WorldWideScience

Sample records for solvated ionic polymer

  1. Monte Carlo Simulation of a Solvated Ionic Polymer with Cluster Morphology

    National Research Council Canada - National Science Library

    Matthews, Jessica L; Lada, Emily K; Weiland, Lisa M; Smith, Ralph C; Leo, Donald J

    2005-01-01

    .... Traditional rotational isomeric state theory is applied in combination with a Monte Carlo methodology to develop a simulation model of the conformation of Nafion polymer chains on a nanoscopic level...

  2. Effects of compatibility of polymer binders with solvate ionic liquid electrolytes on discharge and charge reactions of lithium-sulfur batteries

    Science.gov (United States)

    Nakazawa, Toshitada; Ikoma, Ai; Kido, Ryosuke; Ueno, Kazuhide; Dokko, Kaoru; Watanabe, Masayoshi

    2016-03-01

    Electrochemical reactions in Li-S cells with a solvate ionic liquid (SIL) electrolyte composed of tetraglyme (G4) and Li[TFSA] (TFSA: bis(trifluoromethanesulfonyl)amide) are studied. The sulfur cathode (S cathode) comprises sulfur, carbon powder, and a polymer binder. Poly(ethylene oxide) (PEO) and poly(vinyl alcohol) (PVA-x) with different degrees of saponification (x%) are used as binders to prepare the composite cathodes. For the Li-S cell containing PEO binder, lithium polysulfides (Li2Sm, 2 ≤ m ≤ 8), reaction intermediates of the S cathode, dissolve into the electrolyte, and Li2Sm acts as a redox shuttle in the Li-S cell. In contrast, in the Li-S cell with PVA-x binder, the dissolution of Li2Sm is suppressed, leading to high columbic efficiencies during charge-discharge cycles. The compatibility of the PVA-x binder with the SIL electrolyte changes depending on the degree of saponification. Decreasing the degree of saponification leads to increased electrolyte uptake by the PVA-x binder, increasing the charge and discharge capacities of Li-S cell. The rate capability of Li-S cell is also enhanced by the partial swelling of the PVA-x binder. The enhanced performance of Li-S cell containing PVA-x is attributed to the lowering of resistance of Li+ ion transport in the composite cathode.

  3. Strong Stretching of Poly(ethylene glycol) Brushes Mediated by Ionic Liquid Solvation.

    Science.gov (United States)

    Han, Mengwei; Espinosa-Marzal, Rosa M

    2017-09-07

    We have measured forces between mica surfaces coated with a poly(ethylene glycol) (PEG) brush solvated by a vacuum-dry ionic liquid, 1-ethyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)imide, with a surface forces apparatus. At high grafting density, the solvation mediated by the ionic liquid causes the brush to stretch twice as much as in water. Modeling of the steric repulsion indicates that PEG behaves as a polyelectrolyte; the hydrogen bonding between ethylene glycol and the imidazolium cation seems to effectively charge the polymer brush, which justifies the strong stretching. Importantly, under strong polymer compression, solvation layers are squeezed out at a higher rate than for the neat ionic liquid. We propose that the thermal fluctuations of the PEG chains, larger in the brush than in the mushroom configuration, maintain the fluidity of the ionic liquid under strong compression, in contrast to the solid-like squeezing-out behavior of the neat ionic liquid. This is the first experimental study of the behavior of a polymer brush solvated by an ionic liquid under nanoconfinement.

  4. Ionic Liquids: Radiation Chemistry, Solvation Dynamics and Reactivity Patterns

    International Nuclear Information System (INIS)

    Wishart, J.F.

    2008-01-01

    Ionic liquids (ILs) are a rapidly expanding family of condensed-phase media with important applications in energy production, nuclear fuel and waste processing, improving the efficiency and safety of industrial chemical processes, and pollution prevention. ILs are generally nonvolatile, noncombustible, highly conductive, recyclable and capable of dissolving a wide variety of materials. They are finding new uses in chemical synthesis, catalysis, separations chemistry, electrochemistry and other areas. Ionic liquids have dramatically different properties compared to conventional molecular solvents, and they provide a new and unusual environment to test our theoretical understanding of charge transfer and other reactions. We are interested in how IL properties influence physical and dynamical processes that determine the stability and lifetimes of reactive intermediates and thereby affect the courses of chemical reactions and product distributions. Successful use of ionic liquids in radiation-filled environments, where their safety advantages could be significant, requires an understanding of ionic liquid radiation chemistry. For example, characterizing the primary steps of IL radiolysis will reveal radiolytic degradation pathways and suggest ways to prevent them or mitigate their effects on the properties of the material. An understanding of ionic liquid radiation chemistry will also facilitate pulse radiolysis studies of general chemical reactivity in ILs, which will aid in the development of applications listed above. Very early in our radiolysis studies it became evident that slow solvation dynamics of the excess electron in ILs (which vary over a wide viscosity range) increases the importance of pre-solvated electron reactivity and consequently alters product distributions. Parallel studies of IL solvation phenomena using coumarin-153 dynamic Stokes shifts and polarization anisotropy decay rates are done to compare with electron solvation studies and to evaluate

  5. IONIC LIQUIDS: RADIATION CHEMISTRY, SOLVATION DYNAMICS AND REACTIVITY PATTERNS

    International Nuclear Information System (INIS)

    WISHART, J.F.

    2007-01-01

    energy production, nuclear fuel and waste processing, improving the efficiency and safety of industrial chemical processes, and pollution prevention. ILs are generally nonvolatile, noncombustible, highly conductive, recyclable and capable of dissolving a wide variety of materials. They are finding new uses in chemical synthesis, catalysis, separations chemistry, electrochemistry and other areas. Ionic liquids have dramatically different properties compared to conventional molecular solvents, and they provide a new and unusual environment to test our theoretical understanding of charge transfer and other reactions. We are interested in how IL properties influence physical and dynamical processes that determine the stability and lifetimes of reactive intermediates and thereby affect the courses of chemical reactions and product distributions. Successful use of ionic liquids in radiation-filled environments, where their safety advantages could be significant, requires an understanding of ionic liquid radiation chemistry. For example, characterizing the primary steps of IL radiolysis will reveal radiolytic degradation pathways and suggest ways to prevent them or mitigate their effects on the properties of the material. An understanding of ionic liquid radiation chemistry will also facilitate pulse radiolysis studies of general chemical reactivity in ILs, which will aid in the development of applications listed above. Very early in our radiolysis studies it became evident that slow solvation dynamics of the excess electron in ILs (which vary over a wide viscosity range) increases the importance of pre-solvated electron reactivity and consequently alters product distributions. Parallel studies of IL solvation phenomena using coumarin-153 dynamic Stokes shifts and polarization anisotropy decay rates are done to compare with electron solvation studies and to evaluate the influence of ILs on charge transport processes. Methods. Picosecond pulse radiolysis studies at BNL

  6. Ionic liquids: radiation chemistry, solvation dynamics and reactivity patterns

    International Nuclear Information System (INIS)

    Wishart, J.F.; Funston, A.M.; Szreder, T.

    2006-01-01

    Ionic liquids (ILs) are a rapidly expanding family of condensed-phase media with important applications in energy production, nuclear fuel and waste processing, improving the efficiency and safety of industrial chemical processes, and pollution prevention. ILs are nonvolatile, noncombustible, highly conductive, recyclable and capable of dissolving a wide variety of materials. They are finding new uses in chemical synthesis, catalysis, separations chemistry, electrochemistry and other areas. Ionic liquids have dramatically different properties compared to conventional molecular solvents, and they provide a new and unusual environment to test our theoretical understanding of charge transfer and other reactions. We are interested in how IL properties influence physical and dynamical processes that determine the stability and lifetimes of reactive intermediates and thereby affect the courses of chemical reactions and product distributions. Successful use of ionic liquids in radiation-filled environments, where their safety advantages could be significant, requires an understanding of ionic liquid radiation chemistry. For example, characterizing the primary steps of IL radiolysis will reveal radiolytic degradation pathways and suggest ways to prevent them or mitigate their effects on the properties of the material. An understanding of ionic liquid radiation chemistry will also facilitate pulse radiolysis studies of general chemical reactivity in ILs, which will aid in the development of energy production, chemical industry and environmental applications. Pulse radiolysis of [R 4 N][NTf 2 ] [R 4 N][N(CN) 2 ], and [R 4 P][N(CN) 2 ] ionic liquids produces solvated electrons that absorb over a broad range in the near infrared and persisting for hundreds of nanoseconds. Systematic cation variation shows that solvated electron's spectroscopic properties depend strongly on the lattice structure of the ionic liquid. Very early in our radiolysis studies it became evident that

  7. Ionic Liquids: Radiation Chemistry, Solvation Dynamics and Reactivity Patterns

    International Nuclear Information System (INIS)

    Wishart, J.F.

    2011-01-01

    Ionic liquids (ILs) are a rapidly expanding family of condensed-phase media with important applications in energy production, nuclear fuel and waste processing, improving the efficiency and safety of industrial chemical processes, and pollution prevention. ILs generally have low volatilities and are combustion-resistant, highly conductive, recyclable and capable of dissolving a wide variety of materials. They are finding new uses in chemical synthesis, catalysis, separations chemistry, electrochemistry and other areas. Ionic liquids have dramatically different properties compared to conventional molecular solvents, and they provide a new and unusual environment to test our theoretical understanding of primary radiation chemistry, charge transfer and other reactions. We are interested in how IL properties influence physical and dynamical processes that determine the stability and lifetimes of reactive intermediates and thereby affect the courses of reactions and product distributions. We study these issues by characterization of primary radiolysis products and measurements of their yields and reactivity, quantification of electron solvation dynamics and scavenging of electrons in different states of solvation. From this knowledge we wish to learn how to predict radiolytic mechanisms and control them or mitigate their effects on the properties of materials used in nuclear fuel processing, for example, and to apply IL radiation chemistry to answer questions about general chemical reactivity in ionic liquids that will aid in the development of applications listed above. Very early in our radiolysis studies it became evident that the slow solvation dynamics of the excess electron in ILs (which vary over a wide viscosity range) increase the importance of pre-solvated electron reactivity and consequently alter product distributions and subsequent chemistry. This difference from conventional solvents has profound effects on predicting and controlling radiolytic yields

  8. Fluorescent probe studies of polarity and solvation within room temperature ionic liquids: a review.

    Science.gov (United States)

    Pandey, Shubha; Baker, Sheila N; Pandey, Siddharth; Baker, Gary A

    2012-09-01

    Ionic liquids display an array of useful and sometimes unconventional, solvent features and have attracted considerable interest in the field of green chemistry for the potential they hold to significantly reduce environmental emissions. Some of these points have a bearing on the chemical reactivity of these systems and have also generated interest in the physical and theoretical aspects of solvation in ionic liquids. This review presents an introduction to the field of ionic liquids, followed by discussion of investigations into the solvation properties of neat ionic liquids or mixed systems including ionic liquids as a major or minor component. The ionic liquid based multicomponent systems discussed are composed of other solvents, other ionic liquids, carbon dioxide, surfactants or surfactant solutions. Although we clearly focus on fluorescence spectroscopy as a tool to illuminate ionic liquid systems, the issues discussed herein are of general relevance to discussions of polarity and solvent effects in ionic liquids. Transient solvation measurements carried out by means of time-resolved fluorescence measurements are particularly powerful for their ability to parameterize the kinetics of the solvation process in ionic liquids and are discussed as well.

  9. Ionic strength independence of charge distributions in solvation of biomolecules

    Energy Technology Data Exchange (ETDEWEB)

    Virtanen, J. J. [Department of Chemistry, University of Chicago, Chicago, Illinois 60637 (United States); James Franck Institute, University of Chicago, Chicago, Illinois 60637 (United States); Sosnick, T. R. [Department of Biochemistry and Molecular Biology, Institute for Biophysical Dynamics, University of Chicago, Chicago, Illinois 60637 (United States); Computation Institute, University of Chicago, Chicago, Illinois 60637 (United States); Freed, K. F. [Department of Chemistry, University of Chicago, Chicago, Illinois 60637 (United States); James Franck Institute, University of Chicago, Chicago, Illinois 60637 (United States); Computation Institute, University of Chicago, Chicago, Illinois 60637 (United States)

    2014-12-14

    Electrostatic forces enormously impact the structure, interactions, and function of biomolecules. We perform all-atom molecular dynamics simulations for 5 proteins and 5 RNAs to determine the dependence on ionic strength of the ion and water charge distributions surrounding the biomolecules, as well as the contributions of ions to the electrostatic free energy of interaction between the biomolecule and the surrounding salt solution (for a total of 40 different biomolecule/solvent combinations). Although water provides the dominant contribution to the charge density distribution and to the electrostatic potential even in 1M NaCl solutions, the contributions of water molecules and of ions to the total electrostatic interaction free energy with the solvated biomolecule are comparable. The electrostatic biomolecule/solvent interaction energies and the total charge distribution exhibit a remarkable insensitivity to salt concentrations over a huge range of salt concentrations (20 mM to 1M NaCl). The electrostatic potentials near the biomolecule's surface obtained from the MD simulations differ markedly, as expected, from the potentials predicted by continuum dielectric models, even though the total electrostatic interaction free energies are within 11% of each other.

  10. Ionic strength independence of charge distributions in solvation of biomolecules

    International Nuclear Information System (INIS)

    Virtanen, J. J.; Sosnick, T. R.; Freed, K. F.

    2014-01-01

    Electrostatic forces enormously impact the structure, interactions, and function of biomolecules. We perform all-atom molecular dynamics simulations for 5 proteins and 5 RNAs to determine the dependence on ionic strength of the ion and water charge distributions surrounding the biomolecules, as well as the contributions of ions to the electrostatic free energy of interaction between the biomolecule and the surrounding salt solution (for a total of 40 different biomolecule/solvent combinations). Although water provides the dominant contribution to the charge density distribution and to the electrostatic potential even in 1M NaCl solutions, the contributions of water molecules and of ions to the total electrostatic interaction free energy with the solvated biomolecule are comparable. The electrostatic biomolecule/solvent interaction energies and the total charge distribution exhibit a remarkable insensitivity to salt concentrations over a huge range of salt concentrations (20 mM to 1M NaCl). The electrostatic potentials near the biomolecule's surface obtained from the MD simulations differ markedly, as expected, from the potentials predicted by continuum dielectric models, even though the total electrostatic interaction free energies are within 11% of each other

  11. Pulse radiolysis study on solvated electrons in ionic liquid with controlling water content

    International Nuclear Information System (INIS)

    Yang Jinfeng; Kondoh, T.; Yoshida, Y.; Nagaishi, R.

    2006-01-01

    Room-temperature ionic liquids, which are nonvolatile and nonflammable, have been proposed as 'green solvents' for new applications in chemical synthesis, separation chemistry, electrochemistry and other areas. In the separation chemistry, the hydrophobic ionic liquids have been practically expected to be alternative to traditional organic solvents for solvent extraction of 4f and 5f elements from the viewpoints of the immiscibility in water, especially in the spent nuclear fuel reprocessing. However, the chemical reaction or kinetics studies are important to apply the ionic liquids for various processes. To understand the effects of ionic liquids on chemical reactions, pulse radiolysis studies of ionic liquid have been carried out on nanosecond scale by using a 27 MeV electron beam and an analyzing light source of xenon lamp. In the experiment, a hydrophobic ionic liquid of diethylmethyl(2-methoxy)ammonium-bis(trifluoromethanesulfonyl)imide (DEMMA-TFSI) salt was used. The ionic liquid of DEMMA-TFSI was prepared by reacting equimolar amounts of diethylmethyl(2-methoxy)ammonium chloride (C 10 H 20 F 6 N 2 O 5 S 2 Cl, >98%, Nisshinbo) with lithium bis(trifluoromethanesulfonyl)imide (LiN(SO 2 CF 3 ) 2 , SynQuest Labs., Inc.) in aqueous solutions at room temperature. The ionic liquid was separated from the aqueous phase, purified by repeated extractions with water to LiCl and excess reagent, and finally dried at 110 degree C under vacuum. The transient absorptions of the ionic liquid were measured at wavelengths from 350 to 1400 nm, in which two photodiodes of silicon ( 1000 nm) were used. The spectrum of solvated electrons in the ionic liquid of DEMMA-TFSI was obtained with an absorption peak of 1060 nm and a wide bandwidth of about 600 nm (FWHM). The decay constant of the solvated electrons in the ionic liquid was 1.54 x 10 7 s -1 , which is independent on the wavelength. The absorption peak of the spectrum was blue-shifted from 1060 to 780 nm with increasing water

  12. Terminology of Polymers Containing Ionizable or Ionic Groups and of Polymers Containing Ions, VII.3

    Directory of Open Access Journals (Sweden)

    Jarm, V.

    2009-10-01

    Full Text Available The class of ionic polymers has widespread application in many areas of everyday life, in industrial production, and in the processes of living matter. The properties of ionic polymers depend on the polymer structure, and the nature, content, and location of the ionic groups. To clear differences among various ionic polymers, the IUPAC recommendations present 34 definitionsfor the ionomer, polyacid, polybase, polyampholytic polymer, ion-exchange polymer, polybetaine, polyelectrolyte, intrinsically conducting polymer, solid polymer electrolyte, etc

  13. Influence of temperature and molecular structure on ionic liquid solvation layers.

    Science.gov (United States)

    Wakeham, Deborah; Hayes, Robert; Warr, Gregory G; Atkin, Rob

    2009-04-30

    Atomic force microscopy (AFM) force profiling is used to investigate the structure of adsorbed and solvation layers formed on a mica surface by various room temperature ionic liquids (ILs) ethylammonium nitrate (EAN), ethanolammonium nitrate (EtAN), ethylammonium formate (EAF), propylammonium formate (PAF), ethylmethylammonium formate (EMAF), and dimethylethylammonium formate (DMEAF). At least seven layers are observed for EAN at 14 degrees C (melting point 13 degrees C), decreasing as the temperature is increased to 30 degrees C due to thermal energy disrupting solvophobic forces that lead to segregation of cation alkyl tails from the charged ammonium and nitrate moieties. The number and properties of the solvation layers can also be controlled by introducing an alcohol moiety to the cation's alkyl tail (EtAN), or by replacing the nitrate anion with formate (EAF and PAF), even leading to the detection of distinct cation and anion sublayers. Substitution of primary by secondary or tertiary ammonium cations reduces the number of solvation layers formed, and also weakens the cation layer adsorbed onto mica. The observed solvation and adsorbed layer structures are discussed in terms of the intermolecular cohesive forces within the ILs.

  14. Applications of ionic liquids in polymer science and technology

    CERN Document Server

    2015-01-01

    This book summarizes the latest knowledge in the science and technology of ionic liquids and polymers in different areas. Ionic liquids (IL) are actively being investigated in polymer science and technology for a number of different applications. In the first part of the book the authors present the particular properties of ionic liquids as speciality solvents. The state-of-the art in the use of ionic liquids in polymer synthesis and modification reactions including polymer recycling is outlined. The second part focuses on the use of ionic liquids as speciality additives such as plasticizers or antistatic agents.  The third part examines the use of ionic liquids in the design of functional polymers (usually called polymeric ionic liquids (PIL) or poly(ionic liquids)). Many important applications in diverse scientific and industrial areas rely on these polymers, like polymer electrolytes in electrochemical devices, building blocks in materials science, nanocomposites, gas membranes, innovative anion sensitive...

  15. Ionic association and solvation in solutions of magnesium and nickel perchlorates in acetonitrile

    Science.gov (United States)

    Kalugin, O. N.; Agieienko, V. N.; Otroshko, N. A.; Moroz, V. V.

    2009-02-01

    The paper presents the conductometric data on solutions of Mg(ClO4)2 and Ni(ClO4)2 in acetonitrile over the temperature ranges 5-55°C for Mg(ClO4)2 and 25-75°C for Ni(ClO4)2. The extended Lee-Wheaton equation for unsymmetrical electrolytes was used to determine the limiting equivalent conductivities of the Mg2+, Ni2+, and ClO{4/-} ions and first-step ionic association constants with the formation of [KtClO4]+ ion pairs. Lower ionic association constants for Ni(ClO4)2 compared with Mg(ClO4)2 were a consequence of stronger non-Coulomb repulsion in the formation of [KtClO4]+ ion pairs because of the formation of a firmer solvation shell by the nickel compared with magnesium cation. The structure-dynamic parameter of ionic solvation was estimated. It was found that spatial-time correlations in the nearest environment of ions increased in the series ClO{4/-} > Mg2+ > Ni2+.

  16. Computational solvation analysis of biomolecules in aqueous ionic liquid mixtures : From large flexible proteins to small rigid drugs.

    Science.gov (United States)

    Zeindlhofer, Veronika; Schröder, Christian

    2018-06-01

    Based on their tunable properties, ionic liquids attracted significant interest to replace conventional, organic solvents in biomolecular applications. Following a Gartner cycle, the expectations on this new class of solvents dropped after the initial hype due to the high viscosity, hydrolysis, and toxicity problems as well as their high cost. Since not all possible combinations of cations and anions can be tested experimentally, fundamental knowledge on the interaction of the ionic liquid ions with water and with biomolecules is mandatory to optimize the solvation behavior, the biodegradability, and the costs of the ionic liquid. Here, we report on current computational approaches to characterize the impact of the ionic liquid ions on the structure and dynamics of the biomolecule and its solvation layer to explore the full potential of ionic liquids.

  17. Ionic Liquids in Polymer Design: From Energy to Health

    Science.gov (United States)

    2016-10-19

    of Papers published in non peer- reviewed journals: Final Report: Ionic Liquids in Polymer Design: From Energy to Health Report Title ACS Symposium...SECURITY CLASSIFICATION OF: ACS Symposium: Ionic Liquids in Polymer Design: From Energy to Health at Fall 2015 ACS Meeting in Boston, MA The...combination of ionic liquids and polymers has emerged as an active field of exploration in polymer science, where new materials have be realized for

  18. Theory of competitive solvation of polymers by two solvents and entropy-enthalpy compensation in the solvation free energy upon dilution with the second solvent.

