na2(PO4)6.

PubMed

Get'man, Evgeni I; Loboda, Stanislav N; Ignatov, Alexey V; Prisedsky, Vadim V; Abdul Jabar, Mohammed A B; Ardanova, Lyudmyla I

2016-03-07

The substitution of rare-earth elements (REEs) for Pb in the lacunary apatite Pb8Na2(PO4)6 with void structural channels was studied by means of powder X-ray diffraction (including the Rietveld refinement), scanning electron microscopy, energy-dispersive X-ray microanalysis, and IR spectroscopy and also measurements of the electrical conductivity. The substitution limits (xmax in Pb8-xLnxNa2(PO4)6Ox/2) at 800 °C were found to decrease with the atomic number of the REE from 1.40 for La to 0.12 for Yb with a rapid drop from light to heavy lanthanides (between Gd and Tb). The REE atoms substitute for Pb predominantly at Pb2 sites of the apatite structure according to the scheme 2Pb(2+) + □ → 2Ln(3+) + O(2-), where □ is a vacancy in the structural channel. The substitution in lacunary apatite produces quite different changes in the structural parameters compared with broadly studied alkaline-earth hydroxyapatites. In spite of the much lower ionic radii of REE than that of Pb(2+), the mean distances ⟨Pb1-O⟩ somewhat increase, whereas the distances ⟨Pb2-Pb2⟩ and ⟨Pb2-O4⟩ do not change considerably with the degree of substitution. This implies control of the substitution by not only spatial and charge accommodation of REE ions but also the availability of a stereochemically active 6s(2) electron pair on Pb(2+). The high-temperature electrical conductivity shows dependence on the degree of substitution with a minimum at x = 0.2 indicative of a possible change of the type of conductivity.

Spectral studies, thermal investigation and biological activity of some metal complexes derived from (E)-N‧-(1-(4-aminophenyl)ethylidene)morpholine-4-carbothiohydrazide

NASA Astrophysics Data System (ADS)

El-Samanody, El-Sayed A.; Polis, Magdy W.; Emara, Esam M.

2017-09-01

A new series of biologically active Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes derived from the novel thiosemicarbazone ligand; (E)-N‧-(1-(4-aminophenyl)ethylidene)morpholine-4-carbothiohydrazide (HL) were synthesized. The mode of bonding of the ligand and the geometrical structures of its metal complexes were achieved by different analytical and spectral methods. The ligand coordinated with metal ions in a neutral bidentate fashion through the thione sulfur and azomethine nitrogen atoms. All metal complexes adopted octahedral geometry, except Cu(II) complexes (3, 6, 7) which have a square planar structure. The general thermal decomposition pathways of the ligand along with its metal complexes were explained. The thermal stability of the complexes is controlled by the number of outer and inner sphere water molecules, ionic radii and the steric hindrance. The activation thermodynamic parameters; (activation energy (E*), enthalpy of activation (ΔH*), entropy of activation (ΔS*) and Gibbs free energy (ΔG*)) along with order of reaction (n) were estimated from DTG curves. The ESR spectra of Cu(II) complexes indicated that (dx2-y2)1 is the ground state with covalence character of metal-ligand bonds. The molluscicidal and biochemical effects of the ligand and its Ni(II); Cu(II) complexes (2; 3, 5, 7) along with their combinations with metaldehyde were screened in vitro on the mucous gland of Eobania vermiculata. The tested compounds exhibited a significant toxicity against the tested animals and have almost the same toxic effect of metaldehyde which increases the mucous secretion of the snails and leads to death.

Enhanced room temperature ferromagnetism in Ni doped SnO2 nanoparticles: A comprehensive study

NASA Astrophysics Data System (ADS)

Ahmed, Ateeq; Ali, T.; Naseem Siddique, M.; Ahmad, Abid; Tripathi, P.

2017-08-01

We emphasized on a detailed investigation of the structural, optical, and magnetic properties of pure and Ni-doped SnO2 nanoparticles (NPs) synthesized by a sol-gel process. An extensive structural study has been carried out using various characterization techniques. The X-ray Diffraction (XRD) spectra show the formation of the single phase tetragonal structure of pure and Ni-doped SnO2 NPs without any noticeable impurity phase such as NiO. XRD results indicate that the crystallite size of SnO2 is found to be decreased with Ni doping, which has also been confirmed by the Field Emission Scanning Electron Microscopy study. X-ray Photoelectron Spectroscopy (XPS) measurements displayed a clear sign for Ni2+ ions occupying the lattice sites of Sn4+ in the SnO2 host which also gives clear evidence for the formation of single phase Sn1-xNixO2 NPs. The optical analysis shows a significant decrease in the energy gap of SnO2, i.e., (from 3.71 eV to 3.28 eV) as Ni concentration increases which may be correlated with the core level valence band XPS analysis. Photoluminescence studies show that Ni doping creates oxygen vacancies due to dissimilar ionic radii of Ni2+ and Sn4+. Superconducting quantum interference device measurements revealed that the Ni doped SnO2 NPs exhibit strong ferromagnetic behavior at room temperature and this analysis has been well fitted with a simple relationship to find out magnetic parameters proposed by Stearns and Cheng et al. Hence, our results demonstrate that Ni-doping has strong impact on the structural, optical, and magnetic properties.