    Science.gov (United States)

    Dudowicz, Jacek; Freed, Karl F; Douglas, Jack F

    2015-06-07

    We develop a statistical mechanical lattice theory for polymer solvation by a pair of relatively low molar mass solvents that compete for binding to the polymer backbone. A theory for the equilibrium mixture of solvated polymer clusters {AiBCj} and free unassociated molecules A, B, and C is formulated in the spirit of Flory-Huggins mean-field approximation. This theoretical framework enables us to derive expressions for the boundaries for phase stability (spinodals) and other basic properties of these polymer solutions: the internal energy U, entropy S, specific heat CV, extent of solvation Φsolv, average degree of solvation 〈Nsolv〉, and second osmotic virial coefficient B2 as functions of temperature and the composition of the mixture. Our theory predicts many new phenomena, but the current paper applies the theory to describe the entropy-enthalpy compensation in the free energy of polymer solvation, a phenomenon observed for many years without theoretical explanation and with significant relevance to liquid chromatography and other polymer separation methods.

  19. Solvation of a Small Metal-Binding Peptide in Room-Temperature Ionic Liquids

    Energy Technology Data Exchange (ETDEWEB)

    Shim, Youngseon; Jung, Younjoon [Seoul National Univ., Seoul (Korea, Republic of); Kim, Hyung J. [Carnegie Mellon Univ., Pittsburgh (United States)

    2012-11-15

    Structural properties of a small hexapeptide molecule modeled after metal-binding siderochrome immersed in a room-temperature ionic liquid (RTIL) are studied via molecular dynamics simulations. We consider two different RTILs, each of which is made up of the same cationic species, 1-butyl-3-methylimidazolium (BMI{sup +}), but different anions, hexafluorophosphate (PF{sub 6}{sup -}) and chloride (Cl{sup -}). We investigate how anionic properties such as hydrophobicity/hydrophilicity or hydrogen bonding capability affect the stabilization of the peptide in RTILs. To examine the effect of peptide-RTIL electrostatic interactions on solvation, we also consider a hypothetical solvent BMI{sup 0}Cl{sup 0}, a non-ionic counter-part of BMI{sup +}Cl{sup -}. For reference, we investigate solvation structures in common polar solvents, water and dimethylsulfoxide (DMSO). Comparison of BMI{sup +}Cl{sup -} and BMI{sup 0}Cl{sup 0} shows that electrostatic interactions of the peptide and RTIL play a significant role in the conformational fluctuation of the peptide. For example, strong electrostatic interactions between the two favor an extended conformation of the peptide by reducing its structural fluctuations. The hydrophobicity/hydrophilicity of RTIL anions also exerts a notable influence; specifically, structural fluctuations of the peptide become reduced in more hydrophilic BMI{sup +}Cl{sup -}, compared with those in more hydrophobic BMI{sup +}PF{sub 6}{sup -}. This is ascribed to the good hydrogen-bond accepting power of chloride anions, which enables them to bind strongly to hydroxyl groups of the peptide and to stabilize its structure. Transport properties of the peptide are examined briefly. Translations of the peptide significantly slow down in highly viscous RTILs.

  20. Effects of functional group substitution on electron spectra and solvation dynamics in a family of ionic liquids

    International Nuclear Information System (INIS)

    Wishart, James F.; Lall-Ramnarine, Sharon I.; Raju, Ravinder; Scumpia, Alexander; Bellevue, Sherly; Ragbir, Revans; Engel, Robert

    2005-01-01

    Ionic liquids containing ether-, alcohol- and alkyl-functionalized quaternary ammonium dications were studied by pulse radiolysis. Spectra on nanosecond timescales revealed that solvation of the excess electron is particularly slow in the case of the alcohol-derivatized ionic liquids. The blue shift of the electron spectrum to the customary 650 nm peak takes 25-40 ns at 21 deg. C. Comparison with the relaxation dynamics observed in viscous 1,2,6-trihydroxyhexane reveals the hindering effect of the ionic liquid lattice on hydroxypropyl side chain reorientation

  1. Conformational Behavior of Polymer Chains of Different Architectures in Strongly Endothermic Solvent Mixtures: Specific Solvation Effects.

    Czech Academy of Sciences Publication Activity Database

    Suchá, L.; Limpouchová, Z.; Procházka, Karel

    2017-01-01

    Roč. 295, č. 8 (2017), s. 1391-1403 ISSN 0303-402X R&D Projects: GA ČR GA15-19542S Institutional support: RVO:67985858 Keywords : cononsolvency * preferential solvation * star polymer Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 1.723, year: 2016

  2. Correlation between ionic conductivity and fluidity of polymer gel ...

    Indian Academy of Sciences (India)

    Unknown

    Ionic conductivity; ion aggregates; FTIR spectroscopy; gels; fluidity. 1. Introduction ... liquid and polymer gel electrolytes have been studied as functions of salt ..... Ratner M A 1987 in Polymer electrolyte reviews (eds) J R. MacCallum and C A ...

  3. Ionic conductivity of polymer gels deriving from alkali metal ionic liquids and negatively charged polyelectrolytes

    International Nuclear Information System (INIS)

    Ogihara, Wataru; Sun Jiazeng; Forsyth, Maria; MacFarlane, Douglas R.; Yoshizawa, Masahiro; Ohno, Hiroyuki

    2004-01-01

    We have prepared polymer gel electrolytes with alkali metal ionic liquids (AMILs) that inherently contain alkali metal ions. The AMIL consisted of sulfate anion, imidazolium cation, and alkali metal cation. AMILs were mixed directly with poly(3-sulfopropyl acrylate) lithium salt or poly(2-acrylamido-2-methylpropanesulfonic acid) lithium salt to form polymer gels. The ionic conductivity of these gels decreased with increasing polymer fraction, as in general ionic liquid/polymer mixed systems. At low polymer concentrations, these gels displayed excellent ionic conductivity of 10 -4 to 10 -3 S cm -1 at room temperature. Gelation was found to cause little change in the 7 Li diffusion coefficient of the ionic liquid, as measured by pulse-field-gradient NMR. These data strongly suggest that the lithium cation migrates in successive pathways provided by the ionic liquids

  4. CL 14: Solvation structure and dynamics of room temperature ionic liquids

    International Nuclear Information System (INIS)

    Musat, Raluca M.; Polyansky, Dmitriy; Crowell, Robert A.; Thomas, Marie; Wishart, James F.; Takahashi, Kenji; Katsumura, Yosuke

    2010-01-01

    Room temperature ionic liquids (RTILs) have emerged as a new class of solvents that, due to their unique properties (e.g., low volatility, large electrochemical window, high conductivity, etc.), have several potential applications. Among these are their possible use in nuclear fuel reprocessing, dye sensitized solar cells, and CO 2 sequestration. The properties of a given class of RTILs depend strongly on the choice of the counter anion. In this contribution we present new results using both static and time-resolved EXAFS (ca. 1 ns resolution) and time resolved optical absorption spectroscopy on a series of bromide containing imidazolium salts. The static results provide detailed information of the solvation shell of the bromide ion while the time-resolved data shed light on the nature and chemical behavior of the lowest lying charge transfer band, the physical motion of the bromine atom and its conversion to di-bromide. The photochemistry of the charge transfer (CT) band of the room temperature ionic liquid 1-hexyl-3-methylimidazolium bromide is investigated using ultrafast transient absorption spectroscopy (TA) in the near-IR and steady state UV absorption. Irradiation of the CT band at 266 nm results in the steady state production of di-bromide which absorbs strongly at 266 nm. It is shown that this photoproduct, which is apparently very stable, adversely affects ultrafast transient absorption measurements. Flowing and simultaneously translating the sample mitigates this effect and reveals new transient species and dynamics within the detection window of 850 nm to 1250 nm. (authors)

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

    Science.gov (United States)

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

    2018-05-01

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

  6. Spectroscopic and computational studies of ionic clusters as models of solvation and atmospheric reactions

    Science.gov (United States)

    Kuwata, Keith T.

    Ionic clusters are useful as model systems for the study of fundamental processes in solution and in the atmosphere. Their structure and reactivity can be studied in detail using vibrational predissociation spectroscopy, in conjunction with high level ab initio calculations. This thesis presents the applications of infrared spectroscopy and computation to a variety of gas-phase cluster systems. A crucial component of the process of stratospheric ozone depletion is the action of polar stratospheric clouds (PSCs) to convert the reservoir species HCl and chlorine nitrate (ClONO2) to photochemically labile compounds. Quantum chemistry was used to explore one possible mechanism by which this activation is effected: Cl- + ClONO2 /to Cl2 + NO3- eqno(1)Correlated ab initio calculations predicted that the direct reaction of chloride ion with ClONO2 is facile, which was confirmed in an experimental kinetics study. In the reaction a weakly bound intermediate Cl2-NO3- is formed, with ~70% of the charge localized on the nitrate moiety. This enables the Cl2-NO3- cluster to be well solvated even in bulk solution, allowing (1) to be facile on PSCs. Quantum chemistry was also applied to the hydration of nitrosonium ion (NO+), an important process in the ionosphere. The calculations, in conjunction with an infrared spectroscopy experiment, revealed the structure of the gas-phase clusters NO+(H2O)n. The large degree of covalent interaction between NO+ and the lone pairs of the H2O ligands is contrasted with the weak electrostatic bonding between iodide ion and H2O. Finally, the competition between ion solvation and solvent self-association is explored for the gas-phase clusters Cl/-(H2O)n and Cl-(NH3)n. For the case of water, vibrational predissociation spectroscopy reveals less hydrogen bonding among H2O ligands than predicted by ab initio calculations. Nevertheless, for n /ge 5, cluster structure is dominated by water-water interactions, with Cl- only partially solvated by the

  7. Generalized linear solvation energy model applied to solute partition coefficients in ionic liquid-supercritical carbon dioxide systems

    Czech Academy of Sciences Publication Activity Database

    Planeta, Josef; Karásek, Pavel; Hohnová, Barbora; Šťavíková, Lenka; Roth, Michal

    2012-01-01

    Roč. 1250, SI (2012), s. 54-62 ISSN 0021-9673 R&D Projects: GA ČR(CZ) GAP206/11/0138; GA ČR(CZ) GAP106/12/0522; GA ČR(CZ) GPP503/11/P523 Institutional research plan: CEZ:AV0Z40310501 Keywords : ionic liquid * supercritical carbon dioxide * solvation energy model Subject RIV: BJ - Thermodynamics Impact factor: 4.612, year: 2012

  8. Dielectric electroactive polymers comprising an ionic supramolecular structure

    DEFF Research Database (Denmark)

    2014-01-01

    The present invention relates to an ionic interpenetrating polymer network comprising at least one elastomer and an ionic supramolecular structure comprising the reaction product of at least two chemical compounds wherein each of said compounds has at least two functional groups and wherein said ...... compounds are able to undergo Lewis acid-base reactions. The interpenetrating polymer network may be used as dielectric electroactive polymers (DEAPs) having a high dielectric permittivity....

  9. Ionic Solution: What Goes Right and Wrong with Continuum Solvation Modeling.

    Science.gov (United States)

    Wang, Changhao; Ren, Pengyu; Luo, Ray

    2017-12-14

    Solvent-mediated electrostatic interactions were well recognized to be important in the structure and function of molecular systems. Ionic interaction is an important component in electrostatic interactions, especially in highly charged molecules, such as nucleic acids. Here, we focus on the quality of the widely used Poisson-Boltzmann surface area (PBSA) continuum models in modeling ionic interactions by comparing with both explicit solvent simulations and the experiment. In this work, the molality-dependent chemical potentials for sodium chloride (NaCl) electrolyte were first simulated in the SPC/E explicit solvent. Our high-quality simulation agrees well with both the previous study and the experiment. Given the free-energy simulations in SPC/E as the benchmark, we used the same sets of snapshots collected in the SPC/E solvent model for PBSA free-energy calculations in the hope to achieve the maximum consistency between the two solvent models. Our comparative analysis shows that the molality-dependent chemical potentials of NaCl were reproduced well with both linear PB and nonlinear PB methods, although nonlinear PB agrees better with SPC/E and the experiment. Our free-energy simulations also show that the presence of salt increases the hydrophobic effect in a nonlinear fashion, in qualitative agreement with previous theoretical studies of Onsager and Samaras. However, the lack of molality-dependency in the nonelectrostatics continuum models dramatically reduces the overall quality of PBSA methods in modeling salt-dependent energetics. These analyses point to further improvements needed for more robust modeling of solvent-mediated interactions by the continuum solvation frameworks.

  10. A dual cryogenic ion trap spectrometer for the formation and characterization of solvated ionic clusters

    Energy Technology Data Exchange (ETDEWEB)

    Marsh, Brett M.; Voss, Jonathan M.; Garand, Etienne, E-mail: egarand@chem.wisc.edu [Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706 (United States)

    2015-11-28

    A new experimental approach is presented in which two separate cryogenic ion traps are used to reproducibly form weakly bound solvent clusters around electrosprayed ions and messenger-tag them for single-photon infrared photodissociation spectroscopy. This approach thus enables the vibrational characterization of ionic clusters comprised of a solvent network around large and non-volatile ions. We demonstrate the capabilities of the instrument by clustering water, methanol, and acetone around a protonated glycylglycine peptide. For water, cluster sizes with greater than twenty solvent molecules around a single ion are readily formed. We further demonstrate that similar water clusters can be formed around ions having a shielded charge center or those that do not readily form hydrogen bonds. Finally, infrared photodissociation spectra of D{sub 2}-tagged GlyGlyH{sup +} ⋅ (H{sub 2}O){sub 1−4} are presented. They display well-resolved spectral features and comparisons with calculations reveal detailed information on the solvation structures of this prototypical peptide.

  11. Ionic association and solvation of the ionic liquid 1-hexyl-3-methylimidazolium chloride in molecular solvents revealed by vapor pressure osmometry, conductometry, volumetry, and acoustic measurements.

    Science.gov (United States)

    Sadeghi, Rahmat; Ebrahimi, Nosaibah

    2011-11-17

    A systematic study of osmotic coefficient, conductivity, volumetric and acoustic properties of solutions of ionic liquid 1-hexyl-3-methylimidazolium chloride ([C(6)mim][Cl]) in various molecular solvents has been made at different temperatures in order to study of ionic association and solvation behavior of [C(6)mim][Cl] in different solutions. Precise measurements on electrical conductances of solutions of [C(6)mim][Cl] in water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and acetonitrile at 293.15, 298.15, and 303.15 K are reported and analyzed with Barthel's low-concentration chemical model (lcCM) to obtain the limiting molar conductivities and association constants of this ionic liquid in the investigated solvents. Strong ion pairing was found for the ionic liquid in 2-propanol, 1-butanol, and 1-propanol, whereas ion association in acetonitrile, methanol and ethanol is rather weak and in water the ionic liquid is fully dissociated. In the second part of this work, the apparent molar volumes and isentropic compressibilities of [C(6)mim][Cl] in water, methanol, ethanol, acetonitrile, 1-propanol, 2-propanol, and 1-butanol are obtained at the 288.15-313.15 K temperature range at 5 K intervals at atmospheric pressure from the precise measurements of density and sound velocity. The infinite dilution apparent molar volume and isentropic compressibility values of the free ions and ion pairs of [C(6)mim][Cl] in the investigated solvents as well as the excess molar volume of the investigated solutions are determined and their variations with temperature and type of solvents are also studied. Finally, the experimental measurements of osmotic coefficient at 318.15 K for binary solutions of [C(6)mim][Cl] in water, methanol, ethanol, 2-propanol, and acetonitrile are taken using the vapor pressure osmometry (VPO) method and from which the values of the solvent activity, vapor pressure, activity coefficients, and Gibbs free energies are calculated. The results are

  12. Towards a stable ion-solvating polymer electrolyte for advanced alkaline water electrolysis

    DEFF Research Database (Denmark)

    Aili, David; Wright, Andrew G.; Kraglund, Mikkel Rykær

    2017-01-01

    Advanced alkaline water electrolysis using ion-solvating polymer membranes as electrolytes represents a new direction in the field of electrochemical hydrogen production. Polybenzimidazole membranes equilibrated in aqueous KOH combine the mechanical robustness and gas-tightness of a polymer...... stability in alkaline environments. The novel electrolytes are extensively characterized with respect to physicochemical and electrochemical properties and the chemical stability is assessed in 0-50 wt% aqueous KOH for more than 6 months at 88 degrees C. In water electrolysis tests using porous 3...

  13. Infrared spectroscopy of model electrochemical interfaces in ultrahigh vacuum: some implications for ionic and chemisorbate solvation at electrode surfaces

    Science.gov (United States)

    Villegas, Ignacio; Kizhakevariam, Naushad; Weaver, Michael J.

    1995-07-01

    The utility of infrared reflection-absorption spectroscopy (IRAS) for examining structure and bonding for model electrochemical interfaces in ultrahigh vacuum (UHV) is illustrated, focusing specifically on the solvation of cations and chemisorbed carbon monoxide on Pt(111). These systems were chosen partly in view of the availability of IRAS data (albeit limited to chemisorbate vibrations) for the corresponding in-situ metal-solution interfaces, enabling direct spectral comparisons to be made with the "UHV electrochemical model" systems. Kelvin probe measurements of the metal-UHV surface potential changes (ΔΦ) attending alterations in the interfacial composition are also described: these provide the required link to the in-situ electrode potentials as well as yielding additional insight into surface solvation. Variations in the negative electronic charge density and, correspondingly, in the cation surface concentration (thereby mimicking charge-induced alterations in the electrode potential below the potential of zero charge) are achieved by potassium atom dosage onto Pt(111). Of the solvents selected for discussion here — deuterated water, methanol, and acetonitrile — the first two exhibit readily detectable vibrational bands which provide information on the ionic solvation structure. Progressively dosing these solvents onto Pt(111) in the presence of low potassium coverages yields marked alterations in the solvent vibrational bands which can be understood in terms of sequential cation solvation. Comparison between these spectra for methanol with analogous data for sequential methanol solvation of gas-phase alkali cations enables the influence of the interfacial environment to be assessed. The effects of solvating chemisorbed CO are illustrated for acetonitrile; the markedly larger shifts in CO frequencies and binding sites for dilute CO adlayers can be accounted for in terms of short-range coadsorbate interactions in addition to longer-range Stark effects

  14. Self-Sensing Ionic Polymer Actuators: A Review

    Directory of Open Access Journals (Sweden)

    Karl Kruusamäe

    2015-03-01

    Full Text Available Ionic electromechanically active polymers (IEAP are laminar composites that can be considered attractive candidates for soft actuators. Their outstanding properties such as low operating voltage, easy miniaturization, and noiseless operation are, however, marred by issues related to the repeatability in the production and operation of these materials. Implementing closed-loop control for IEAP actuators is a viable option for overcoming these issues. Since IEAP laminates also behave as mechanoelectrical sensors, it is advantageous to combine the actuating and sensing functionalities of a single device to create a so-called self-sensing actuator. This review article systematizes the state of the art in producing self-sensing ionic polymer actuators. The IEAPs discussed in this paper are conducting (or conjugated polymers actuators (CPA, ionic polymer-metal composite (IPMC, and carbonaceous polymer laminates.

  15. Boundary layer friction of solvate ionic liquids as a function of potential.

    Science.gov (United States)

    Li, Hua; Rutland, Mark W; Watanabe, Masayoshi; Atkin, Rob

    2017-07-01

    Atomic force microscopy (AFM) has been used to investigate the potential dependent boundary layer friction at solvate ionic liquid (SIL)-highly ordered pyrolytic graphite (HOPG) and SIL-Au(111) interfaces. Friction trace and retrace loops of lithium tetraglyme bis(trifluoromethylsulfonyl)amide (Li(G4) TFSI) at HOPG present clearer stick-slip events at negative potentials than at positive potentials, indicating that a Li + cation layer adsorbed to the HOPG lattice at negative potentials which enhances stick-slip events. The boundary layer friction data for Li(G4) TFSI shows that at HOPG, friction forces at all potentials are low. The TFSI - anion rich boundary layer at positive potentials is more lubricating than the Li + cation rich boundary layer at negative potentials. These results suggest that boundary layers at all potentials are smooth and energy is predominantly dissipated via stick-slip events. In contrast, friction at Au(111) for Li(G4) TFSI is significantly higher at positive potentials than at negative potentials, which is comparable to that at HOPG at the same potential. The similarity of boundary layer friction at negatively charged HOPG and Au(111) surfaces indicates that the boundary layer compositions are similar and rich in Li + cations for both surfaces at negative potentials. However, at Au(111), the TFSI - rich boundary layer is less lubricating than the Li + rich boundary layer, which implies that anion reorientations rather than stick-slip events are the predominant energy dissipation pathways. This is confirmed by the boundary friction of Li(G4) NO 3 at Au(111), which shows similar friction to Li(G4) TFSI at negative potentials due to the same cation rich boundary layer composition, but even higher friction at positive potentials, due to higher energy dissipation in the NO 3 - rich boundary layer.

  16. Application of a room temperature ionic liquid for nuclear spent fuel reprocessing: speciation of trivalent europium and solvatation effects

    International Nuclear Information System (INIS)

    Moutiers, G.; Mekki, S.; Billard, I.

    2007-01-01

    study. In the second chapter, we present the study of europium solvation in the ionic liquid media. In the third part, we expose the results concerning TTA solvation and its complexation with europium in bumimTf 2 N under different conditions. Finally in the last chapter, we present the results obtained for the europium extraction in a three-stage extraction system: water/bumimTf 2 N/supercritical CO 2 . This work highlights the potential use of ionic liquids and particularly bumimTf 2 N in the spent nuclear fuel reprocessing. The ability to extract quantitatively a trivalent lanthanide has been demonstrated. This fundamental study can be regarded as a feasibility demonstration to build an ionic liquid-containing extraction system, in the aim of possible large-scale application. (authors)

  17. Ionic Liquid-Doped Gel Polymer Electrolyte for Flexible Lithium-Ion Polymer Batteries

    Science.gov (United States)

    Zhang, Ruisi; Chen, Yuanfen; Montazami, Reza

    2015-01-01

    Application of gel polymer electrolytes (GPE) in lithium-ion polymer batteries can address many shortcomings associated with liquid electrolyte lithium-ion batteries. Due to their physical structure, GPEs exhibit lower ion conductivity compared to their liquid counterparts. In this work, we have investigated and report improved ion conductivity in GPEs doped with ionic liquid. Samples containing ionic liquid at a variety of volume percentages (vol %) were characterized for their electrochemical and ionic properties. It is concluded that excess ionic liquid can damage internal structure of the batteries and result in unwanted electrochemical reactions; however, samples containing 40–50 vol % ionic liquid exhibit superior ionic properties and lower internal resistance compared to those containing less or more ionic liquids.

  18. Ionic Liquid-Doped Gel Polymer Electrolyte for Flexible Lithium-Ion Polymer Batteries

    Directory of Open Access Journals (Sweden)

    Ruisi Zhang

    2015-05-01

    Full Text Available Application of gel polymer electrolytes (GPE in lithium-ion polymer batteries can address many shortcomings associated with liquid electrolyte lithium-ion batteries. Due to their physical structure, GPEs exhibit lower ion conductivity compared to their liquid counterparts. In this work, we have investigated and report improved ion conductivity in GPEs doped with ionic liquid. Samples containing ionic liquid at a variety of volume percentages (vol % were characterized for their electrochemical and ionic properties. It is concluded that excess ionic liquid can damage internal structure of the batteries and result in unwanted electrochemical reactions; however, samples containing 40–50 vol % ionic liquid exhibit superior ionic properties and lower internal resistance compared to those containing less or more ionic liquids.

  19. Where do ions solvate?

    Indian Academy of Sciences (India)

    We study a simple model of ionic solvation inside a water cluster. The cluster is modeled as a spherical dielectric continuum. It is found that unpolarizable ions always prefer the bulk solvation. On the other hand, for polarizable ions, there exists a critical value of polarization above which surface solvation becomes ...

  20. Phase Equilibria and Ionic Solvation in the Lithium Tetrafluoroborate-Dimethylsulfoxide System

    Science.gov (United States)

    Gafurov, M. M.; Kirillov, S. A.; Gorobets, M. I.; Rabadanov, K. Sh.; Ataev, M. B.; Tretyakov, D. O.; Aydemirov, K. M.

    2015-01-01

    The phase diagram and electrical conductivity isotherms for the lithium tetrafluoroborate (LiBF4)-dimethylsulfoxide (DMSO) system and Raman spectra of DMSO and the LiBF4-DMSO solution were studied. Spectroscopic signatures of a H-bond between DMSO and BF4 - ions were found. The bonds of Li+ ions to the solvent were stronger than the bonds in DMSO dimers because formation of the solvate destroyed dimeric DMSO molecules. The τω values for DMSO molecules in the Li+-ion solvate shell of the LiBF4-DMSO system were similar to those for associated solvent molecules.

  1. Ion solvation in polymer blends and block copolymer melts: effects of chain length and connectivity on the reorganization of dipoles.

    Science.gov (United States)

    Nakamura, Issei

    2014-05-29

    We studied the thermodynamic properties of ion solvation in polymer blends and block copolymer melts and developed a dipolar self-consistent field theory for polymer mixtures. Our theory accounts for the chain connectivity of polymerized monomers, the compressibility of the liquid mixtures under electrostriction, the permanent and induced dipole moments of monomers, and the resultant dielectric contrast among species. In our coarse-grained model, dipoles are attached to the monomers and allowed to rotate freely in response to electrostatic fields. We demonstrate that a strong electrostatic field near an ion reorganizes dipolar monomers, resulting in nonmonotonic changes in the volume fraction profile and the dielectric function of the polymers with respect to those of simple liquid mixtures. For the parameter sets used, the spatial variations near an ion can be in the range of 1 nm or larger, producing significant differences in the solvation energy among simple liquid mixtures, polymer blends, and block copolymers. The solvation energy of an ion depends substantially on the chain length in block copolymers; thus, our theory predicts the preferential solvation of ions arising from differences in chain length.

  2. Modeling of ionic transport in solid polymer electrolytes

    International Nuclear Information System (INIS)

    Cheang, P L; Teo, L L; Lim, T L

    2010-01-01

    A Monte Carlo model describing the ionic trans port in solid polyme relectrolyte is developed. Single cation simulation is carried out using hopping rate to study the transport mechanism of a thermally activated ion in solid polymer electrolyte. In our model, the ion is able to hop along a polymer chain and to jump between different chains, surmounting energy barriers that consist of polymer's activation energy and the externally applied electric field. The model is able to trace the motion of ion across polymer electrolyte. The mean hopping distance is calculated based on the available open bond in the next nearest side. Random numbers are used to determine the hopping distances, free flight times, final energy and direction of the cation after successful hop. Drift velocity and energy of cation are simulated in our work. The model is expected to be able to simulate the lithium-polymer battery in future.

  3. Rapid, facile synthesis of conjugated polymer zwitterions in ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Page, Zachariah A. [Polymer Science & Engineering Department; Conte Center for Polymer Research; University of Massachusetts; Amherst, USA; Liu, Feng [Polymer Science & Engineering Department; Conte Center for Polymer Research; University of Massachusetts; Amherst, USA; Russell, Thomas P. [Polymer Science & Engineering Department; Conte Center for Polymer Research; University of Massachusetts; Amherst, USA; Emrick, Todd [Polymer Science & Engineering Department; Conte Center for Polymer Research; University of Massachusetts; Amherst, USA

    2014-01-01

    Ionic liquids (ILs) were utilized for the rapid air-stable Suzuki polymerization of polar zwitterionic thiophene monomers, precluding the need for volatile organic solvents, phosphine ligands and phase transfer catalysts typically used in conjugated polymer synthesis.

  4. Synthesis and Characterization of Branched Ionomers for Performance in Ionic Liquid â Swollen Ionic Polymer Transducers

    OpenAIRE

    Duncan, Andrew Jay

    2009-01-01

    Ionic polymer transducers (IPT) are a class of electroactive polymer devices that exhibit electromechanical coupling through charge transport in ionomeric membranes that contain a charge mobilizing diluent and are interfaced with conducting electrodes. Applications of these active materials have been broadly developed in the field of actuators and sensors. Advances in fundamental understanding of IPT performance mechanisms and tuning of the device components has primarily focused on transduce...

  5. Predictions of flavonoid solubility in ionic liquids by COSMO-RS: experimental verification, structural elucidation, and solvation characterization

    DEFF Research Database (Denmark)

    Guo, Zheng; Lue, Bena-Marie; Thomsen, Kaj

    2007-01-01

    Predictions of the solubility of flavonoids in a large variety of ionic liquids (ILs) with over 1800 available structures were examined based on COSMO-RS computation. The results show that the solubilities of flavonoids are strongly anion-dependent. Experimental measurement of the solubilities...... of esculin and rutin in 12 ILs with varying anions and cations show that predicted and experimental results generally have a good agreement. Based on the sound physical basis of COSMO-RS, the solubility changes of flavonoids were quantitatively associated with solvation interactions and structural...... characteristics of ILs. COSMO-RS derived parameters, i.e. misfit, H-bonding and van der Waals interaction energy, are shown to be capable of characterizing the complicated multiple interactions in the IL system effectively. H-bonding interaction is the most dominant interaction for ILs (followed by misfit and van...

  6. [Experimental and computation studies of polar solvation

    International Nuclear Information System (INIS)

    1990-01-01

    This report from the Pennsylvania State University contains seven sections: (1) radiative rate effects in solvatlvatochromic probes; (2) intramolecular charge transfer reactions; (3) Solvation dynamics in low temperature alcohols; (4) Ionic solvation dynamics; (5) solvation and proton-transfer dynamics in 7-azaindole; (6) computer simulations of solvation dynamics; (7) solvation in supercritical fluids. 20 refs., 11 figs

  7. Self-consistent field theory of polymer-ionic molecule complexation

    OpenAIRE

    Nakamura, Issei; Shi, An-Chang

    2010-01-01

    A self-consistent field theory is developed for polymers that are capable of binding small ionic molecules (adsorbates). The polymer-ionic molecule association is described by Ising-like binding variables, C_(i)^(a)(kΔ)(= 0 or 1), whose average determines the number of adsorbed molecules, nBI. Polymer gelation can occur through polymer-ionic molecule complexation in our model. For polymer-polymer cross-links through the ionic molecules, three types of solutions for nBI are obtained, depending...

  8. A shell-resolved analysis of preferential solvation of coffee ingredients in aqueous mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate

    Science.gov (United States)

    Zeindlhofer, Veronika; Berger, Magdalena; Steinhauser, Othmar; Schröder, Christian

    2018-05-01

    Ionic liquids increase the solubility of various coffee ingredients in aqueous solution but little is known about the underlying mechanism. Kirkwood-Buff integrals as well as the potential of mean force indicate that the imidazolium cations are accumulated at the surface of the solutes, removing water molecules from the solute surface. Although hydrogen bonding of the anions to hydroxy groups of the solutes can be detected, their concentration at the surface is less enhanced compared to the cations. The decomposition into solvation shells by Voronoi tessellation reveals that structural features are only observed in the first solvation shell. Nevertheless, the depletion of water and the excess concentration of the ions and, in particular, of the cations are visible in the next solvation shells as well. Therefore, classical arguments of hydrotropic theory fail to explain this behavior.

  9. Dispersion and Solvation Effects on the Structure and Dynamics of N719 Adsorbed to Anatase Titania (101) Surfaces in Room-Temperature Ionic Liquids: An ab Initio Molecular Simulation Study

    KAUST Repository

    Byrne, Aaron; English, Niall J.; Schwingenschlö gl, Udo; Coker, David F.

    2015-01-01

    Ab initio, density functional theory (DFT)-based molecular dynamics (MD) has been carried out to investigate the effect of explicit solvation on the dynamical and structural properties of a [bmim][NTf2] room-temperature ionic liquid (RTIL

  10. Tridimensional ionic polymer metal composites: optimization of the manufacturing techniques

    International Nuclear Information System (INIS)

    Bonomo, C; Brunetto, P; Fortuna, L; Graziani, S; Bottino, M; Di Pasquale, G; Pollicino, A

    2010-01-01

    Ionic polymer metal composites (IPMCs) belong to electroactive polymers (EAPs) and have been suggested for various applications due to their light weight and to the fact that they react mechanically when stimulated by an electrical signal and vice versa. Thick IPMCs (3D-IPMCs) have been fabricated by hot pressing several Nafion ® 117 films. Additional post-processes (more cycles of Pt electroless plating and dispersing agents) have been applied to improve the 3D-IPMC performance. The electromechanical response of 3D-IPMCs has been examined by applying electrical signals and measuring the displacement and blocking force produced

  11. Thin Films Formed from Conjugated Polymers with Ionic, Water-Soluble Backbones

    NARCIS (Netherlands)

    Voortman, Thomas P; Chiechi, Ryan C

    2015-01-01

    This paper compares the morphologies of films of conjugated polymers in which the backbone (main chain) and pendant groups are varied between ionic/hydrophilic and aliphatic/hydrophobic. We observe that conjugated polymers in which the pendant groups and backbone are matched, either ionic-ionic or

  12. SO2 Solvation in the 1-Ethyl-3-Methylimidazolium Thiocyanate Ionic Liquid by Incorporation into the Extended Cation-Anion Network.

    Science.gov (United States)

    Firaha, Dzmitry S; Kavalchuk, Mikhail; Kirchner, Barbara

    We have carried out an ab initio molecular dynamics study on the sulfur dioxide (SO 2 ) solvation in 1-ethyl-3-methylimidazolium thiocyanate for which we have observed that both cations and anions play an essential role in the solvation of SO 2 . Whereas, the anions tend to form a thiocyanate- and much less often an isothiocyanate-SO 2 adduct, the cations create a "cage" around SO 2 with those groups of atoms that donate weak interactions like the alkyl hydrogen atoms as well as the heavy atoms of the [Formula: see text]-system. Despite these similarities between the solvation of SO 2 and CO 2 in ionic liquids, an essential difference was observed with respect to the acidic protons. Whereas CO 2 avoids accepting hydrogen bonds form the acidic hydrogen atoms of the cations, SO 2 can from O(SO 2 )-H(cation) hydrogen bonds and thus together with the strong anion-adduct it actively integrates in the hydrogen bond network of this particular ionic liquid. The fact that SO 2 acts in this way was termed a linker effect by us, because the SO 2 can be situated between cation and anion operating as a linker between them. The particular contacts are the H(cation)[Formula: see text]O(SO 2 ) hydrogen bond and a S(anion)-S(SO 2 ) sulfur bridge. Clearly, this observation provides a possible explanation for the question of why the SO 2 solubility in these ionic liquids is so high.

  13. Solvation behaviour of L-leucine in aqueous ionic liquid at different temperatures: Volumetric approach

    Science.gov (United States)

    Sharma, Samriti; Sandarve, Sharma, Amit K.; Sharma, Meena

    2018-05-01

    For the investigation of interactions of L-leucine in aqueous solutions of an ionic liquid (1-butyl-3-methylimidazolium tetra fluoroborate [Bmim][BF4]) at atmospheric pressure over a temperature range of (293.15K to 313.16K), we use the volumetric approach. By using the density data we have calculated the apparent molar volume, VΦ, limiting apparent molar volume, V0Φ, the slope, Sv, partial molar volume of transfer, V0Φ,tr. The values of these acoustical parameters have been used for the interpretation of different interactions like hydrophilic-hydrophilic, hydrophilic-hydrophobic, ion hydrophilic, solute-solvent and solute-solute interactions in the amino acid and ionic liquid solutions.

  14. Recent applications of ionic liquids in the sol-gel process for polymer-silica nanocomposites with ionic interfaces

    Czech Academy of Sciences Publication Activity Database

    Donato, K. Z.; Matějka, Libor; Mauler, R. S.; Donato, R. K.

    2017-01-01

    Roč. 1, č. 1 (2017), s. 1-25, č. článku 5. E-ISSN 2504-5377 Institutional support: RVO:61389013 Keywords : ionic liquids * sol-gel * ionic interfaces Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science

  15. Ionic electroactive polymer artificial muscles in space applications.

    Science.gov (United States)

    Punning, Andres; Kim, Kwang J; Palmre, Viljar; Vidal, Frédéric; Plesse, Cédric; Festin, Nicolas; Maziz, Ali; Asaka, Kinji; Sugino, Takushi; Alici, Gursel; Spinks, Geoff; Wallace, Gordon; Must, Indrek; Põldsalu, Inga; Vunder, Veiko; Temmer, Rauno; Kruusamäe, Karl; Torop, Janno; Kaasik, Friedrich; Rinne, Pille; Johanson, Urmas; Peikolainen, Anna-Liisa; Tamm, Tarmo; Aabloo, Alvo

    2014-11-05

    A large-scale effort was carried out to test the performance of seven types of ionic electroactive polymer (IEAP) actuators in space-hazardous environmental factors in laboratory conditions. The results substantiate that the IEAP materials are tolerant to long-term freezing and vacuum environments as well as ionizing Gamma-, X-ray, and UV radiation at the levels corresponding to low Earth orbit (LEO) conditions. The main aim of this material behaviour investigation is to understand and predict device service time for prolonged exposure to space environment.

  16. Interaction Studies between Newly Synthesized Photosensitive Polymer and Ionic Liquids

    Directory of Open Access Journals (Sweden)

    In Tae Kim

    2015-01-01

    Full Text Available In this information age, different kinds of photosensitive materials have been used in the manufacture of information storage devices. But these photosensitive materials have the bane of low diffraction efficiency. In order to solve this problem, we have synthesized a novel photosensitive polymer from epoxy-based azopolymers (with three types of azochromophores. Furthermore, we have studied the interaction between this newly synthesized azopolymer and ionic liquids (ILs. For this purpose, we have used the ammonium and imidazolium families of ILs, such as diethylammonium dihydrogen phosphate (DEAP, tributylammonium methyl sulfate (TBMS, triethylammonium 4-aminotoluene-3-sulfonic acid (TASA, and 1-methylimidazolium chloride ([Mim]Cl. To investigate the molecular interaction between azopolymer and ILs, we have used the following spectroscopic methods of analysis: UV-visible spectroscopy, photoluminescence (PL spectroscopy, Fourier transformed infrared spectroscopy (FT-IR, and confocal Raman spectroscopy. In this study, we have developed new photosensitive materials by combining polymer with ILs.

  17. Separation process for lanthanides based on solvation properties of non ionic surfactants

    International Nuclear Information System (INIS)

    Draye, M.; Favre-Reguillon, A.; Foos, J.; Cote, G.

    2004-01-01

    In the present study, cloud-point extraction is used with a lipophilic chelating agent (8-hydroxyquinoline) to extract and separate lanthanum (III) and gadolinium (III) from an aqueous solution. The methodology used is based on the formation of lanthanide (III) organic complexes that are soluble in a micellar phase of non-ionic surfactant. The lanthanide (III) complexes are then extracted into the surfactant-rich phase at a temperature above the cloud-point temperature. The cloud-point temperature, the structure of the lipophilic part of the nonionic surfactant and the chelating agent - metal molar ratio are identified as factors determining the extraction efficiency and selectivity. With Triton X-114, high selectivity and decontamination factor for Gd(III) is observed indicating that micelle mediated extraction involving cloud-point extraction is promising for the specific separation of actinide ions from nuclear waste solution. (authors)

  18. Ionic Polymer Microactuator Activated by Photoresponsive Organic Proton Pumps

    Directory of Open Access Journals (Sweden)

    Khaled M. Al-Aribe

    2015-10-01

    Full Text Available An ionic polymer microactuator driven by an organic photoelectric proton pump transducer is described in this paper. The light responsive transducer is fabricated by using molecular self-assembly to immobilize oriented bacteriorhodopsin purple membrane (PM patches on a bio-functionalized porous anodic alumina (PAA substrate. When exposed to visible light, the PM proton pumps produce a unidirectional flow of ions through the structure’s nano-pores and alter the pH of the working solution in a microfluidic device. The change in pH is sufficient to generate an osmotic pressure difference across a hydroxyethyl methacrylate-acrylic acid (HEMA-AA actuator shell and induce volume expansion or contraction. Experiments show that the transducer can generate an ionic gradient of 2.5 μM and ionic potential of 25 mV, producing a pH increase of 0.42 in the working solution. The ΔpH is sufficient to increase the volume of the HEMA-AA microactuator by 80%. The volumetric transformation of the hydrogel can be used as a valve to close a fluid transport micro-channel or apply minute force to a mechanically flexible microcantilever beam.

  19. Micro-mechanics of ionic electroactive polymer actuators

    Science.gov (United States)

    Punning, Andres; Põldsalu, Inga; Kaasik, Friedrich; Vunder, Veiko; Aabloo, Alvo

    2015-04-01

    Commonly, modeling of the bending behavior of the ionic electroactive polymer (IEAP) actuators is based on the classical mechanics of cantilever beam. It is acknowledged, that the actuation of the ionic electroactive polymer (IEAP) actuators is symmetric about the centroid - the convex side of the actuator is expanding and the concave side is contracting for exactly the same amount, while the thickness of the actuator remains invariant. Actuating the IEAP actuators and sensors under scanning electron microscope (SEM), in situ, reveals that for some types of them this approach is incorrect. Comparison of the SEM micrographs using the Digital Image Correction (DIC) method results with the precise strain distribution of the IEAP actuators in two directions: in the axial direction, and in the direction of thickness. This information, in turn, points to the physical processes taking place within the electrodes as well as membrane of the trilayer laminate of sub-millimeter thickness. Comparison of the EAP materials, engaged as an actuator as well as a sensor, reveals considerable differences between the micro-mechanics of the two modes.

  20. Ionomer design for augmented charge transport in novel ionic polymer transducers

    International Nuclear Information System (INIS)

    Duncan, Andrew J; Akle, Barbar J; Long, Timothy E; Leo, Donald J

    2009-01-01

    Ionic polymer transducers are devices that display electromechanical transduction and are projected to have extensive applications as actuators and sensors. This study employs novel, highly branched sulfonated polysulfones (sBPS) as part of an investigation into the contribution of polymer topology to electromechanical transduction. Specifically, the ionomers are combined with an ionic liquid to determine the optimal ratio and method for maximizing ionic conductivity, where charge transport is essential to device performance. Two uptake methods are assessed for introduction of ionic liquid into the central ionomeric membrane. The effects of casting membranes in the presence of ionic liquid and swelling preformed membranes in ionic liquid on film stability and ionic conductivity are examined. Membranes cast from a solution of the ionomer and ionic liquid allow for direct targeting of the component ratio and a single-step process for membrane formation. Swelling conditions for preformed neat membranes combine time, temperature, and the presence of organic co-diluents to achieve the maximum stable uptake of ionic liquid. Comparison of optimal conditions for the various methods reveals that swelling with co-diluents achieves ionic conductivity of the imbibed membrane per uptake higher than the levels achieved with the casting process for highly sulfonated sBPS. However, for less sulfonated sBPS the casting process successfully produced membranes with ionic conductivities unreachable with the co-diluent process. Both methods will enable the production of high performance ionic polymer transducers constructed from novel sBPS ionomers and ionic liquids

  1. Effect of ionic liquid on the solvation behavior of nonaqueous N,N′-salicylidenephenylediamine Schiff base (Salophen) solutions at 298.15 K

    International Nuclear Information System (INIS)

    Shekaari, Hemayat; Elhami-Kalvanagh, Rasoul; Bezaatpour, Abolfazl

    2013-01-01

    Highlights: • Salophen schiff base and ionic liquid, [BMIm]Br were synthesized. • Thermodynamic properties of Salophen + [BMIm]Br + organic solvents were measured. • The calculated parameters were used to interpretation of the solute–solvent interactions. • The results show that the predominant interactions are nonpolar–nonpolar interactions. • Solubility of Salophen increase with increasing of [BMIm]Br concentrations. -- Abstract: Thermodynamic properties of N,N′-salicylidenephenylediamine Schiff base (Salophen) in the solutions of ionic liquid, 1-butyl-3-methylimidazolium bromide ([BMIm]Br) + organic solvents (N,N-dimethylacetamide DMA, and dimethylsulfoxide DMSO) have been measured at 298.15 K. The measured density and viscosity values have been used to calculate apparent molar volumes, V ϕ , standard partial molar volumes, V ϕ 0 , standard partial molar volumes of transfer, Δ tr V ϕ 0 , viscosity B-coefficients, and solvation numbers, B/V ϕ 0 , for the solutions being studied. All of these parameters were used to interpret the solute–solvent interactions and solvation process occurring between ionic liquid and Salophen

  2. Ionic polymer metal composites with polypyrrole-silver electrodes

    Science.gov (United States)

    Cellini, F.; Grillo, A.; Porfiri, M.

    2015-03-01

    Ionic polymer metal composites (IPMCs) are a class of soft active materials that are finding increasing application in robotics, environmental sensing, and energy harvesting. In this letter, we demonstrate the fabrication of IPMCs via in-situ photoinduced polymerization of polypyrrole-silver electrodes on an ionomeric membrane. The composition, morphology, and sheet resistance of the electrodes are extensively characterized through a range of experimental techniques. We experimentally investigate IPMC electrochemistry through electrochemical impedance spectroscopy, and we propose a modified Randle's model to interpret the impedance spectrum. Finally, we demonstrate in-air dynamic actuation and sensing and assess IPMC performance against more established fabrication methods. Given the simplicity of the process and the short time required for the formation of the electrodes, we envision the application of our technique in the development of a rapid prototyping technology for IPMCs.