Investigation of structural, morphological and electromagnetic properties of Mg0.25Mn0.25Zn0.5-xSrxFe2O4 ferrites

NASA Astrophysics Data System (ADS)

Rahaman, Md. D.; Nusrat, Tania; Maleque, Rumana; Hossain, A. K. M. Akther

2018-04-01

Polycrystalline Mg0.25Mn0.25Zn0.5-xSrxFe2O4 (0 ≤ x ≤ 0.20) ferrites were synthesized using the solid state reaction sintering at 1373 K and 1473 K for 4 h. The XRD patterns revealed the formation of single phase cubic spinel with Sr2FeO4 and SrFe12O19 as impurity phases. The decrement in the lattice parameter for Sr2+ substituted samples is attributed to the difference in ionic radii of cations. The crystallite size decreases with increase in Sr2+ content. Low frequency dielectric dispersion is attributed due to the Maxwell-Wagner interfacial polarization. The appearance of the peak in dielectric loss spectrum for x = 0.15 and 0.20 at 1373 K and x = 0.20 at 1473 K suggests the presence of relaxing dipoles. The loss peak shifts towards lower frequency side with Sr2+ content at 1373 K which is due to the strengthening of dipole-dipole interactions. The complex impedance spectra clearly revealed that the both grain and grain boundary effects on the electrical properties. A complex electric modulus spectrum indicates that a non-Debye type of conductivity relaxation exists. The saturation magnetization and remanence gradually decreases with Sr2+ substitution which may be due to the existence of non-magnetic phase in the space between the magnetic particles and the substitution of Zn2+ cation in Mg0.25Mn0.25Zn0.5Fe2O4 ferrite lattice by Sr2+ content. The permeability decreases significantly while the cut-off frequency increases with the Sr2+ content at 1373 K and decreases at 1473 K, obeying the Snoek's law. The decrease in permeability with Sr2+ content is attributed due to the decrease in magnetization because non-magnetic ions weaken the inter-site exchange interaction.

Sulfide bonded atomic radii

NASA Astrophysics Data System (ADS)

Gibbs, G. V.; Ross, N. L.; Cox, D. F.

2017-09-01

The bonded radius, r b(S), of the S atom, calculated for first- and second-row non-transition metal sulfide crystals and third-row transition metal sulfide molecules and crystals indicates that the radius of the sulfur atom is not fixed as traditionally assumed, but that it decreases systematically along the bond paths of the bonded atoms with decreasing bond length as observed in an earlier study of the bonded radius of the oxygen atom. When bonded to non-transition metal atoms, r b(S) decreases systematically with decreasing bond length from 1.68 Å when the S atom is bonded to the electropositive VINa atom to 1.25 Å when bonded to the more electronegative IVP atom. In the case of transition metal atoms, rb(S) likewise decreases with decreasing bond length from 1.82 Å when bonded to Cu and to 1.12 Å when bonded to Fe. As r b(S) is not fixed at a given value but varies substantially depending on the bond length and the field strength of the bonded atoms, it is apparent that sets of crystal and atomic sulfide atomic radii based on an assumed fixed radius for the sulfur atom are satisfactory in that they reproduce bond lengths, on the one hand, whereas on the other, they are unsatisfactory in that they fail to define the actual sizes of the bonded atoms determined in terms of the minima in the electron density between the atoms. As such, we urge that the crystal chemistry and the properties of sulfides be studied in terms of the bond lengths determined by adding the radii of either the atomic and crystal radii of the atoms but not in terms of existing sets of crystal and atomic radii. After all, the bond lengths were used to determine the radii that were experimentally determined, whereas the individual radii were determined on the basis of an assumed radius for the sulfur atom.

Studies on the solvation dynamics of coumarin 153 in 1-ethyl-3-methylimidazolium alkylsulfate ionic liquids: dependence on alkyl chain length.

PubMed

Das, Sudhir Kumar; Sarkar, Moloy

2012-08-06

Steady-state and time-resolved fluorescence behavior of coumarin 153 (C153) is investigated in a series of 1-ethyl-3-methylimidazolium alkylsulfate ([C(2)mim][C(n)OSO(3)]) ionic liquids differing only in the length of the linear alkyl chain (n = 4, 6, and 8) in the anion. The aim of the present study is to understand the role of alkyl chain length in solute rotation and solvation dynamics of C153 in these ionic liquids. The blueshift observed in the steady-state absorption and emission maxima of C153 on going from the C(4)OSO(3) to the C(8)OSO(3) system indicates increasing nonpolar character of the microenvironment of the solute with increasing length of the alkyl side chain of the anion of the ionic liquids. The average solvation time is also found to increase on changing the substituent from butyl to octyl, and this is attributed to the increase in the bulk viscosity of the ILs. A steady blueshift of the time-zero maximum of the fluorescence spectrum with increasing alkyl chain length also indicates that the probe molecule experiences a less polar environment in the early part of the dynamics. Rotational dynamics of C153 are also analyzed by using the Stokes-Einstein-Debye (SED), Gierer-Wirtz (GW), and Dote-Kivelson-Schwartz (DKS) theories. Analyses of the results seem to suggest decoupling of the rotational motion of the probe from solvent viscosity. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.