  3. A resonant force sensor based on ionic polymer metal composites

    International Nuclear Information System (INIS)

    Bonomo, Claudia; Fortuna, Luigi; Giannone, Pietro; Graziani, Salvatore; Strazzeri, Salvatore

    2008-01-01

    In this paper a novel force sensor, based on ionic polymer metal composites (IPMCs), is presented. The system has DC sensing capabilities and is able to work in the range of a few millinewtons. IPMCs are emerging materials used to realize motion actuators and sensors. An IPMC strip is activated in a beam fixed/simply-supported configuration. The beam is tightened at the simply-supported end by a force. This influences the natural resonant frequency of the beam; the value of the resonant frequency is used in the proposed system to estimate the force applied in the axial direction. The performance of the system based on the IPMC material has proved to be comparable with that of sensors based on other sensing mechanisms. This suggests the possibility of using this class of polymeric devices to realize PMEMS (plastic micro electrical mechanical systems) sensors

  4. A model for ionic polymer metal composites as sensors

    Science.gov (United States)

    Bonomo, C.; Fortuna, L.; Giannone, P.; Graziani, S.; Strazzeri, S.

    2006-06-01

    This paper introduces a comprehensive model of sensors based on ionic polymer metal composites (IPMCs) working in air. Significant quantities ruling the sensing properties of IPMC-based sensors are taken into account and the dynamics of the sensors are modelled. A large amount of experimental evidence is given for the excellent agreement between estimations obtained using the proposed model and the observed signals. Furthermore, the effect of sensor scaling is investigated, giving interesting support to the activities involved in the design of sensing devices based on these novel materials. We observed that the need for a wet environment is not a key issue for IPMC-based sensors to work well. This fact allows us to put IPMC-based sensors in a totally different light to the corresponding actuators, showing that sensors do not suffer from the same drawbacks.

  5. A resonant force sensor based on ionic polymer metal composites

    Science.gov (United States)

    Bonomo, Claudia; Fortuna, Luigi; Giannone, Pietro; Graziani, Salvatore; Strazzeri, Salvatore

    2008-02-01

    In this paper a novel force sensor, based on ionic polymer metal composites (IPMCs), is presented. The system has DC sensing capabilities and is able to work in the range of a few millinewtons. IPMCs are emerging materials used to realize motion actuators and sensors. An IPMC strip is activated in a beam fixed/simply-supported configuration. The beam is tightened at the simply-supported end by a force. This influences the natural resonant frequency of the beam; the value of the resonant frequency is used in the proposed system to estimate the force applied in the axial direction. The performance of the system based on the IPMC material has proved to be comparable with that of sensors based on other sensing mechanisms. This suggests the possibility of using this class of polymeric devices to realize PMEMS (plastic micro electrical mechanical systems) sensors.

  6. Electromechanical modelling of tapered ionic polymer metal composites transducers

    Directory of Open Access Journals (Sweden)

    Rakesha Chandra Dash

    2016-09-01

    Full Text Available Ionic polymer metal composites (IPMCs are relatively new smart materials that exhibit a bidirectional electromechanical coupling. IPMCs have large number of important engineering applications such as micro robotics, biomedical devices, biomimetic robotics etc. This paper presents a comparison between tapered and uniform cantilevered Nafion based IPMCs transducer. Electromechanical modelling is done for the tapered beam. Thickness can be varied according to the requirement of force and deflection. Numerical results pertaining to the force and deflection characteristics of both type IPMCs transducer are obtained. It is shown that the desired amount of force and deflections for tapered IPMCs can be achieved for a given voltage. Different fixed end (t0 and free end (t1 thickness values have been taken to justify the results using MATLAB.

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

    Science.gov (United States)

    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 %.

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

    Science.gov (United States)

    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.

  9. High-throughput screening of ionic conductivity in polymer membranes

    International Nuclear Information System (INIS)

    Zapata, Pedro; Basak, Pratyay; Carson Meredith, J.

    2009-01-01

    Combinatorial and high-throughput techniques have been successfully used for efficient and rapid property screening in multiple fields. The use of these techniques can be an advantageous new approach to assay ionic conductivity and accelerate the development of novel materials in research areas such as fuel cells. A high-throughput ionic conductivity (HTC) apparatus is described and applied to screening candidate polymer electrolyte membranes for fuel cell applications. The device uses a miniature four-point probe for rapid, automated point-to-point AC electrochemical impedance measurements in both liquid and humid air environments. The conductivity of Nafion 112 HTC validation standards was within 1.8% of the manufacturer's specification. HTC screening of 40 novel Kynar poly(vinylidene fluoride) (PVDF)/acrylic polyelectrolyte (PE) membranes focused on varying the Kynar type (5x) and PE composition (8x) using reduced sample sizes. Two factors were found to be significant in determining the proton conducting capacity: (1) Kynar PVDF series: membranes containing a particular Kynar PVDF type exhibited statistically identical mean conductivity as other membranes containing different Kynar PVDF types that belong to the same series or family. (2) Maximum effective amount of polyelectrolyte: increments in polyelectrolyte content from 55 wt% to 60 wt% showed no statistically significant effect in increasing conductivity. In fact, some membranes experienced a reduction in conductivity.

  10. Effect of a novel amphipathic ionic liquid on lithium deposition in gel polymer electrolytes

    International Nuclear Information System (INIS)

    Choi, Nam-Soon; Koo, Bonjae; Yeon, Jin-Tak; Lee, Kyu Tae; Kim, Dong-Won

    2011-01-01

    Highlights: · Synthesis of a dimeric ionic liquid. · Gel polymer electrolytes providing uniform lithium deposit pathway. · An amphipathic ionic liquid locates at the interface between an electrolyte-rich phase and a polymer matrix in a gel polymer electrolyte. · The presence of PDMITFSI ionic liquid leads to the suppression of dendritic lithium formation on a lithium metal electrode. - Abstract: A novel dimeric ionic liquid based on imidazolium cation and bis(trifluoromethanesulfonyl) imide (TFSI) anion has been synthesized through a metathesis reaction. Its chemical shift values and thermal properties are identified via 1 H nuclear magnetic resonance (NMR) imaging and differential scanning calorimetry (DSC). The effect of the synthesized dimeric ionic liquid on the interfacial resistance of gel polymer electrolytes is described. Differences in the SEM images of lithium electrodes after lithium deposition with and without the 1,1'-pentyl-bis(2,3-dimethylimidazolium) bis(trifluoromethane-sulfonyl)imide (PDMITFSI) ionic liquid in gel polymer electrolytes are clearly discernible. This occurs because the PDMITFSI ionic liquid with hydrophobic moieties and polar groups modulates lithium deposit pathways onto the lithium metal anode. Moreover, high anodic stability for a gel polymer electrolyte with the PDMITFSI ionic liquid was clearly observed.

  11. Effect of Preferential Solvation of Polymer Chains on Vapor-Pressure Osmometry Results. Computer Simulation Study.

    Czech Academy of Sciences Publication Activity Database

    Svoboda, Martin; Lísal, Martin; Limpouchová, Z.; Procházka, Karel

    2018-01-01

    Roč. 23, č. 3 (2018), s. 244-251 ISSN 1023-666X R&D Projects: GA ČR GA15-19542S Institutional support: RVO:67985858 Keywords : vapor-pressure osmometry * simulation * solvatation Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry

  12. Evidence for Reduced Hydrogen-Bond Cooperativity in Ionic Solvation Shells from Isotope-Dependent Dielectric Relaxation

    Science.gov (United States)

    Cota, Roberto; Ottosson, Niklas; Bakker, Huib J.; Woutersen, Sander

    2018-05-01

    We find that the reduction in dielectric response (depolarization) of water caused by solvated ions is different for H2O and D2O . This isotope dependence allows us to reliably determine the kinetic contribution to the depolarization, which is found to be significantly smaller than predicted by existing theory. The discrepancy can be explained from a reduced hydrogen-bond cooperativity in the solvation shell: we obtain quantitative agreement between theory and experiment by reducing the Kirkwood correlation factor of the solvating water from 2.7 (the bulk value) to ˜1.6 for NaCl and ˜1 (corresponding to completely uncorrelated motion of water molecules) for CsCl.

  13. Studies on the solvation dynamics of coumarin 153 in 1-ethyl-3-methylimidazolium alkylsulfate ionic liquids: dependence on alkyl chain length.

    Science.gov (United States)

    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.

  14. Encapsulation of ionic electroactive polymers: reducing the interaction with environment

    Science.gov (United States)

    Jaakson, P.; Aabloo, A.; Tamm, T.

    2016-04-01

    Ionic electro-active polymer (iEAP) actuators are composite materials that change their mechanical properties in response to external electrical stimulus. The interest in these devices is mainly driven by their capability to generate biomimetic movements, and their potential use in soft robotics. The driving voltage of an iEAP-actuator (0.5… 3 V) is at least an order of magnitude lower than that needed for other types of electroactive polymers. To apply iEAP-actuators in potential real-world applications, the capability of operating in different environments (open air, different solvents) must be available. In their natural form, the iEAP-actuators are capable of interacting with the surrounding environment (evaporation of solvent from the electrolyte solution, ion or solvent exchange, humidity effects), therefore, for prevention of unpredictable behavior of the actuator and the contamination of the environment, encapsulation of the actuator is needed. The environmental contamination aspect of the encapsulation material is substantial when selecting an applicable encapsulant. The suitable encapsulant should form thin films, be light in weight, elastic, fit tightly, low cost, and easily reproducible. The main goal of the present study is to identify and evaluate the best potential encapsulation techniques for iEAPactuators. Various techniques like thin film on liquid coating, dip coating, hot pressing, hot rolling; and several materials like polydimethylsiloxane, polyurethane, nitrocellulose, paraffin-composite-films were investigated. The advantages and disadvantages of the combinations of the above mentioned techniques and materials are discussed. Successfully encapsulated iEAP-actuators gained durability and were stably operable for long periods of time under ambient conditions. The encapsulation process also increased the stability of the iEAP-actuator by minimizing the environment effects. This makes controlling iEAP-actuators more straight-forward and

  15. Nanothorn electrodes for ionic polymer-metal composite artificial muscles.

    Science.gov (United States)

    Palmre, Viljar; Pugal, David; Kim, Kwang J; Leang, Kam K; Asaka, Kinji; Aabloo, Alvo

    2014-08-22

    Ionic polymer-metal composites (IPMCs) have recently received tremendous interest as soft biomimetic actuators and sensors in various bioengineering and human affinity applications, such as artificial muscles and actuators, aquatic propulsors, robotic end-effectors, and active catheters. Main challenges in developing biomimetic actuators are the attainment of high strain and actuation force at low operating voltage. Here we first report a nanostructured electrode surface design for IPMC comprising platinum nanothorn assemblies with multiple sharp tips. The newly developed actuator with the nanostructured electrodes shows a new way to achieve highly enhanced electromechanical performance over existing flat-surfaced electrodes. We demonstrate that the formation and growth of the nanothorn assemblies at the electrode interface lead to a dramatic improvement (3- to 5-fold increase) in both actuation range and blocking force at low driving voltage (1-3 V). These advances are related to the highly capacitive properties of nanothorn assemblies, increasing significantly the charge transport during the actuation process.

  16. Ionic polymer-metal composite enabled robotic manta ray

    Science.gov (United States)

    Chen, Zheng; Um, Tae I.; Bart-Smith, Hilary

    2011-04-01

    The manta ray, Manta birostris, demonstrates excellent swimming capabilities; generating highly efficient thrust via flapping of dorsally flattened pectoral fins. In this paper, we present an underwater robot that mimics the swimming behavior of the manta ray. An assembly-based fabrication method is developed to create the artificial pectoral fins, which are capable of generating oscillatory with a large twisting angle between leading and trailing edges. Ionic polymer-metal composite (IPMC) actuators are used as artificial muscles in the fin. Each fin consists of four IPMC beams bonded with a compliant poly(dimethylsiloxane) (PDMS) membrane. By controlling each individual IPMC strips, we are able to generate complex flapping motions. The fin is characterized in terms of tip deflection, tip blocking force, twist angle, and power consumption. Based on the characteristics of the artificial pectoral fin, a small size and free-swimming robotic manta ray is developed. The robot consists of two artificial pectoral fins, a rigid body, and an on-board control unit with a lithium ion rechargeable battery. Experimental results show that the robot swam at a speed of up to 0.055 body length per second (BL/sec).

  17. Bio-applications of ionic polymer metal composite transducers

    International Nuclear Information System (INIS)

    Aw, K C; McDaid, A J

    2014-01-01

    Traditional robotic actuators have advanced performance which in some aspects can surpass that of humans, however they are lacking when it comes to developing devices which are capable of operating together with humans. Bio-inspired transducers, for example ionic polymer metal composites (IPMC), which have similar properties to human tissue and muscle, demonstrate much future promise as candidates for replacing traditional robotic actuators in medical robotics applications. This paper outlines four biomedical robotics applications, an IPMC stepper motor, an assistive glove exoskeleton/prosthetic hand, a surgical robotic tool and a micromanipulation system. These applications have been developed using mechanical design/modelling techniques with IPMC ‘artificial muscle’ as the actuation system. The systems are designed by first simulating the performance using an IPMC model and dynamic models of the mechanical system; the appropriate advanced adaptive control schemes are then implemented to ensure that the IPMCs operate in the correct manner, robustly over time. This paper serves as an overview of the applications and concludes with some discussion on the future challenges of developing real-world IPMC applications

  18. A nonlinear model for ionic polymer metal composites as actuators

    Science.gov (United States)

    Bonomo, C.; Fortuna, L.; Giannone, P.; Graziani, S.; Strazzeri, S.

    2007-02-01

    This paper introduces a comprehensive nonlinear dynamic model of motion actuators based on ionic polymer metal composites (IPMCs) working in air. Significant quantities ruling the acting properties of IPMC-based actuators are taken into account. The model is organized as follows. As a first step, the dependence of the IPMC absorbed current on the voltage applied across its thickness is taken into account; a nonlinear circuit model is proposed to describe this relationship. In a second step the transduction of the absorbed current into the IPMC mechanical reaction is modelled. The model resulting from the cascade of both the electrical and the electromechanical stages represents a novel contribution in the field of IPMCs, capable of describing the electromechanical behaviour of these materials and predicting relevant quantities in a large range of applied signals. The effect of actuator scaling is also investigated, giving interesting support to the activities involved in the design of actuating devices based on these novel materials. Evidence of the excellent agreement between the estimations obtained by using the proposed model and experimental signals is given.

  19. Ionic Liquid based polymer electrolytes for electrochemical sensors

    Directory of Open Access Journals (Sweden)

    Jakub Altšmíd

    2015-09-01

    Full Text Available Amperometric NO2 printed sensor with a new type of solid polymer electrolyte and a carbon working electrode has been developed. The electrolytes based on 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonylimide [EMIM][N(Tf2], 1-butyl-3-methylimidazolium trifluoromethanesulfonate [BMIM][CF3SO3] and 1-ethyl-3-methylimidazolium tetrafluoroborate [EMIM][BF4] ionic liquids were immobilized in poly(vinylidene fluoride matrix [PVDF]. The analyte, gaseous nitrogen dioxide, was detected by reduction at -500 mV vs. platinum pseudoreference electrode. The sensors showed a linear behavior in the whole tested range, i.e., 0 - 5 ppm and their sensitivities were in order of 0.3 x∙10-6 A/ppm. The sensor sensitivity was influenced by the electric conductivity of printing formulation; the higher the conductivity, the higher the sensor sensitivity. The rise/recovery times were in order of tens of seconds. The use of  screen printing technology and platinum pseudoreference electrode simplify the sensor fabrication and it does not have any negative effect on the sensor stability.DOI: http://dx.doi.org/10.5755/j01.ms.21.3.7371

  20. Bio-applications of ionic polymer metal composite transducers

    Science.gov (United States)

    Aw, K. C.; McDaid, A. J.

    2014-07-01

    Traditional robotic actuators have advanced performance which in some aspects can surpass that of humans, however they are lacking when it comes to developing devices which are capable of operating together with humans. Bio-inspired transducers, for example ionic polymer metal composites (IPMC), which have similar properties to human tissue and muscle, demonstrate much future promise as candidates for replacing traditional robotic actuators in medical robotics applications. This paper outlines four biomedical robotics applications, an IPMC stepper motor, an assistive glove exoskeleton/prosthetic hand, a surgical robotic tool and a micromanipulation system. These applications have been developed using mechanical design/modelling techniques with IPMC ‘artificial muscle’ as the actuation system. The systems are designed by first simulating the performance using an IPMC model and dynamic models of the mechanical system; the appropriate advanced adaptive control schemes are then implemented to ensure that the IPMCs operate in the correct manner, robustly over time. This paper serves as an overview of the applications and concludes with some discussion on the future challenges of developing real-world IPMC applications.

  1. Possible use of ionic polymers for treatment of radioactive liquid waste

    International Nuclear Information System (INIS)

    Siyam, T.; Nofal, M.; Eldessouky, M.I.; Aly, H.F.

    1992-01-01

    Water-soluble nonionic polymers such as polyacrylamide is recently introduced for treatment of radioactive liquid waste. Eater-soluble ionic polymers such as: poly (sodium acrylate) [anionic polymer], poly (acrylamide-CO-sodium acrylate) [anionic copolymer] and poly (acrylamide-sodium acrylate-diallyldiethylammonium chloride) [amphoteric terpolymer] were prepared by gamma radiation-initiated polymerization of the corresponding monomer solutions. The prepared polymers were assessed for use in treatment of radionuclides that might be present in radioactive waste effluents. It was found that the polymer efficiency for cobalt-60 was affected by the composition of the copolymer and the degree of ionization of the polymer. The efficiency of the polymer increases with increasing the concentration of the polymer. The mechanism of sludge formation for each type of polymer was discussed. It was found that the anionic copolymer is more selective for cobalt than the prepared polymers. Amphoteric terpolymer has different selectivity for cations and anions. 3 figs, 1 tab

  2. Halide anion solvation and recognition by a macro tri-cyclic tetra-ammonium host in an ionic liquid: a molecular dynamics stud

    International Nuclear Information System (INIS)

    Chaumont, A.; Wipff, G.

    2006-01-01

    We report a molecular dynamics study of halide anions X - and their inclusion complexes X - - L 4+ with a macro-tri-cyclic tetrahedral host L 4+ built from four quaternary ammonium sites, in an ionic liquid (IL) based on the 1-butyl-3-methyl-imidazolium (BMI + ) cation and the PF 6 - anion. The 'dry' and 'humid' forms of the [BMI][PF 6 ] IL are compared, showing the importance of IL ions in the 'dry' IL and, in some cases, of water molecules in the 'humid' IL. In the 'dry' IL the F - , Cl - , Br - and I - un-complexed halides are surrounded by 4-5 BMI + cations whose binding mode evolves from hydrogen bonding to facial coordination along this series. Solvent humidity has the largest impact on the solvation of F - whose first shell BMI + cations are all displaced by H 2 O molecules, while the first solvation shell of Cl - , Br - and I - comprises 3-4 BMI + cations plus ca. 4 H 2 O molecules. The solvation of the L 4+ host and of its X - - L 4+ complex mainly involves PF 6 - anions in the 'dry' IL, and additional H 2 O molecules in the 'humid' IL. The question of anion binding selectivity is addressed by free energy perturbation calculations which predict that, in the 'dry' liquid, F - is preferred over Cl - , Br - and I - , which contrasts with the aqueous solution where L 4+ is selective for Cl - . In the 'humid' liquid however, there is no F - /Cl - discrimination, showing the importance of small amounts of water on the complexation selectivity. (authors)

  3. Comparative Experimental Study on Ionic Polymer Mental Composite based on Nafion and Aquivion Membrane as Actuators

    Science.gov (United States)

    Luo, B.; Chen, Z.

    2017-11-01

    Most ionic polymer mental composites employ Nafion as the polymer matrix, Aquivion can also manufactured as ionic polymer mental composite while research was little. This paper researched on two kinds of ionic polymer mental composite based on Aquivion and Nafion matrix with palladium electrode called Aquivion-IPMC and Nafion-IPMC. The samples were fabricated by the same preparation process. The current and deformation responses of the samples were measured at voltage to characterize the mechano-electrical properties. The experimental observations revealed that shorter flexible side chains in Aquivion-IPMC provide a larger force than Nafion-IPMC, while the displacement properties were similar in two different samples. The results also showed that Aquivion membrane can also replace Nafion to reproduce IPMC application in soft robots, MEMS, and so on.

  4. Cycling performance of lithium polymer cells assembled by in situ polymerization of a non-flammable ionic liquid monomer

    International Nuclear Information System (INIS)

    Lee, Yoon-Sung; Kim, Dong-Won

    2013-01-01

    Highlights: • Gel polymer electrolytes were synthesized by in situ polymerization of ionic liquid in the lithium polymer cells. • Flammability of the electrolyte was significantly reduced by polymerizing electrolyte containing a non-flammable ionic liquid monomer. • The cells assembled with polymeric ionic liquid-based electrolytes exhibited reversible cycling behavior with good capacity retention. -- Abstract: Lithium polymer cells composed of a lithium negative electrode and a LiCoO 2 positive electrode were assembled with a gel polymer electrolyte obtained by in situ polymerization of an electrolyte solution containing an ionic liquid monomer with vinyl groups. The polymerization of the electrolyte solution containing the non-flammable ionic liquid monomer resulted in a significant reduction of the flammability of the gel polymer electrolytes. The lithium polymer cell assembled with the stable gel polymer electrolyte delivered a discharge capacity of 134.3 mAh g −1 at ambient temperature and exhibited good capacity retention

  5. Self-consistent field theory of polymer-ionic molecule complexation.

    Science.gov (United States)

    Nakamura, Issei; Shi, An-Chang

    2010-05-21

    A self-consistent field theory is developed for polymers that are capable of binding small ionic molecules (adsorbates). The polymer-ionic molecule association is described by Ising-like binding variables, C(i) ((a))(kDelta)(=0 or 1), whose average determines the number of adsorbed molecules, n(BI). Polymer gelation can occur through polymer-ionic molecule complexation in our model. For polymer-polymer cross-links through the ionic molecules, three types of solutions for n(BI) are obtained, depending on the equilibrium constant of single-ion binding. Spinodal lines calculated from the mean-field free energy exhibit closed-loop regions where the homogeneous phase becomes unstable. This phase instability is driven by the excluded-volume interaction due to the single occupancy of ion-binding sites on the polymers. Moreover, sol-gel transitions are examined using a critical degree of conversion. A gel phase is induced when the concentration of adsorbates is increased. At a higher concentration of the adsorbates, however, a re-entrance from a gel phase into a sol phase arises from the correlation between unoccupied and occupied ion-binding sites. The theory is applied to a model system, poly(vinyl alcohol) and borate ion in aqueous solution with sodium chloride. Good agreement between theory and experiment is obtained.

  6. Driving mechanisms of ionic polymer actuators having electric double layer capacitor structures.

    Science.gov (United States)

    Imaizumi, Satoru; Kato, Yuichi; Kokubo, Hisashi; Watanabe, Masayoshi

    2012-04-26

    Two solid polymer electrolytes, composed of a polyether-segmented polyurethaneurea (PEUU) and either a lithium salt (lithium bis(trifluoromethanesulfonyl)amide: Li[NTf2]) or a nonvolatile ionic liquid (1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide: [C2mim][NTf2]), were prepared in order to utilize them as ionic polymer actuators. These salts were preferentially dissolved in the polyether phases. The ionic transport mechanism of the polyethers was discussed in terms of the diffusion coefficients and ionic transference numbers of the incorporated ions, which were estimated by means of pulsed-field gradient spin-echo (PGSE) NMR. There was a distinct difference in the ionic transport properties of each polymer electrolyte owing to the difference in the magnitude of interactions between the cations and the polyether. The anionic diffusion coefficient was much faster than that of the cation in the polyether/Li[NTf2] electrolyte, whereas the cation diffused faster than the anion in the polyether/[C2mim][NTf2] electrolyte. Ionic polymer actuators, which have a solid-state electric-double-layer-capacitor (EDLC) structure, were prepared using these polymer electrolyte membranes and ubiquitous carbon materials such as activated carbon and acetylene black. On the basis of the difference in the motional direction of each actuator against applied voltages, a simple model of the actuation mechanisms was proposed by taking the difference in ionic transport properties into consideration. This model discriminated the behavior of the actuators in terms of the products of transference numbers and ionic volumes. The experimentally observed behavior of the actuators was successfully explained by this model.

  7. Polymer synthesis in ionic liquids : towards a green industry

    NARCIS (Netherlands)

    Guerrero-Sanchez, C.A.; Schubert, U.S.

    2004-01-01

    The screening of six ionic liqs. used as reaction media in free radical polymn. of Me methacrylate and styrene was performed. AIBN was used as initiator for the polymn. of Me methacrylate and benzoyl peroxide in the case of styrene. Soly. of the used ionic liqs. in these monomers and water was also

  8. Electrospun polymer membrane activated with room temperature ionic liquid: Novel polymer electrolytes for lithium batteries

    Science.gov (United States)

    Cheruvally, Gouri; Kim, Jae-Kwang; Choi, Jae-Won; Ahn, Jou-Hyeon; Shin, Yong-Jo; Manuel, James; Raghavan, Prasanth; Kim, Ki-Won; Ahn, Hyo-Jun; Choi, Doo Seong; Song, Choong Eui

    A new class of polymer electrolytes (PEs) based on an electrospun polymer membrane incorporating a room-temperature ionic liquid (RTIL) has been prepared and evaluated for suitability in lithium cells. The electrospun poly(vinylidene fluoride- co-hexafluoropropylene) P(VdF-HFP) membrane is activated with a 0.5 M solution of LiTFSI in 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMITFSI) or a 0.5 M solution of LiBF 4 in 1-butyl-3-methylimidazolium tetrafluoroborate (BMIBF 4). The resulting PEs have an ionic conductivity of 2.3 × 10 -3 S cm -1 at 25 °C and anodic stability at >4.5 V versus Li +/Li, making them suitable for practical applications in lithium cells. A Li/LiFePO 4 cell with a PE based on BMITFSI delivers high discharge capacities when evaluated at 25 °C at the 0.1 C rate (149 mAh g -1) and the 0.5 C rate (132 mAh g -1). A very stable cycle performance is also exhibited at these low current densities. The properties decrease at the higher, 1 C rate, when operated at 25 °C. Nevertheless, improved properties are obtained at a moderately elevated temperature of operation, i.e. 40 °C. This is attributed to enhanced conductivity of the electrolyte and faster reaction kinetics at higher temperatures. At 40 °C, a reversible capacity of 140 mAh g -1 is obtained at the 1 C rate.

  9. Solvation Mechanism of Task-Specific Ionic Liquids in Water: A Combined Investigation Using Classical Molecular Dynamics and Density Functional Theory.

    Science.gov (United States)

    Yuvaraj, Surya V J; Zhdanov, Ravil K; Belosludov, Rodion V; Belosludov, Vladimir R; Subbotin, Oleg S; Kanie, Kiyoshi; Funaki, Kenji; Muramatsu, Atsushi; Nakamura, Takashi; Kawazoe, Yoshiyuki

    2015-10-08

    The solvation behavior of task-specific ionic liquids (TSILs) containing a common, L-histidine derived imidazolium cation [C20H28N3O3](+) and different anions, bromide-[Br](-) and bis(trifluoromethylsulfonyl)amide-[NTF2](-), in water is examined, computationally. These amino acid functionalized ionic liquids (ILs) are taken into account because of their ability to react with rare earth metal salts. It has been noted that the TSIL with [Br](-) is more soluble than its counterpart TSIL with [NTF2](-), experimentally. In this theoretical work, the combined classical molecular dynamics (CMD) and density functional theory (DFT) calculations are performed to study the behavior of the bulk phase of these two TSILs in the vicinity of water (H2O) molecules with different concentrations. Initially, all the constructed systems are equilibrated using the CMD method. The final structures of the equilibrated systems are extracted for DFT calculations. Under CMD operation, the radial distribution function (RDF) plots and viscosity of TSILs are analyzed to understand the effect of water on TSILs. In the DFT regime, binding energy per H2O, charge transfer, charge density mapping, and electronic density of states (EDOS) analyses are done. The CMD results along with the DFT results are consolidated to support the hydrophilic and hydrophobic nature of the TSILs. Interestingly, we have found a strong correlation between the viscosity and the EDOS results that leads to an understanding of the hydration properties of the TSILs.

  10. Ionic-Liquid-Based Polymer Electrolytes for Battery Applications.

    Science.gov (United States)

    Osada, Irene; de Vries, Henrik; Scrosati, Bruno; Passerini, Stefano

    2016-01-11

    The advent of solid-state polymer electrolytes for application in lithium batteries took place more than four decades ago when the ability of polyethylene oxide (PEO) to dissolve suitable lithium salts was demonstrated. Since then, many modifications of this basic system have been proposed and tested, involving the addition of conventional, carbonate-based electrolytes, low molecular weight polymers, ceramic fillers, and others. This Review focuses on ternary polymer electrolytes, that is, ion-conducting systems consisting of a polymer incorporating two salts, one bearing the lithium cation and the other introducing additional anions capable of plasticizing the polymer chains. Assessing the state of the research field of solid-state, ternary polymer electrolytes, while giving background on the whole field of polymer electrolytes, this Review is expected to stimulate new thoughts and ideas on the challenges and opportunities of lithium-metal batteries. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Solvation consequences of polymer PVP with biological buffers MES, MOPS, and MOPSO in aqueous solutions

    International Nuclear Information System (INIS)

    Gupta, Bhupender S.; Chen, Bo-Ren; Lee, Ming-Jer

    2015-01-01

    Highlights: • Densities and viscosities data for aqueous solutions with PVP and/or buffer. • The studied buffers include MES, MOPS, and MOPSO. • DFT was used to estimate the binding energies of the (PVP + buffer) complexes. • The viscosity data were correlated with the Jones–Dole equation. • The investigated buffers behave as Kosmotropies. - Abstract: Densities and viscosities were measured for the aqueous buffer (MES, MOPS, or MOPSO) solutions containing different concentrations of polyvinylpyrrolidone (PVP) (5, 10, 15, 20 and 30) mass% at temperatures from (298.15 to 318.15) K under atmospheric pressure. The DFT calculations were also performed and the binding energies of the possible (PVP + buffer) complexes were obtained. The experimental and computational results reveal the interactions of the PVP with the constituent compounds in the aqueous buffer solutions. Additionally we have explored the solvation behavior of the buffers by measuring the densities and the viscosities data of the aqueous buffer solutions from (0.0 to 1.0) mol · kg"−"1 at temperatures from (298.15 to 318.15) K. The viscosity results were correlated with the Jones–Dole equation. The correlated results confirmed that all the investigated buffers behave as Kosmotropes (structure makers).

  12. Printable polymer actuators from ionic liquid, soluble polyimide, and ubiquitous carbon materials.

    Science.gov (United States)

    Imaizumi, Satoru; Ohtsuki, Yuto; Yasuda, Tomohiro; Kokubo, Hisashi; Watanabe, Masayoshi

    2013-07-10

    We present here printable high-performance polymer actuators comprising ionic liquid (IL), soluble polyimide, and ubiquitous carbon materials. Polymer electrolytes with high ionic conductivity and reliable mechanical strength are required for high-performance polymer actuators. The developed polymer electrolytes comprised a soluble sulfonated polyimide (SPI) and IL, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([C2mim][NTf2]), and they exhibited acceptable ionic conductivity up to 1 × 10(-3) S cm(-1) and favorable mechanical properties (elastic modulus >1 × 10(7) Pa). Polymer actuators based on SPI/[C2mim][NTf2] electrolytes were prepared using inexpensive activated carbon (AC) together with highly electron-conducting carbon such as acetylene black (AB), vapor grown carbon fiber (VGCF), and Ketjen black (KB). The resulting polymer actuators have a trilaminar electric double-layer capacitor structure, consisting of a polymer electrolyte layer sandwiched between carbon electrode layers. Displacement, response speed, and durability of the actuators depended on the combination of carbons. Especially the actuators with mixed AC/KB carbon electrodes exhibited relatively large displacement and high-speed response, and they kept 80% of the initial displacement even after more than 5000 cycles. The generated force of the actuators correlated with the elastic modulus of SPI/[C2mim][NTf2] electrolytes. The displacement of the actuators was proportional to the accumulated electric charge in the electrodes, regardless of carbon materials, and agreed well with the previously proposed displacement model.

  13. Influence of ionic strength on the viscosities and water loss of bentonite suspensions containing polymers

    Directory of Open Access Journals (Sweden)

    Luciana Viana Amorim

    2007-03-01

    Full Text Available A study was made of the influence of ionic strength (S on the apparent (AV and plastic (PV viscosities and water loss (WL of sodium bentonite suspension with polymers. Na-bentonite was dispersed in water (4.86% w/w of different ionic strengths (S = 0.0, 0.015, 0.030 and 0.045 M followed by the addition of polymer. Three polymer samples were studied, i.e., low viscosity carboxymethyl cellulose (CMC BV, polyanionic cellulose (PAC, and partially hydrolyzed polyacrylamide (HPAM. The results indicated that the presence of salts and increased salinity greatly influence the apparent and plastic viscosities and water loss of bentonite suspensions with polymer.

  14. Solvation of ionic liquids based on N-methyl-N-alkyl morpholinium cations in dimethylsulfoxide – volumetric and compressibility studies

    International Nuclear Information System (INIS)

    Marcinkowski, Łukasz; Kloskowski, Adam; Czub, Jacek; Namieśnik, Jacek; Warmińska, Dorota

    2015-01-01

    Highlights: • In DMSO both volumes and compressibilities of ionic liquids were studied. • Molecular dynamics simulations were performed for all studied ionic liquids. • V Φ of DMSO solutions of [Mor 1,R ][TFSI] decrease with increasing IL concentration. • Results indicate that [Mor 1,R ][TFSI] are structure breakers in dimethylsulfoxide. • Obtained results are the consequence of the cation size of the ionic liquid. - Abstract: The density and sound velocity of the solutions of ionic liquids based on N-alkyl-N-methyl-morpholinium cations, N-ethyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide, N-butyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide, N-methyl-N-octyl-morpholinium bis(trifluoromethanesulfonyl)imide and N-decyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide in dimethylsulfoxide were measured at T = (298.15 to 318.15) K and at atmospheric pressure. The apparent molar volume and apparent molar compressibility values were evaluated from density and sound velocity values and fitted to the Masson equation from which the partial molar volume and partial molar isentropic compressibility of the ILs at infinite dilution were also calculated at working temperatures. By using the density values, the limiting apparent molar expansibilities were estimated. The effect of the alkyl chain length of the ILs and experimental temperature on these thermodynamic properties is discussed. In addition, molecular dynamics simulations were used to interpret the measured properties in terms of interactions of ILs with solvent molecules. Both, volumetric measurements results and molecular dynamics simulations for ionic liquids in dimethylsulfoxide were compared and discussed with results obtained for the same IL in acetonitrile

  15. The effects of functional ionic liquid on properties of solid polymer electrolyte

    International Nuclear Information System (INIS)

    An Yongxin; Cheng Xinqun; Zuo Pengjian; Liao Lixia; Yin Geping

    2011-01-01

    Highlights: → The functional ionic liquid(IL)-polymer electrolytes were successfully prepared. → The ionic conductivity of PEO electrolytes was raised to above 10-4 S.cm-1 at room temperature by functional IL. → The cells using functional IL-PEO electrolyte show higher reversible capacity and long cycle life. - Abstract: Polyethylene oxide (PEO) based solid state electrolytes have been thought as promising electrolytes to replace the organic liquid electrolyte for lithium ion batteries. But the lower ionic conductivities at room temperature restrict their application. In this paper, functional ionic liquid and polymer mixed electrolytes are prepared from N-methyoxymethyl-N-methylpiperidinium bis(trifluoromethanesulfonyl)imide (PP1.1O1TFSI) and polyethylene oxide. The PP1.1O1TFSI, a kind of room-temperature molten salt, was added to the conventional P(EO) 20 LiTFSI polymer electrolyte and resulted in a significant improvement of the ionic conductivity at room temperature. LiFePO 4 /Li and Li 4 Ti 5 O 12 /Li cells using this kind of electrolyte show high reversible capacity and stable cycle performance.

  16. Ion beam irradiation as a tool to improve the ionic conductivity in solid polymer electrolyte systems

    Energy Technology Data Exchange (ETDEWEB)

    Manjunatha, H., E-mail: h-manjunath@blr.amrita.edu; Kumaraswamy, G. N. [Department of Physics, Amrita Vishwa Vidyapeetham, Bengaluru-560 035 (India); Damle, R. [Department of Physics, Bangalore University, Bengaluru-560 056 (India)

    2016-05-06

    Solid polymer electrolytes (SPEs) have potential applications in solid state electronic and energy devices. The optimum conductivity of SPEs required for such applications is about 10{sup −1} – 10{sup −3} Scm{sup −1}, which is hard to achieve in these systems. It is observed that ionic conductivity of SPEs continuously increase with increasing concentration of inorganic salt in the host polymer. However, there is a critical concentration of the salt beyond which the conductivity of SPEs decreases due to the formation of ion pairs. In the present study, solid polymer thin films based on poly (ethylene oxide) (PEO) complexed with NaBr salt with different concentrations have been prepared and the concentration at which ion pair formation occurs in PEO{sub x}NaBr is identified. The microstructure of the SPE with highest ionic conductivity is modified by irradiating it with low energy O{sup +1} ion (100 keV) of different fluencies. It is observed that the ionic conductivity of irradiated SPEs increases by one order in magnitude. The increase in ionic conductivity may be attributed to the enhanced segmental motion of the polymer chains due to radiation induced micro structural modification.

  17. Derivation of finite element formulation for electrochemical governing equations of ionic polymer actuators

    International Nuclear Information System (INIS)

    Kang, Sung Soo

    2013-01-01

    Ionic polymer actuators have recently attracted a great deal of interest as electroactive materials with potentials as soft actuators, sensors, artificial muscles, robotics, and microelectromechanical systems because of their numerous advantages, including low voltage requirement, high compliance, lightness, and flexibility. The platinum-plated Nafion, a perfluorosulfonic acid membrane made by Dupont, is commonly used as a polyelectrolyte in actuator applications. The bending of the ionic polymer actuators in an electric field is dominated by the electro-osmosis of hydrated ions and slow diffusion of free water molecules. The changes in hydration cause a local volumetric strain resulting in bending deformation, such as expansion and contraction. In this study, a two-dimensional finite element (FE) formulation based on the Galerkin method is derived for the governing equations describing these electrochemical responses. In addition, a three-dimensional FE deformation analysis is conducted on the bending behaviors of the platinum-plated ionic polymer actuators. Several numerical studies for ionic polymer actuators, such as plates with various electrode arrangements and disk models in electric field, are performed to confirm the validity of the proposed formulation.

  18. Adsorbed polymers in aqueous media. The relation between zeta-potential, layer thickness and ionic strength

    NARCIS (Netherlands)

    Cohen Stuart, M.A.; Mulder, J.W.

    1985-01-01

    Streaming potentials for glass capillaries with and without adsorbed poly(vinyl pyrrolidone) were used to determine the thickness of the adsorbed polymer layer. It was found that the thickness determined in this way is a strong function of the ionic strength of the solution. The results are compared

  19. Ionic motion in PEDOT and PPy conducting polymer bilayers

    DEFF Research Database (Denmark)

    Zainudeen, Umer L.; Careem, M.A.; Skaarup, Steen

    2006-01-01

    Conducting polymer bilayers with poly(3,4-ethylenedioxythiophene) (PEDOT) and polypyrrole (PPy), each containing dodecyl benzenesulfonate (DBS) as immobile dopant species, were synthesized galvanostatically. The electrochemical behaviour of the bilayers was investigated using cyclic voltammetry...

  20. Effect of Dimethyl Carbonate Plasticizer on Ionic Conductivity of Methyl Cellulose-Based Polymer Electrolytes

    International Nuclear Information System (INIS)

    Mustafa, M.F.; Ridwan, N.I.M.; Hatta, F.F.; Yahya, M.Z.A.

    2012-01-01

    Influences of dimethyl carbonate (DMC) plasticizer on ionic conductivity, dielectric permittivity and electrical modulus formalism of methyl cellulose (MC)-based polymer electrolytes have been studied. The room temperature electrical conductivity as measured by impedance spectroscopy shows that a methyl cellulose film has a conductivity of ∼10 -10 S cm -1 . In this study, other than KOH ionic dopant, DMC plasticizer is also added to the polymer with the aim of enhancing the electrical conductivity of the polymer. The highest room temperature conductivity of the plasticised sample is ∼10 -5 S cm -1 . The plot of log σ versus 10 3 / T for the highest conducting sample obeys Arrhenius rule indicating that the conductivity occurs by thermally activated mechanism. (author)

  1. Crosslinked Polymer Ionic Liquid/Ionic Liquid Blends Prepared by Photopolymerization as Solid-State Electrolytes in Supercapacitors.

    Science.gov (United States)

    Wang, Po-Hsin; Wang, Tzong-Liu; Lin, Wen-Churng; Lin, Hung-Yin; Lee, Mei-Hwa; Yang, Chien-Hsin

    2018-04-07

    A photopolymerization method is used to prepare a mixture of polymer ionic liquid (PIL) and ionic liquid (IL). This mixture is used as a solid-state electrolyte in carbon nanoparticle (CNP)-based symmetric supercapacitors. The solid electrolyte is a binary mixture of a PIL and its corresponding IL. The PIL matrix is a cross-linked polyelectrolyte with an imidazole salt cation coupled with two anions of Br - in PIL-M-(Br) and TFSI - in PIL-M-(TFSI), respectively. The corresponding ionic liquids have imidazolium salt cation coupled with two anions of Br - and TFSI - , respectively. This study investigates the electrochemical characteristics of PILs and their corresponding IL mixtures used as a solid electrolyte in supercapacitors. Results show that a specific capacitance, maximum power density and energy density of 87 and 58 F·g - ¹, 40 and 48 kW·kg - ¹, and 107 and 59.9 Wh·kg - ¹ were achieved in supercapacitors based on (PIL-M-(Br)) and (PIL-M-(TFSI)) solid electrolytes, respectively.

  2. Crosslinked Polymer Ionic Liquid/Ionic Liquid Blends Prepared by Photopolymerization as Solid-State Electrolytes in Supercapacitors

    Science.gov (United States)

    Wang, Po-Hsin; Wang, Tzong-Liu; Lin, Wen-Churng; Lin, Hung-Yin; Lee, Mei-Hwa; Yang, Chien-Hsin

    2018-01-01

    A photopolymerization method is used to prepare a mixture of polymer ionic liquid (PIL) and ionic liquid (IL). This mixture is used as a solid-state electrolyte in carbon nanoparticle (CNP)-based symmetric supercapacitors. The solid electrolyte is a binary mixture of a PIL and its corresponding IL. The PIL matrix is a cross-linked polyelectrolyte with an imidazole salt cation coupled with two anions of Br− in PIL-M-(Br) and TFSI− in PIL-M-(TFSI), respectively. The corresponding ionic liquids have imidazolium salt cation coupled with two anions of Br− and TFSI−, respectively. This study investigates the electrochemical characteristics of PILs and their corresponding IL mixtures used as a solid electrolyte in supercapacitors. Results show that a specific capacitance, maximum power density and energy density of 87 and 58 F·g−1, 40 and 48 kW·kg−1, and 107 and 59.9 Wh·kg−1 were achieved in supercapacitors based on (PIL-M-(Br)) and (PIL-M-(TFSI)) solid electrolytes, respectively. PMID:29642456

  3. Crosslinked Polymer Ionic Liquid/Ionic Liquid Blends Prepared by Photopolymerization as Solid-State Electrolytes in Supercapacitors

    Directory of Open Access Journals (Sweden)

    Po-Hsin Wang

    2018-04-01

    Full Text Available A photopolymerization method is used to prepare a mixture of polymer ionic liquid (PIL and ionic liquid (IL. This mixture is used as a solid-state electrolyte in carbon nanoparticle (CNP-based symmetric supercapacitors. The solid electrolyte is a binary mixture of a PIL and its corresponding IL. The PIL matrix is a cross-linked polyelectrolyte with an imidazole salt cation coupled with two anions of Br− in PIL-M-(Br and TFSI− in PIL-M-(TFSI, respectively. The corresponding ionic liquids have imidazolium salt cation coupled with two anions of Br− and TFSI−, respectively. This study investigates the electrochemical characteristics of PILs and their corresponding IL mixtures used as a solid electrolyte in supercapacitors. Results show that a specific capacitance, maximum power density and energy density of 87 and 58 F·g−1, 40 and 48 kW·kg−1, and 107 and 59.9 Wh·kg−1 were achieved in supercapacitors based on (PIL-M-(Br and (PIL-M-(TFSI solid electrolytes, respectively.

  4. Dispersion and Solvation Effects on the Structure and Dynamics of N719 Adsorbed to Anatase Titania (101) Surfaces in Room-Temperature Ionic Liquids: An ab Initio Molecular Simulation Study

    KAUST Repository

    Byrne, Aaron

    2015-12-24

    Ab initio, density functional theory (DFT)-based molecular dynamics (MD) has been carried out to investigate the effect of explicit solvation on the dynamical and structural properties of a [bmim][NTf2] room-temperature ionic liquid (RTIL), solvating a N719 sensitizing dye adsorbed onto an anatase titania (101) surface. The effect of explicit dispersion on the properties of this dye-sensitized solar cell (DSC) interface has also been studied. Upon inclusion of dispersion interactions in simulations of the solvated system, the average separation between the cations and anions decreases by 0.6 Å; the mean distance between the cations and the surface decreases by about 0.5 Å; and the layering of the RTIL is significantly altered in the first layer surrounding the dye, with the cation being on average 1.5 Å further from the center of the dye. Inclusion of dispersion effects when a solvent is not explicitly included (to dampen longer-range interactions) can result in unphysical "kinking" of the adsorbed dye\\'s configuration. The inclusion of solvent shifts the HOMO and LUMO levels of the titania surface by +3 eV. At this interface, the interplay between the effects of dispersion and solvation combines in ways that are often subtle, such as enhancement or inhibition of specific vibrational modes. © 2015 American Chemical Society.

  5. Influence of the Ionic Liquid Type on the Gel Polymer Electrolytes Properties

    Directory of Open Access Journals (Sweden)

    Juan P. Tafur

    2015-11-01

    Full Text Available Gel Polymer Electrolytes (GPEs composed by ZnTf2 salt, poly(vinylidene fluoride-co-hexafluoropropylene (PVdF-HFP, and different ionic liquids are synthesized using n-methyl-2-pyrrolidone (NMP as solvent. Three different imidazolium-based ionic liquids containing diverse cations and anions have been explored. Structural and electrical properties of the GPEs varying the ZnTf2 concentration are analyzed by ATR-FTIR, DSC, TG, and cyclic voltammetry. Free salt IL-GPEs present distinct behavior because they are influenced by the different IL cations and anions composition. However, inclusion of ZnTf2 salt inside the polymers provide GPEs with very similar characteristics, pointing out that ionic transport properties are principally caused by Zn2+ and triflate movement. Whatever the IL used, the presence of NMP solvent inside the polymer’s matrix turns out to be a key factor for improving the Zn2+ transport inside the GPE due to the interaction between Zn2+ cations and carbonyl groups of the NMP. High values of ionic conductivity, low activation energy values, and good voltammetric reversibility obtained regardless of the ionic liquid used enable these GPEs to be applied in Zn batteries. Capacities of 110–120 mAh·g−1 have been obtained for Zn/IL-GPE/MnO2 batteries discharged at −1 mA·cm−2.

  6. Enhancing ionic conductivity in composite polymer electrolytes with well-aligned ceramic nanowires

    Science.gov (United States)

    Liu, Wei; Lee, Seok Woo; Lin, Dingchang; Shi, Feifei; Wang, Shuang; Sendek, Austin D.; Cui, Yi

    2017-04-01

    In contrast to conventional organic liquid electrolytes that have leakage, flammability and chemical stability issues, solid electrolytes are widely considered as a promising candidate for the development of next-generation safe lithium-ion batteries. In solid polymer electrolytes that contain polymers and lithium salts, inorganic nanoparticles are often used as fillers to improve electrochemical performance, structure stability, and mechanical strength. However, such composite polymer electrolytes generally have low ionic conductivity. Here we report that a composite polymer electrolyte with well-aligned inorganic Li+-conductive nanowires exhibits an ionic conductivity of 6.05 × 10-5 S cm-1 at 30 ∘C, which is one order of magnitude higher than previous polymer electrolytes with randomly aligned nanowires. The large conductivity enhancement is ascribed to a fast ion-conducting pathway without crossing junctions on the surfaces of the aligned nanowires. Moreover, the long-term structural stability of the polymer electrolyte is also improved by the use of nanowires.

  7. Ionic Liquids as the MOFs/Polymer Interfacial Binder for Efficient Membrane Separation.

    Science.gov (United States)

    Lin, Rijia; Ge, Lei; Diao, Hui; Rudolph, Victor; Zhu, Zhonghua

    2016-11-23

    Obtaining strong interfacial affinity between filler and polymer is critical to the preparation of mixed matrix membranes (MMMs) with high separation efficiency. However, it is still a challenge for micron-sized metal organic frameworks (MOFs) to achieve excellent compatibility and defect-free interface with polymer matrix. Thin layer of ionic liquid (IL) was immobilized on micron-sized HKUST-1 to eliminate the interfacial nonselective voids in MMMs with minimized free ionic liquid (IL) in polymer matrix, and then the obtained IL decorated HKUST-1 was incorporated into 4,4'-(hexafluoroisopropylidene)diphthalic anhydride-2,3,5,6-tetramethyl-1,3-phenyldiamine (6FDA-Durene) to fabricate MMMs. Acting as a filler/polymer interfacial binder, the favorable MOF/IL and IL/polymer interaction can facilitate the enhancement of MOF/polymer affinity. Compared to MMM with only HKUST-1 incorporation, MMM with IL decorated HKUST-1 succeeded in restricting the formation of nonselective interfacial voids, leading to an increment in CO 2 selectivity. The IL decoration method can be an effective approach to eliminate interfacial voids in MMMs, extending the filler selection to a wide range of large-sized fillers.

  8. Ionic conductivity and dielectric permittivity of polymer electrolyte plasticized with polyethylene glycol

    Science.gov (United States)

    Das, S.; Ghosh, A.

    2016-05-01

    We have studied ionic conductivity and dielectric permittivity of PEO-LiClO4 solid polymer electrolyte plasticized with polyethylene glycol (PEG). The temperature dependence of the ionic conductivity has been well interpreted using Vogel-Tamman-Fulcher equation. The maximum dielectric constant is observed for 30 wt. % of PEG content. To get further insights into the ion dynamics, the complex dielectric permittivity has been studied with Havriliak-Negami function. The variation of relaxation time with inverse temperature obtained from HN formalism follows VTF nature.

  9. Morphology, optical and ionic conductivity studies of electron beam irradiated polymer electrolyte film

    Science.gov (United States)

    Devendrappa, H.; Yesappa, L.; Niranjana, M.; Ashokkumar, S. P.; Vijeth, H.; Ganesh, S.

    2018-04-01

    The effects of electron beam (EB) irradiation on morphology, optical properties and ionic conductivity of (PVdF-co-HFP: LiClO4=90:10, PHL10) electrolyte films. The FESEM image reveal increasing porous morphology with increasing EB dose confirms the polymer degradation as result more amorphousity. The optical absorbance was found to be increase with red shift in UV region and direct optical band gaps was found decreased upon EB dose from 3.70 eV to 2.65 eV. The ionic conductivity increases slowly in lower frequency, whereas rapidly increases at the high frequency and found about 8.28×10-4 S/cm at 120 kGy dose. The obtained results suggest that the physical properties of polymer electrolytes can be changed using EB irradiation as requirement.

  10. Synthesis, ionic conductivity, and thermal properties of proton conducting polymer electrolyte for high temperature fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Itoh, Takahito; Hamaguchi, Yohei; Uno, Takahiro; Kubo, Masataka [Department of Chemistry for Materials, Faculty of Engineering, Mie University, 1577 Kurima Machiya-cho, Tsu, Mie 514-8507 (Japan); Aihara, Yuichi; Sonai, Atsuo [Samsung Yokohama Research Institute, 2-7 Sugasawa-cho, Tsurumi-ku, Yokohama 230-0027 (Japan)

    2006-01-16

    Hyperbranched polymer (poly-1a) with sulfonic acid groups at the end of chains was successfully synthesized. Interpenetration reaction of poly-1a with a hyperbranched polymer with acryloyl groups at the end of chains (poly-1b) as a cross-linker afforded a tough electrolyte membrane. The poly-1a and the resulting electrolyte membrane showed the ionic conductivities of 7x10{sup -4} and 8x10{sup -5} S/cm, respectively, at 150C under dry condition. The ionic conductivities of the poly-1a and the electrolyte membrane exhibited the VTF type temperature dependence. And also, both poly-1a and the resulting electrolyte membrane were thermally stable up to 200C. (author)

  11. Progress in Imidazolium Ionic Liquids Assisted Fabrication of Carbon Nanotube and Graphene Polymer Composites

    Directory of Open Access Journals (Sweden)

    Xiaolin Xie

    2013-06-01

    Full Text Available Carbon nanotubes (CNTs and graphene sheets are the most promising fillers for polymer nanocomposites due to their superior mechanical, electrical, thermal optical and gas barrier properties, as well as high flame-retardant efficiency. The critical challenge, however, is how to uniformly disperse them into the polymer matrix to achieve a strong interface for good load transfer between the two. This problem is not new but more acute in CNTs and graphene, both because they are intrinsically insoluble and tend to aggregate into bundles and because their surfaces are atomically smooth. Over the past decade, imidazolium ionic liquids (Imi-ILs have played a multifunctional role (e.g., as solvents, dispersants, stabilizers, compatibilizers, modifiers and additives in the fabrication of polymer composites containing CNTs or graphene. In this review, we first summarize the liquid-phase exfoliation, stabilization, dispersion of CNTs and graphene in Imi-ILs, as well as the chemical and/or thermal reduction of graphene oxide to graphene with the aid of Imi-ILs. We then present a full survey of the literature on the Imi-ILs assisted fabrication of CNTs and graphene-based nanocomposites with a variety of polymers, including fluoropolymers, hydrocarbon polymers, polyacrylates, cellulose and polymeric ionic liquids. Finally, we give a future outlook in hopes of facilitating progress in this emerging area.

  12. Performance of solid state supercapacitors based on polymer electrolytes containing different ionic liquids

    Science.gov (United States)

    Tiruye, Girum Ayalneh; Muñoz-Torrero, David; Palma, Jesus; Anderson, Marc; Marcilla, Rebeca

    2016-09-01

    Four Ionic Liquid based Polymer Electrolytes (IL-b-PE) were prepared by blending a Polymeric Ionic Liquid, Poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide (PILTFSI), with four different ionic liquids: 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) (IL-b-PE1), 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide (PYR14FSI) (IL-b-PE2), 1-(2-hydroxy ethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (HEMimTFSI) (IL-b-PE3), and 1-Butyl-1-methylpyrrolidinium dicyanamide, (PYR14DCA) (IL-b-PE4). Physicochemical properties of IL-b-PE such as ionic conductivity, thermal and electrochemical stability were found to be dependent on the IL properties. For instance, ionic conductivity was significantly higher for IL-b-PE2 and IL-b-PE4 containing IL with small size anions (FSI and DCA) than IL-b-PE1 and IL-b-PE3 bearing IL with bigger anion (TFSI). On the other hand, wider electrochemical stability window (ESW) was found for IL-b-PE1 and IL-b-PE2 having ILs with electrochemically stable pyrrolidinium cation and FSI and TFSI anions. Solid state Supercapacitors (SCs) were assembled with activated carbon electrodes and their electrochemical performance was correlated with the polymer electrolyte properties. Best performance was obtained with SC having IL-b-PE2 that exhibited a good compromise between ionic conductivity and electrochemical window. Specific capacitance (Cam), real energy (Ereal) & real power densities (Preal) as high as 150 F g-1, 36 Wh kg-1 & 1170 W kg-1 were found at operating voltage of 3.5 V.

  13. Ternary polymer electrolytes with 1-methylimidazole based ionic liquids and aprotic solvents

    Czech Academy of Sciences Publication Activity Database

    Reiter, Jakub; Vondrák, Jiří; Michálek, Jiří; Mička, Z.

    2006-01-01

    Roč. 52, č. 3 (2006), s. 1398-1408 ISSN 0013-4686 R&D Projects: GA MŠk LC523; GA MŽP SN/3/171/05 Institutional research plan: CEZ:AV0Z40320502; CEZ:AV0Z40500505 Keywords : polymer gel electrolyte * ionic liquids * lithium-ion batteries Subject RIV: CA - Inorganic Chemistry Impact factor: 2.955, year: 2006

  14. Effect of the alkyl chain length of the ionic liquid anion on polymer electrolytes properties

    International Nuclear Information System (INIS)

    Leones, Rita; Sentanin, Franciani; Nunes, Sílvia Cristina; Esperança, José M.S.S.; Gonçalves, Maria Cristina

    2015-01-01

    New polymer electrolytes (PEs) based on chitosan and three ionic liquid (IL) families ([C 2 mim][C n SO 3 ], [C 2 mim][C n SO 4 ] and [C 2 mim][diC n PO 4 ]) were synthesized by the solvent casting method. The effect of the length of the alkyl chain of the IL anion on the thermal, morphological and electrochemical properties of the PEs was studied. The solid polymer electrolytes SPE membranes were analyzed by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), polarized optical microscopy (POM), atomic force microscopy (AFM), complex impedance spectroscopy (ionic conductivity) and cyclic voltammetry (CV). The obtained results evidenced an influence of the alkyl chain length of the IL anion on the temperature of degradation, birefringence, surface roughness and ionic conductivity of the membranes. The DSC, XRD and CV results showed independency from the length of the IL-anion-alkyl chain. The PEs displayed an predominantly amorphous morphology, a minimum temperature of degradation of 135 °C, a room temperature (T = 25 °C) ionic conductivity of 7.78 × 10 −4 S cm −1 and a wide electrochemical window of ∼ 4.0 V.

  15. Study of the effect hydrogen binding in the solvation of alkaline earth cations with MeOH in nitromethane using 1 H NMR technique and determination of ionic solvation number

    CERN Document Server

    Alizadeh, N

    2001-01-01

    A proton NMR method for the study of the effect hydrogen binding and determination of solvation numbers of alkaline earth cations with methanol (MeOH) in in tromethane (NM) as diluent is described. The method is based on monitoring the resonance frequency of MeOH protons as a function of MeOH to metal ion mole ratio at constant metal ion concentration. the average solvation number of cation, n, at any MeOH/ metal ion mole ration was calculated from the NMR chemical shift-mole ration data and was plotted against the mole ration values. The solvation numbers of alkaline earth cations were obtained from the limiting values of the corresponding n, vs. mole ratio plots.

  16. Study of the effect hydrogen binding in the solvation of alkaline earth cations with MeOH in nitromethane using 1 H NMR technique and determination of ionic solvation number

    International Nuclear Information System (INIS)

    Alizadeh, N.

    2001-01-01

    A proton NMR method for the study of the effect hydrogen binding and determination of solvation numbers of alkaline earth cations with methanol (MeOH) in in tromethane (NM) as diluent is described. The method is based on monitoring the resonance frequency of MeOH protons as a function of MeOH to metal ion mole ratio at constant metal ion concentration. the average solvation number of cation, n, at any MeOH/ metal ion mole ration was calculated from the NMR chemical shift-mole ration data and was plotted against the mole ration values. The solvation numbers of alkaline earth cations were obtained from the limiting values of the corresponding n, vs. mole ratio plots

  17. Ionic Liquid Confined in Mesoporous Polymer Membrane with Improved Stability for CO2/N2 Separation

    Directory of Open Access Journals (Sweden)

    Ming Tan

    2017-09-01

    Full Text Available Supported ionic liquid membranes (SILMs have a promising prospect of application in flue gas separation, owing to its high permeability and selectivity of CO2. However, existing SILMs have the disadvantage of poor stability due to the loss of ionic liquid from the large pores of the macroporous support. In this study, a novel SILM with high stability was developed by confining ionic liquid in a mesoporous polymer membrane. First, a mesoporous polymer membrane derived from a soluble, low-molecular-weight phenolic resin precursor was deposited on a porous Al2O3 support, and then 1-ethyl-3-methylimidazolium tetrafluoroborate ([emim][BF4] was immobilized inside mesopores of phenolic resin, forming the SILM under vacuum. Effects of trans-membrane pressure difference on the SILM separation performance were investigated by measuring the permeances of CO2 and N2. The SILM exhibits a high ideal CO2/N2 selectivity of 40, and an actual selectivity of approximately 25 in a mixed gas (50% CO2 and 50% N2 at a trans-membrane pressure difference of 2.5 bar. Compared to [emim][BF4] supported by polyethersulfone membrane with a pore size of around 0.45 μm, the [emim][BF4] confined in a mesoporous polymer membrane exhibits an improved stability, and its separation performance remained stable for 40 h under a trans-membrane pressure difference of 1.5 bar in a mixed gas before the measurement was intentionally stopped.

  18. Adaptive neuro-fuzzy control of ionic polymer metal composite actuators

    International Nuclear Information System (INIS)

    Thinh, Nguyen Truong; Yang, Young-Soo; Oh, Il-Kwon

    2009-01-01

    An adaptive neuro-fuzzy controller was newly designed to overcome the degradation of the actuation performance of ionic polymer metal composite actuators that show highly nonlinear responses such as a straightening-back problem under a step excitation. An adaptive control algorithm with the merits of fuzzy logic and neural networks was applied for controlling the tip displacement of the ionic polymer metal composite actuators. The reference and actual displacements and the change of the error with the electrical inputs were recorded to generate the training data. These data were used for training the adaptive neuro-fuzzy controller to find the membership functions in the fuzzy control algorithm. Software simulation and real-time experiments were conducted by using the Simulink and dSPACE environments. Present results show that the current adaptive neuro-fuzzy controller can be successfully applied to the reliable control of the ionic polymer metal composite actuator for which the performance degrades under long-time actuation

  19. A membrane actuator based on an ionic polymer network and carbon nanotubes: the synergy of ionic transport and mechanical properties

    International Nuclear Information System (INIS)

    Dai, Chi-An; Hsiao, Chih-Chun; Weng, Shih-Chun; Kao, An-Cheng; Liu, Chien-Pan; Tsai, Wei-Bor; Chen, Wen-Shiang; Liu, Wei-Ming; Shih, Wen-Pin; Ma, Chien-Ching

    2009-01-01

    There is a growing interest in the development of ionic polymer–metal composites (IPMC) as sensors and actuators for biomedical applications due to their large deformation under low driving voltage. In this study, we employed poly(vinyl alcohol)/poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PVA/PAMPS) blend membranes as semi-interpenetrating polymer networks for ion exchange in IPMC construction. To improve the mechanical and electrical properties of the IPMC, multi-walled carbon nanotubes (MWNT) were added into PVA/PAMPS membranes. The actuator performance of the membranes was measured as a function of their water uptake, ion exchange capacity, ionic conductivity and the amount of MWNT in the membrane. The dispersion quality of the modified MWNT in the PVA/PAMPS membrane was measured using transmission electron microscopy. The cantilever-type IPMC actuator bends under applied voltage and its bending angle and the generative tip force were measured. Under an applied voltage, IPMC with ∼1 wt% MWNT showed the largest deflection and generated the largest blocking tip force compared with those of IPMC with other various amounts of MWNT. These results show that a small addition of MWNT can optimize the actuation performance of IPMC. The result indicates that IPMC with MWNT shows potential for use as biomimetic artificial muscle

  20. Investigation of ionic conduction in PEO-PVDF based blend polymer electrolytes

    Science.gov (United States)

    Patla, Subir Kumar; Ray, Ruma; Asokan, K.; Karmakar, Sanat

    2018-03-01

    We investigate the effect of blend host polymer on solid polymer electrolyte (SPE) films doped with ammonium iodide (NH4I) salt using a variety of experimental techniques. Structural studies on the composite SPEs show that the blending of Poly(ethylene oxide) (PEO)-Poly(vinylidene fluoride) (PVDF) polymers in a suitable ratio enhances the amorphous fraction of the polymer matrix and facilitates fast ion conduction through it. We observe that the addition of a small amount of PVDF in the PEO host polymer enhances the ion - polymer interaction leading to more ion dissociation. As a result, the effective number of mobile charge carriers within the polymer matrix increases. Systematic investigation in these blend SPEs shows that the maximum conductivity (1.01 × 10-3 S/cm) is obtained for PEO - rich (80 wt. % PEO, 20 wt. % PVDF) composites at 35 wt. % NH4I concentration at room temperature. Interestingly, at higher salt concentrations (above 35 wt. %), the conductivity is found to decrease in this system. The reduction of conductivity at higher salt concentrations is the consequence of decrease in the carrier concentration due to the formation of an ion pair and ion aggregates. PVDF-rich compositions (20 wt. % PEO and 80 wt. % PVDF), on the other hand, show a very complex porous microstructure. We also observe a much lower ionic conductivity (maximum ˜ 10-6 S/cm at 15 wt. % salt) in these composite systems relative to PEO-rich composites.

  1. Improvement in the diffraction efficiency of a polymer using an ionic liquid

    Directory of Open Access Journals (Sweden)

    Kim Sung Ho

    2018-01-01

    Full Text Available In this paper, photosensitive materials for information storage devices are presented. The polymers were prepared using surface relief-grating (SRG fabrication with a diode-pumped solid-state (DPSS laser of 532 nm, and the diffraction efficiency (DE of the polymers were assessed with a low-power DPSS laser at 633 nm. However, the diffraction efficiency of the azo-functionalized epoxy-based polymer was low, even after 15 min of exposure. To improve the efficiency and reduce the time it takes for the DE measurements of the photosensitive polymer, the polymer was combined ionic liquids (ILs. Various ILs, i.e., 1-methylimidazolium chloride ([Mim]Cl from the imidazolium family of ILs and diethylammonium dihydrogen phosphate (DEAP, triethylammonium 4-aminotoluene-3-sulfonic acid (TASA and tributylmethylammonium methyl sulphate (TBMS from the ammonium family of ILs, were investigated. For the first time, it was observed that DE dramatically increased the DEAP–polymer mixture in 4 min compared to the polymer (alone and other polymer–IL mixtures. Therefore, DEAP IL could help improve the efficiency of DE measurements in a shorter time.

  2. Solid-state supercapacitors with ionic liquid based gel polymer electrolyte: Effect of lithium salt addition

    Science.gov (United States)

    Pandey, G. P.; Hashmi, S. A.

    2013-12-01

    Performance characteristics of the solid-state supercapacitors fabricated with ionic liquid (IL) incorporated gel polymer electrolyte and acid treated multiwalled carbon nanotube (MWCNT) electrodes have been studied. The effect of Li-salt (LiPF6) addition in the IL (1-ethyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate, EMImFAP) based gel electrolyte on the performance of supercapacitors has been specifically investigated. The LiPF6/IL/poly(vinylidine fluoride-co-hexafluoropropylene) (PVdF-HFP) gel electrolyte film possesses excellent electrochemical window of 4 V (from -2.0 to 2.0 V), high ionic conductivity ∼2.6 × 10-3 S cm-1 at 20 °C and high enough thermal stability. The comparative performance of supercapacitors employing electrolytes with and without lithium salt has been evaluated by impedance spectroscopy and cyclic voltammetric studies. The acid-treated MWCNT electrodes show specific capacitance of ∼127 F g-1 with IL/LiPF6 containing gel polymer electrolyte as compared to that with the gel polymer electrolyte without Li-salt, showing the value of ∼76 F g-1. The long cycling stability of the solid state supercapacitor based on the Li-salt containing gel polymer electrolyte confirms the electrochemical stability of the electrolyte.

  3. Colloidal behavior of aqueous montmorillonite suspensions in the presence of non-ionic polymer

    Science.gov (United States)

    Gareche, M.; Azri, N.; Allal, A.; Zeraibi, N.

    2015-04-01

    In this paper we characterized at first, the rheological behavior of the bentonite suspensions and the aqueous solutions of polyethylene oxide (PEO), then we were investigated the influence of this polymer in a water-based drilling fluid model (6% of bentonite suspension). The objective is to exhibit how the non ionic polymer with molecular weight 6×103 g/mol. of varying concentration mass (0.7%, 1%, 2% et 3%) significantly alter the rheological properties (yield stress, viscosity, loss and elastic modulus) of the bentonite suspensions. The rheological measurements made in simple shear and in dynamic on the mixture (water-bentonite-PEO), showed rheological properties of bentonite suspensions both in the presence and absence of non-ionic polymer. The PEO presents an affinity for the bentonite particles slowing down their kinetic aggregation. The analysis by X-rays diffraction also allowed understanding the structure of this mixture. It had revealed the intercalation between of the clay platelets on one hand, and the links bridges assured by the chains of polymer between bentonite particles beyond a critical concentration in PEO on the other hand. The Herschel- Bulkley rheological model is used for the correlation of our experimental results.

  4. Colloidal behavior of aqueous montmorillonite suspensions in the presence of non-ionic polymer

    International Nuclear Information System (INIS)

    Gareche, M; Azri, N; Zeraibi, N; Allal, A

    2015-01-01

    In this paper we characterized at first, the rheological behavior of the bentonite suspensions and the aqueous solutions of polyethylene oxide (PEO), then we were investigated the influence of this polymer in a water-based drilling fluid model (6% of bentonite suspension). The objective is to exhibit how the non ionic polymer with molecular weight 6×10 3 g/mol. of varying concentration mass (0.7%, 1%, 2% et 3%) significantly alter the rheological properties (yield stress, viscosity, loss and elastic modulus) of the bentonite suspensions. The rheological measurements made in simple shear and in dynamic on the mixture (water-bentonite-PEO), showed rheological properties of bentonite suspensions both in the presence and absence of non-ionic polymer. The PEO presents an affinity for the bentonite particles slowing down their kinetic aggregation. The analysis by X-rays diffraction also allowed understanding the structure of this mixture. It had revealed the intercalation between of the clay platelets on one hand, and the links bridges assured by the chains of polymer between bentonite particles beyond a critical concentration in PEO on the other hand. The Herschel- Bulkley rheological model is used for the correlation of our experimental results. (paper)

  5. Selectivity in inter polymer complexation involving phenolic copolymer, poly electrolytes, non-ionic polymers and transition metal ions

    International Nuclear Information System (INIS)

    Vasheghani Farahani, B.; Hosseinpour Rajabi, F.

    2006-01-01

    Selectivity in inter polymer complex formation involving a typical four-component phenolic copolymer (ρ-chloro phenol-ρ-aminophenol-ρ-toluidine-ρ-cresol- HCHO copolymer), poly electrolytes such as polyethylene imine and polyacrylic acid, a non-ionic homopolymer polyvinyl pyrrolidone, and some transition metal ions (e.g., Cu (II), Ni (11)) have been studied in dimethylformamide-methanol solvents mixture. The coordinating groups of phenolic copolymer form complexes through hydrogen bonding and ion-dipole interactions. The different stages of interactions have been studied by several experimental techniques, e.g., viscometry, potentiometry and conductometry. Some schemes have been suggested to explain the mode of interaction between these components

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

    Energy Technology Data Exchange (ETDEWEB)

    Praveen, D. [Department of Physics, Amrita Viswha Vidyapeetham, Bangalore, India, E-mail: d-praveen@blr.amrita.edu (India); Damle, Ramakrishna [Department of Physics, Bangalore University, Bangalore, India. E-mail: ramkrishnadamle@bub.ernet.in (India)

    2016-05-23

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

  7. Stretchable supercapacitors based on highly stretchable ionic liquid incorporated polymer electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Tamilarasan, P.; Ramaprabhu, S., E-mail: ramp@iitm.ac.in

    2014-11-14

    Mechanical stability of electrolyte in all-solid-state supercapacitor attains immense attention as it addresses safety aspects. In this study, we have demonstrated, the fabrication of stretchable supercapacitor based on stretchable electrolyte and hydrogen exfoliated graphene electrode. We synthesized ionic liquid incorporated stretchable Poly(methyl methacrylate) electrolyte which plays dual role as electrolyte and stretchable support for electrode material. The molecular vibration studies show composite nature of the electrolyte. At least four-fold stretchability has been observed along with good ionic conductivity (0.78 mS cm{sup −1} at 28 °C) for this polymer electrolyte. This stretchable supercapacitor shows a low equivalent series resistance (16 Ω) due to the compatibility at electrode–electrolyte interface. The performance of the device has been determined under strain as well. - Highlights: • A stretchable supercapacitor has been fabricated using stretchable electrolyte. • Here ionic liquid incorporated polymer plays dual role as electrolyte and stretchable support. • The developed device shows low equivalent series resistance. • The device has specific capacitance of 83 F g{sup −1}, at the specific current of 2.67 A g{sup −1}. • The energy density and power density of 25.7 Wh kg{sup −1} and 35.2 kW kg{sup −1}, respectively.

  8. Comparing Triflate and Hexafluorophosphate Anions of Ionic Liquids in Polymer Electrolytes for Supercapacitor Applications

    Directory of Open Access Journals (Sweden)

    Chiam-Wen Liew

    2014-05-01

    Full Text Available Two different ionic liquid-based biopolymer electrolyte systems were prepared using a solution casting technique. Corn starch and lithium hexafluorophosphate (LiPF6 were employed as polymer and salt, respectively. Additionally, two different counteranions of ionic liquids, viz. 1-butyl-3-methylimidazolium hexafluorophosphate (BmImPF6 and 1-butyl-3-methylimidazolium trifluoromethanesulfonate (also known as 1-butyl-3-methylimidazolium triflate (BmImTf were used and studied in this present work. The maximum ionic conductivities of (1.47 ± 0.02 × 10−4 and (3.21 ± 0.01 × 10−4 S∙cm−1 were achieved with adulteration of 50 wt% of BmImPF6 and 80 wt% of BmImTf, respectively at ambient temperature. Activated carbon-based electrodes were prepared and used in supercapacitor fabrication. Supercapacitors were then assembled using the most conducting polymer electrolyte from each system. The electrochemical properties of the supercapacitors were then analyzed. The supercapacitor containing the triflate-based biopolymer electrolyte depicted a higher specific capacitance with a wider electrochemical stability window compared to that of the hexafluorophosphate system.

  9. Experimental Characterization of Ionic Polymer Metal Composite as a Novel Fractional Order Element

    Directory of Open Access Journals (Sweden)

    Riccardo Caponetto

    2013-01-01

    Full Text Available Ionic polymer metal composites (IPMCs are electroactive materials made of ionic polymer thin membranes with platinum metallization on their surfaces. They are interesting materials due to not only their electromechanical applications as transducers but also to their electrochemical features and the relationship between the ionic/solvent current and the potential field. Their electrochemical properties thus suggest the possibility for exploiting them as compact fractional-order elements (FOEs with a view of defining fabrication processes and production strategies that assure the desired performances. In this paper, the experimental electrical characterization of a brand new IPMC setup in a fixed sandwich configuration is proposed. Two IPMC devices with different platinum absorption times (5 h and 20 h are characterized through experimental data: first, a preliminary linearity study is performed for a fixed input voltage amplitude in order to determine the frequency region where IPMC can be approximated as linear; then, a frequency analysis is carried out in order to identify a coherent fractional-order dynamics in the bode diagrams. Such analyses take the first steps towards a simplified model of IPMC as a compact electronic FOE for which the fractional exponent value depends on fabrication parameters as the absorption time.

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

    International Nuclear Information System (INIS)

    Praveen, D.; Damle, Ramakrishna

    2016-01-01

    Solid Polymer Electrolytes (SPEs) lack better conducting properties at ambient temperatures. Various methods to enhance their ionic conductivity like irradiation with swift heavy ions, γ-rays, swift electrons and quenching at low temperature etc., have been explored in the literature. Among these, one of the oldest methods is incorporation of different conducting species into the polymer matrix and/or addition of nano-sized inert particles into SPEs. Various new salts like LiBr, Mg(ClO_4)_2, NH_4I etc., have already been tried in the past with some success. Also various nanoparticles like Al_2O_3, TiO_2 etc., have been tried in the past. In this article, we have investigated an SPE containing Rubidium as a conducting species. Rubidium has a larger ionic size compared to lithium and sodium ions which have been investigated in the recent past. In the present article, we have investigated the conductivity of large sized conducting species and shown the enhancement in the ionic conductivity by addition of nano-sized inert particles.

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

    Science.gov (United States)

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

    2017-09-04

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

  12. IMIDAZOLE-BASED IONIC LIQUIDS FOR USE IN POLYMER ELECTROLYTE MEMBRANE FUEL CELLS: EFFECT OF ELECTRON-WITHDRAWING AND ELECTRON-DONATING SUBSTITUENTS

    Energy Technology Data Exchange (ETDEWEB)

    Chang, E.; Fu, Y.; Kerr, J.

    2009-01-01

    Current polymer electrolyte membrane fuel cells (PEMFCs) require humidifi cation for acceptable proton conductivity. Development of a novel polymer that is conductive without a water-based proton carrier is desirable for use in automobiles. Imidazole (Im) is a possible replacement for water as a proton solvent; Im can be tethered to the polymer structure by means of covalent bonds, thereby providing a solid state proton conducting membrane where the solvating groups do not leach out of the fuel cell. These covalent bonds can alter the electron availability of the Im molecule. This study investigates the effects of electron-withdrawing and electron-donating substituents on the conductivity of Im complexed with methanesulfonic acid (MSA) in the form of ionic liquids. Due to the changes in the electronegativity of nitrogen, it is expected that 2-phenylimidazole (2-PhIm, electron-withdrawing) will exhibit increased conductivity compared to Im, while 2-methylimidazole (2-MeIm, electron-donating) will exhibit decreased conductivity. Three sets of ionic liquids were prepared at defi ned molar ratios: Im-MSA, 2-PhIm-MSA, and 2-MeIm- MSA. Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and 1H-NMR were used to characterize each complex. Impedance analysis was used to determine the conductivity of each complex. Both the 2-PhIm-MSA and 2-MeIm-MSA ionic liquids were found to be less conductive than the Im-MSA complex at base-rich compositions, but more conductive at acid-rich compositions. 1H-NMR data shows a downfi eld shift of the proton on nitrogen in 2-PhIm compared to Im, suggesting that other factors may diminish the electronic effects of the electron withdrawing group at base-rich compositions. Further studies examining these effects may well result in increased conductivity for Im-based complexes. Understanding the conductive properties of Im-derivatives due to electronic effects will help facilitate the development of a new electrolyte

  13. Ions-induced nanostructuration: effect of specific ionic adsorption on hydrophobic polymer surfaces.

    Science.gov (United States)

    Siretanu, Igor; Chapel, Jean-Paul; Bastos-González, Delfi; Drummond, Carlos

    2013-06-06

    The effect of surface charges on the ionic distribution in close proximity to an interface has been extensively studied. On the contrary, the influence of ions (from dissolved salts) on deformable interfaces has been barely investigated. Ions can adsorb from aqueous solutions on hydrophobic surfaces, generating forces that can induce long-lasting deformation of glassy polymer films, a process called ion-induced polymer nanostructuration, IPN. We have found that this process is ion-specific; larger surface modifications are observed in the presence of water ions and hydrophobic and amphiphilic ions. Surface structuration is also observed in the presence of certain salts of lithium. We have used streaming potential and atomic force microscopy to study the effect of dissolved ions on the surface properties of polystyrene films, finding a good correlation between ionic adsorption and IPN. Our results also suggest that the presence of strongly hydrated lithium promotes the interaction of anions with polystyrene surfaces and more generally with hydrophobic polymer surfaces, triggering then the IPN process.

  14. Modelling and Control of Ionic Electroactive Polymer Actuators under Varying Humidity Conditions

    Directory of Open Access Journals (Sweden)

    S. Sunjai Nakshatharan

    2018-02-01

    Full Text Available In this work, we address the problem of position control of ionic electroactive polymer soft actuators under varying relative humidity conditions. The impact of humidity on the actuation performance of ionic actuators is studied through frequency response and impedance spectroscopy analysis. Considering the uncertain performance of the actuator under varying humidity conditions, an adaptable model using the neural network method is developed. The model uses relative humidity magnitude as one of the model parameters, making it robust to different environmental conditions. Utilizing the model, a closed-loop controller based on the model predictive controller is developed for position control of the actuator. The developed model and controller are experimentally verified and found to be capable of predicting and controlling the actuators with excellent tracking accuracy under relative humidity conditions varying in the range of 10–90%.

  15. Transparent and flexible quantum dot-polymer composites using an ionic liquid as compatible polymerization medium

    International Nuclear Information System (INIS)

    Woelfle, Caroline; Claus, Richard O

    2007-01-01

    Quantum dot (QD)-polymer composites were fabricated based on a solution of QDs dispersed in an ionic liquid. Positively charged water-soluble nanocrystals were obtained from solutions of CdSe/ZnS QDs dispersed in toluene by ligand exchange with 2-dimethylaminoethanethiol (DAET). The resulting QDs were further transferred into a hydrophobic ionic liquid HMITFSI (1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) by cation exchange, resulting in a CdSe/ZnS-HMITFSI solution, which was used as a compatible medium for the polymerization and cross-linking of polymethyl methacrylate networks. Transparent, fluorescent and flexible materials resulted. The quantum yields of the composites depended on the initial properties of the QDs dispersed in toluene, and medium-size QDs (2.6 nm) resulted in the highest quantum yields

  16. Finite element modeling of the electromechanical coupling in ionic polymer transducers

    Science.gov (United States)

    Akle, Barbar; Habchi, Wassim; Wallmersperger, Thomas; Leo, Donald

    2010-04-01

    Several researchers are actively studying Ionomeric polymer transducers (IPT) as a large strain low voltage Electro- Active Polymer (EAP) actuator. EAPs are devices that do not contain any moving parts leading to a potential large life time. Furthermore, they are light weight and flexible. An IPT is made of an ion saturated polymer usually Nafion, sandwiched between two electrodes made of a mixture of Nafion and electrically conductive particles usually RuO2 or platinum. Nafion is an acid membrane in which the cations are mobile while the anions are covalently fixed to the polymer structure. Upon the application of an electric potential on the order of 2V at the electrodes the mobile positive ions migrate towards the cathode leading to bending strains in the order of 5%. Our earlier studies demonstrate that the cations develop thin boundary layers around the electrode. Later developments in this finite element model captured the importance of adding particles in the electrode. This study presents the electromechanical coupling in ionic polymer transducers. Since all our earlier models were restricted to the electro-chemical part, here we will introduce the chemomechanical coupling. This coupling is performed based on previous studies (Akle and Leo) in which the authors experimentally showed that the mechanical strain in IPTs is proportional to a linear term and a quadratic term of the charge accumulated at the electrode. The values of the linear and quadratic terms are extracted from experimental data.

  17. Modeling of robotic fish propelled by an ionic polymer-metal composite caudal fin

    Science.gov (United States)

    Chen, Zheng; Shatara, Stephan; Tan, Xiaobo

    2009-03-01

    In this paper, a model is proposed for a biomimetic robotic fish propelled by an ionic polymer metal composite (IPMC) actuator with a rigid passive fin at the end. The model incorporates both IPMC actuation dynamics and the hydrodynamics, and predicts the steady-state speed of the robot under a periodic actuation voltage. Experimental results have shown that the proposed model can predict the fish motion for different tail dimensions. Since its parameters are expressed in terms of physical properties and geometric dimensions, the model is expected to be instrumental in optimal design of the robotic fish.

  18. Ionic liquids and their hosting by polymers for HT-PEMFC membranes

    Energy Technology Data Exchange (ETDEWEB)

    Hana, M.; Martinez, M.; Cointeaux, L.; Lepretre, J.C. [LEPMI-ELSA, PHELMA, UMR 5631, CNRS, Grenoble INP, UJF, Saint-Martin-d' Heres (France); Molmeret, Y.; El Kissi, N. [Laboratoire de Rheologie, UMR 5520 CNRS-INPG-UJF, ENSHMG, Grenoble (France); Teles, J.; Judeinstein, P. [Institut de Chimie Moleculaire et des Materiaux d' Orsay, CNRS 8182, Orsay (France); Iojoiu, C.; Sanchez, J.Y.

    2010-10-15

    The paper deals with proton-conducting ionic liquids (PCILs) for use, in combination with functional polymers, in membranes operating in high temperature PEMFC. Monoammoniums derived from monoamines and half-neutralised diamines were investigated in the form of triflates. Promising results were obtained with the half-neutralised diamine-based PCIL, its conduction being governed by both Grotthuss-like and vehicular mechanisms, the respective contributions of which depend on temperature. In addition, their blending with Nafion results in a distinct reinforcement of the membrane. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  19. Polymer Electrolytes

    Science.gov (United States)

    Hallinan, Daniel T.; Balsara, Nitash P.

    2013-07-01

    This review article covers applications in which polymer electrolytes are used: lithium batteries, fuel cells, and water desalination. The ideas of electrochemical potential, salt activity, and ion transport are presented in the context of these applications. Potential is defined, and we show how a cell potential measurement can be used to ascertain salt activity. The transport parameters needed to fully specify a binary electrolyte (salt + solvent) are presented. We define five fundamentally different types of homogeneous electrolytes: type I (classical liquid electrolytes), type II (gel electrolytes), type III (dry polymer electrolytes), type IV (dry single-ion-conducting polymer electrolytes), and type V (solvated single-ion-conducting polymer electrolytes). Typical values of transport parameters are provided for all types of electrolytes. Comparison among the values provides insight into the transport mechanisms occurring in polymer electrolytes. It is desirable to decouple the mechanical properties of polymer electrolyte membranes from the ionic conductivity. One way to accomplish this is through the development of microphase-separated polymers, wherein one of the microphases conducts ions while the other enhances the mechanical rigidity of the heterogeneous polymer electrolyte. We cover all three types of conducting polymer electrolyte phases (types III, IV, and V). We present a simple framework that relates the transport parameters of heterogeneous electrolytes to homogeneous analogs. We conclude by discussing electrochemical stability of electrolytes and the effects of water contamination because of their relevance to applications such as lithium ion batteries.

  20. Pattern Formation During Phase Separation of Polymer-Ionic Liquid Co-Solutions

    Science.gov (United States)

    Meng, Zhiyong; Osuji, Chinedum

    2010-03-01

    Co-solutions of polystyrene (PS) with a 1-butyl-3-methylimidazolium based ionic liquid (IL) in DMF phase separated into IL-rich and PS-rich domains on solvent evaporation. Over a limited range of polymer molecular weights and substrate temperatures, a variety of striped and cellular or polygonal structures were found on the resulting film surface, as visualized using bright-field and phase-contrast optical microscopy. This effect appears to be due to a Benard-Marangoni instability at the free surface of the liquid film as it undergoes evaporation, setting up convection rolls inside the fluid which become locked in place as the system vitrifies on solvent removal. Differential scanning calorimetry shows that the IL does not significantly plasticize the polymer, suggesting that the viscosity of the polystyrene solution itself controls the formation of this instability.

  1. Formation of Gd coordination polymer with 1D chains mediated by Bronsted acidic ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Qianqian; Han, Ying [Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai (China); Lin, Hechun, E-mail: hclin@ee.ecnu.edu.cn [Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai (China); Zhang, Yuanyuan; Duan, Chungang [Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai (China); Peng, Hui, E-mail: hpeng@ee.ecnu.edu.cn [Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai (China); Collaborative Innovation Center of Extreme Optics, Shanxi University, Taiyuan, Shanxi 030006 (China)

    2017-03-15

    One dimensional coordination polymer Gd[(SO{sub 4})(NO{sub 3})(C{sub 2}H{sub 6}SO){sub 2}] (1) is prepared through the mediation of Bronsted acid ionic liquid, which crystallized in the monoclinic space of C2/c. In this polymer, adjacent Gd atoms are linked by two SO{sub 4}{sup 2-} ions to generate a 1-D chain, and all oxygen atoms in SO{sub 4}{sup 2-} groups are connected to three nearest Gd atoms in µ{sup 3}:η{sup 1}:η{sup 1}:η{sup 2} fashion. Gd, S and N from SO{sub 4}{sup 2-} and NO{sub 3}{sup -} are precisely coplanar. The planar is coordinated by a pair of DMSO molecules, which is parallel and linked by hydrogen bonding to form a three-dimensional supramolecular network. Magnetic susceptibility measurement of 1 reveals weak antiferromagnetic interactions between the Gd (III) ions. It exhibits relatively large magneto-caloric effect with –ΔS{sub m}=28.8 J Kg{sup −1} K{sup −1} for ΔH=7 T. - Graphical abstract: Coordination polymer Gd[(SO{sub 4})(NO{sub 3})(C{sub 2}H{sub 6}SO){sub 2}] was obtained mediated by Bronsted acid Ionic Liquid, which presents a 1-D chains collected by SO{sub 4}{sup 2-} groups. Magnetic susceptibility of the polymer reveals weak antiferromagnetic interactions between the Gd(III) ions with the relatively large magneto-caloric effect of –ΔS{sub m}=28.8 J Kg{sup −1} K{sup −1} for ΔH= 7T.

  2. Ionic conductivity and dielectric permittivity of PEO-LiClO4 solid polymer electrolyte plasticized with propylene carbonate

    Directory of Open Access Journals (Sweden)

    S. Das

    2015-02-01

    Full Text Available We have studied ionic conductivity and dielectric permittivity of PEO-LiClO4 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 free 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.

  3. Ionic conductivity and dielectric permittivity of PEO-LiClO{sub 4} solid polymer electrolyte plasticized with propylene carbonate

    Energy Technology Data Exchange (ETDEWEB)

    Das, S.; Ghosh, A., E-mail: sspag@iacs.res.in [Department of Solid State Physics, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032 (India)

    2015-02-15

    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 free 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.

  4. Fused filament 3D printing of ionic polymer-metal composites (IPMCs)

    Science.gov (United States)

    Carrico, James D.; Traeden, Nicklaus W.; Aureli, Matteo; Leang, Kam K.

    2015-12-01

    This paper describes a new three-dimensional (3D) fused filament additive manufacturing (AM) technique in which electroactive polymer filament material is used to build soft active 3D structures, layer by layer. Specifically, the unique actuation and sensing properties of ionic polymer-metal composites (IPMCs) are exploited in 3D printing to create electroactive polymer structures for application in soft robotics and bio-inspired systems. The process begins with extruding a precursor material (non-acid Nafion precursor resin) into a thermoplastic filament for 3D printing. The filament is then used by a custom-designed 3D printer to manufacture the desired soft polymer structures, layer by layer. Since at this stage the 3D-printed samples are not yet electroactive, a chemical functionalization process follows, consisting in hydrolyzing the precursor samples in an aqueous solution of potassium hydroxide and dimethyl sulfoxide. Upon functionalization, metal electrodes are applied on the samples through an electroless plating process, which enables the 3D-printed IPMC structures to be controlled by voltage signals for actuation (or to act as sensors). This innovative AM process is described in detail and the performance of 3D printed IPMC actuators is compared to an IPMC actuator fabricated from commercially available Nafion sheet material. The experimental results show comparable performance between the two types of actuators, demonstrating the potential and feasibility of creating functional 3D-printed IPMCs.

  5. Polymer Conformations in Ionic Microgels in the Presence of Salt: Theoretical and Mesoscale Simulation Results

    Directory of Open Access Journals (Sweden)

    Hideki Kobayashi

    2017-01-01

    Full Text Available We investigate the conformational properties of polymers in ionic microgels in the presence of salt ions by molecular dynamics simulations and analytical theory. A microgel particle consists of coarse-grained linear polymers, which are tetra-functionally crosslinked. Counterions and salt ions are taken into account explicitly, and charge-charge interactions are described by the Coulomb potential. By varying the charge interaction strength and salt concentration, we characterize the swelling of the polyelectrolytes and the charge distribution. In particular, we determine the amount of trapped mobile charges inside the microgel and the Debye screening length. Moreover, we analyze the polymer extension theoretically in terms of the tension blob model taking into account counterions and salt ions implicitly by the Debye–Hückel model. Our studies reveal a strong dependence of the amount of ions absorbed in the interior of the microgel on the electrostatic interaction strength, which is related to the degree of the gel swelling. This implies a dependence of the inverse Debye screening length κ on the ion concentration; we find a power-law increase of κ with the Coulomb interaction strength with the exponent 3 / 5 for a salt-free microgel and an exponent 1 / 2 for moderate salt concentrations. Additionally, the radial dependence of polymer conformations and ion distributions is addressed.

  6. Fused filament 3D printing of ionic polymer-metal composites (IPMCs)

    International Nuclear Information System (INIS)

    Carrico, James D; Traeden, Nicklaus W; Leang, Kam K; Aureli, Matteo

    2015-01-01

    This paper describes a new three-dimensional (3D) fused filament additive manufacturing (AM) technique in which electroactive polymer filament material is used to build soft active 3D structures, layer by layer. Specifically, the unique actuation and sensing properties of ionic polymer-metal composites (IPMCs) are exploited in 3D printing to create electroactive polymer structures for application in soft robotics and bio-inspired systems. The process begins with extruding a precursor material (non-acid Nafion precursor resin) into a thermoplastic filament for 3D printing. The filament is then used by a custom-designed 3D printer to manufacture the desired soft polymer structures, layer by layer. Since at this stage the 3D-printed samples are not yet electroactive, a chemical functionalization process follows, consisting in hydrolyzing the precursor samples in an aqueous solution of potassium hydroxide and dimethyl sulfoxide. Upon functionalization, metal electrodes are applied on the samples through an electroless plating process, which enables the 3D-printed IPMC structures to be controlled by voltage signals for actuation (or to act as sensors). This innovative AM process is described in detail and the performance of 3D printed IPMC actuators is compared to an IPMC actuator fabricated from commercially available Nafion sheet material. The experimental results show comparable performance between the two types of actuators, demonstrating the potential and feasibility of creating functional 3D-printed IPMCs. (paper)

  7. Experimental investigation of the streaming potential hypothesis for ionic polymer transducers in sensing

    International Nuclear Information System (INIS)

    Kocer, Bilge; Weiland, Lisa Mauck

    2013-01-01

    Ionic polymer transducers (IPTs) are ionomers that are plated with conductive media such as metals, leading to capacitive behavior. IPTs exhibit bending deformation when a voltage difference is applied across the surfaces of the transducer, thus displaying actuation. A current is generated when they are deformed, thus exhibiting sensing. However, the mechanisms responsible for actuation and sensing differ; research to date has focused predominantly on actuation, while identification of the dominant mechanism responsible for IPT sensing remains an open topic. The goal of this work is to initiate experimental investigations of the streaming potential hypothesis for IPT sensing. This hypothesis argues that the presence of unbound counter-ions within the hydrophilic phase of an ionic polymer behaves as an electrolyte in the presence of the electrode. Thus, as per classic streaming potential analyses, relative motion of the electrolyte with respect to the electrode will result in the evolution of a streaming potential. According to this hypothesis, the extent of communication between the electrode and electrolyte becomes important in the evolution of an electrical signal. This study experimentally explores the effect of electrode architecture on the sensing response where the IPTs are prepared via the direct assembly process (DAP). The DAP is selected because it enables control over the fabrication of the electrode structure. In this study, cantilevered IPT samples having different electrode composition are tested under several step input tip displacements. The experimental outcomes are consistent with predicted trends via streaming potential theory. (paper)

  8. Removal of anionic azo dyes from aqueous solution by functional ionic liquid cross-linked polymer

    International Nuclear Information System (INIS)

    Gao, Hejun; Kan, Taotao; Zhao, Siyuan; Qian, Yixia; Cheng, Xiyuan; Wu, Wenli; Wang, Xiaodong; Zheng, Liqiang

    2013-01-01

    Highlights: • Equilibrium, kinetic and thermodynamic of adsorption of dyes onto PDVB-IL was investigated. • PDVB-IL has a high adsorption capacity to treat dyes solution. • Higher adsorption capacity is due to the functional groups of PDVB-IL. • Molecular structure of dyes influences the adsorption capacity. -- Abstract: A novel functional ionic liquid based cross-linked polymer (PDVB-IL) was synthesized from 1-aminoethyl-3-vinylimidazolium chloride and divinylbenzene for use as an adsorbent. The physicochemical properties of PDVB-IL were investigated by Fourier transform infrared spectroscopy, scanning electron microscopy and thermogravimetric analysis. The adsorptive capacity was investigated using anionic azo dyes of orange II, sunset yellow FCF, and amaranth as adsorbates. The maximum adsorption capacity could reach 925.09, 734.62, and 547.17 mg/g for orange II, sunset yellow FCF and amaranth at 25 °C, respectively, which are much better than most of the other adsorbents reported earlier. The effect of pH value was investigated in the range of 1–8. The result shows that a low pH value is found to favor the adsorption of those anionic azo dyes. The adsorption kinetics and isotherms are well fitted by a pseudo second-order model and Langmuir model, respectively. The adsorption process is found to be dominated by physisorption. The introduction of functional ionic liquid moieties into cross-linked poly(divinylbenzene) polymer constitutes a new and efficient kind of adsorbent

  9. Solvation thermodynamics

    CERN Document Server

    Ben-Naim, Arieh

    1987-01-01

    This book deals with a subject that has been studied since the beginning of physical chemistry. Despite the thousands of articles and scores of books devoted to solvation thermodynamics, I feel that some fundamen­ tal and well-established concepts underlying the traditional approach to this subject are not satisfactory and need revision. The main reason for this need is that solvation thermodynamics has traditionally been treated in the context of classical (macroscopic) ther­ modynamics alone. However, solvation is inherently a molecular pro­ cess, dependent upon local rather than macroscopic properties of the system. Therefore, the starting point should be based on statistical mechanical methods. For many years it has been believed that certain thermodynamic quantities, such as the standard free energy (or enthalpy or entropy) of solution, may be used as measures of the corresponding functions of solvation of a given solute in a given solvent. I first challenged this notion in a paper published in 1978 b...

  10. Cycling Performance of Li4Ti5O12 Electrodes in Ionic Liquid-Based Gel Polymer Electrolytes

    International Nuclear Information System (INIS)

    Kim, Jin Hee; Kim, Dong Won; Kang, Yong Ku

    2012-01-01

    We investigated the cycling behavior of Li 4 Ti 5 O 12 electrode in a cross-linked gel polymer electrolyte based on non-flammable ionic liquid consisting of 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide and vinylene carbonate. The Li 4 Ti 5 O 12 electrodes in ionic liquid-based gel polymer electrolytes exhibited reversible cycling behavior with good capacity retention. Cycling data and electrochemical impedance spectroscopy analyses revealed that the optimum content of the cross-linking agent necessary to ensure both acceptable initial discharge capacity and good capacity retention was about 8 wt %

  11. Ionic liquids in a poly ethylene oxide cross-linked gel polymer as an electrolyte for electrical double layer capacitor

    Science.gov (United States)

    Chaudoy, V.; Tran Van, F.; Deschamps, M.; Ghamouss, F.

    2017-02-01

    In the present work, we developed a gel polymer electrolyte via the incorporation of a room temperature ionic liquid into a cross-linked polymer matrix. The cross-linked gel electrolyte was prepared using a free radical polymerization of methacrylate and dimethacrylate oligomers dissolved in 1-propyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide. Combining the advantages of the ionic liquids and of conventional polymers, the cross-linked gel polymer electrolyte was used both as a separator and as an electrolyte for a leakage-free and non-flammable EDLC supercapacitor. The quasi-all solid-state supercapacitors showed rather good capacitance, power and energy densities by comparison to a liquid electrolyte-based EDLC.

  12. Influence of Ambient Humidity on the Voltage Response of Ionic Polymer-Metal Composite Sensor.

    Science.gov (United States)

    Zhu, Zicai; Horiuchi, Tetsuya; Kruusamäe, Karl; Chang, Longfei; Asaka, Kinji

    2016-03-31

    Electrical potential based on ion migration exists not only in natural systems but also in ionic polymer materials. In order to investigate the influence of ambient humidity on voltage response, classical Au-Nafion IPMC was chosen as the reference sample. Voltage response under a bending deformation was measured in two ways: first, continuous measurement of voltage response in the process of absorption and desorption of water to study the tendency of voltage variation at all water states; second, measurements at multiple fixed ambient humidity levels to characterize the process of voltage response quantitatively. Ambient humidity influences the voltage response mainly by varying water content in ionic polymer. Under a step bending, the amplitude of initial voltage peak first increases and then decreases as the ambient humidity and the inherent water content decrease. This tendency is explained semiquantitatively by mass storage capacity related to the stretchable state of the Nafion polymer network. Following the initial peak, the voltage shows a slow decay to a steady state, which is first characterized in this paper. The relative voltage decay during the steady state always decreases as the ambient humidity is lowered. It is ascribed to progressive increase of the ratio between the water molecules in the cation hydration shell to the free water. Under sinusoidal mechanical bending excitation in the range of 0.1-10 Hz, the voltage magnitude increases with frequency at high ambient humidity but decreases with frequency at low ambient humidity. The relationship is mainly controlled by the voltage decay effect and the response speed.

  13. Selective transport of Fe(III) using ionic imprinted polymer (IIP) membrane particle

    Science.gov (United States)

    Djunaidi, Muhammad Cholid; Jumina, Siswanta, Dwi; Ulbricht, Mathias

    2015-12-01

    The membrane particles was prepared from polyvinyl alcohol (PVA) and polymer IIP with weight ratios of 1: 2 and 1: 1 using different adsorbent templates and casting thickness. The permeability of membrane towards Fe(III) and also mecanism of transport were studied. The selectivity of the membrane for Fe(III) was studied by performing adsorption experiments also with Cr(III) separately. In this study, the preparation of Ionic Imprinted Polymer (IIP) membrane particles for selective transport of Fe (III) had been done using polyeugenol as functional polymer. Polyeugenol was then imprinted with Fe (III) and then crosslinked with PEGDE under alkaline condition to produce polyeugenol-Fe-PEGDE polymer aggregates. The agrregates was then crushed and sieved using mesh size of 80 and the powder was then used to prepare the membrane particles by mixing it with PVA (Mr 125,000) solution in 1-Methyl-2-pyrrolidone (NMP) solvent. The membrane was obtained after casting at a speed of 25 m/s and soaking in NaOH solution overnight. The membrane sheet was then cut and Fe(III) was removed by acid to produce IIP membrane particles. Analysis of the membrane and its constituent was done by XRD, SEM and size selectivity test. Experimental results showed the transport of Fe(III) was faster with the decrease of membrane thickness, while the higher concentration of template ion correlates with higher Fe(III) being transported. However, the transport of Fe(III) was slower for higher concentration of PVA in the membrane. IImparticles works through retarded permeation mechanism, where Fe(III) was bind to the active side of IIP. The active side of IIP membrane was dominated by the -OH groups. The selectivity of all IIP membranes was confirmed as they were all unable to transport Cr (III), while NIP (Non-imprinted Polymer) membrane was able transport Cr (III).

  14. FTIR Spectroscopic and DC Ionic conductivity Studies of PVDF-HFP: LiBF4: EC Plasticized Polymer Electrolyte Membrane

    Science.gov (United States)

    Sangeetha, M.; Mallikarjun, A.; Jaipal Reddy, M.; Siva Kumar, J.

    2017-08-01

    In the present paper; the FTIR and Temperature dependent DC Ionic conductivity studies of polymer (80 Wt% PVDF-HFP) with inorganic lithium tetra fluoroborate salt (20 Wt% LiBF4) as ionic charge carrier and plasticized with various weight ratios of Ethylene carbonate plasticizer (10 Wt% to 70 Wt% EC) as gel polymer electrolytes. Solution casting method is used for the preparation of plasticized polymer-salt electrolyte films. FTIR analysis shows the good complexation between PVDF-HFP: LiBF4 and the presence of functional groups in the plasticized polymer-salt electrolyte membrane. Also the analysis and results show that the highest DC ionic conductivity of 1.66 × 10-3 SCm -1 was found at 373 K for a particular concentration of 80 Wt% PVDF-HFP: 20 Wt% LiBF4: 40 Wt% EC porous gel type polymer-salt plasticized porous membrane. Increase of temperature results expansion and segmental motion of polymer chain that generates free volume in turn promotes hopping of the lithium ions satisfying Vogel-Tammann-Fulcher equation.

  15. A study of water electrolysis using ionic polymer-metal composite for solar energy storage

    Science.gov (United States)

    Keow, Alicia; Chen, Zheng

    2017-04-01

    Hydrogen gas can be harvested via the electrolysis of water. The gas is then fed into a proton exchange membrane fuel cell (PEMFC) to produce electricity with clean emission. Ionic polymer-metal composite (IPMC), which is made from electroplating a proton-conductive polymer film called Nafion encourages ion migration and dissociation of water under application of external voltage. This property has been proven to be able to act as catalyst for the electrolysis of pure water. This renewable energy system is inspired by photosynthesis. By using solar panels to gather sunlight as the source of energy, the generation of electricity required to activate the IPMC electrolyser is acquired. The hydrogen gas is collected as storable fuel and can be converted back into energy using a commercial fuel cell. The goal of this research is to create a round-trip energy efficient system which can harvest solar energy, store them in the form of hydrogen gas and convert the stored hydrogen back to electricity through the use of fuel cell with minimal overall losses. The effect of increasing the surface area of contact is explored through etching of the polymer electrolyte membrane (PEM) with argon plasma or manually sanding the surface and how it affects the increase of energy conversion efficiency of the electrolyser. In addition, the relationship between temperature and the IPMC is studied. Experimental results demonstrated that increases in temperature of water and changes in surface area contact correlate with gas generation.

  16. Fused filament 3D printing of ionic polymer-metal composites for soft robotics

    Science.gov (United States)

    Carrico, James D.; Leang, Kam K.

    2017-04-01

    Additive manufacturing techniques are used to create three-dimensional structures with complex shapes and features from polymer and/or metal materials. For example, fused filament three-dimensional (3D) printing utilizes non-electroactive polymers, such as acrylonitrile butadiene styrene (ABS) and polylactic acid (PLA), to build structures and components in a layer-by-layer fashion for a wide variety of applications. Presented here is a summary of recent work on a fused filament 3D-printing technique to create 3D ionic polymer-metal composite (IPMC) structures for applications in soft robotics. The 3D printing technique overcomes some of the limitations of existing manufacturing processes for creating IPMCs, such as limited shapes and sizes and time-consuming manufacturing steps. In the process described, first a precursor material (non-acid Nafion precursor resin) is extruded into a thermoplastic filament for 3D printing. Then, a custom-designed 3D printer is described that utilizes the precursor filament to manufacture custom-shaped structures. Finally, the 3D-printed samples are functionalized by hydrolyzing them in an aqueous solution of potassium hydroxide and dimethyl sulfoxide, followed by application of platinum electrodes. Presented are example 3D-printed single and multi-degree-of-freedom IPMC actuators and characterization results, as well as example soft-robotic devices to demonstrate the potential of this process.

  17. Synthesis and characterization of gold nanoparticles in a self-assembled ionic liquid polymer nanocomposite

    Science.gov (United States)

    Magurudeniya, Harsha; Ringstrand, Bryan; Jungjohann, Katherine; Firestone, Millicent

    Incorporation of nanoparticles(NPs) into polymer matrices has attracted interest, offering a means to create multi-functional materials combining the attributes of polymers (flexibility, processability, mechanical durability) with the opto-electrical properties of NPs. Synthesis of a self-supporting, hierarchically structured Au NP-network polymer was accomplished via a ``one-pot'' reaction employing a mesophase of AuCl3 and an imidazolium based-ionic liquid (IL) containing a acrylate group. In-situ generation of NPs was achieved by reduction of Au3+which in turn yields concomitant initiation of the polymerization of the mesophase. FT-IR and thermal analysis confirmed acrylate cross-linking. X-ray scattering confirms preservation of the mesophase within the NP composite. TEM showed a distribution of the NPs within the composite of primarily non-spherical morphologies. The co-integration of a macromer, PEG diacrylate, served as a reducing agent for the Au and the amount incorporated into the mesophase allowed for manipulation of the swelling factor of the resultant nanocomposite in a ethanol, providing means to modulate the plasmonic resonance of the NPs. This methodology provides means for organizing NPs within the structured regions of the poly(IL) matrix. Such composites may be of interest for photonic/sensing applications.

  18. Energy harvesting using ionic electro-active polymer thin films with Ag-based electrodes

    International Nuclear Information System (INIS)

    Anand, S V; Arvind, K; Bharath, P; Roy Mahapatra, D

    2010-01-01

    In this paper we employ the phenomenon of bending deformation induced transport of cations via the polymer chains in the thickness direction of an electro-active polymer (EAP)–metal composite thin film for mechanical energy harvesting. While EAPs have been applied in the past in actuators and artificial muscles, promising applications of such materials in hydrodynamic and vibratory energy harvesting are reported in this paper. For this, functionalization of EAPs with metal electrodes is the key factor in improving the energy harvesting efficiency. Unlike Pt-based electrodes, Ag-based electrodes have been deposited on an EAP membrane made of Nafion. The developed ionic metal polymer composite (IPMC) membrane is subjected to a dynamic bending load, hydrodynamically, and evaluated for the voltage generated against an external electrical load. An increase of a few orders of magnitude has been observed in the harvested energy density and power density in air, deionized water and in electrolyte solutions with varying concentrations of sodium chloride (NaCl) as compared to Pt-based IPMC performances reported in the published literature. This will have potential applications in hydrodynamic and residual environmental energy harvesting to power sensors and actuators based on micro-and nano-electro-mechanical systems (MEMS and NEMS) for biomedical, aerospace and oceanic applications

  19. (1-Butyl-4-methyl-pyridinium)[Cu(SCN)2]: a coordination polymer and ionic liquid.

    Science.gov (United States)

    Spielberg, Eike T; Edengeiser, Eugen; Mallick, Bert; Havenith, Martina; Mudring, Anja-Verena

    2014-04-25

    The compound (C4C1py)[Cu(SCN)2], (C4C1py = 1-Butyl-4-methyl-pyridinium), which can be obtained from CuSCN and the ionic liquid (C4C1py)(SCN), turns out to be a new organic-inorganic hybrid material as it qualifies both, as a coordination polymer and an ionic liquid. It features linked [Cu(SCN)2](-) units, in which the thiocyanates bridge the copper ions in a μ1,3-fashion. The resulting one-dimensional chains run along the a axis, separated by the C4C1py counterions. Powder X-ray diffraction not only confirms the single-crystal X-ray structure solution but proves the reformation of the coordination polymer from an isotropic melt. However, the materials shows a complex thermal behavior often encountered for ionic liquids such as a strong tendency to form a supercooled melt. At a relatively high cooling rate, glass formation is observed. When heating this melt in differential scanning calorimetry (DSC) and temperature-dependent polarizing optical microscopy (POM), investigations reveal the existence of a less thermodynamically stable crystalline polymorph. Raman measurements conducted at 10 and 100 °C point towards the formation of polyanionic chain fragments in the melt. Solid-state UV/Vis spectroscopy shows a broad absorption band around 18,870 cm(-1) (530 nm) and another strong one below 20,000 cm(-1) (<500 nm). The latter is attributed to the d(Cu(I))→π*(SCN)-MLCT (metal-to-ligand charge transfer) transition within the coordination polymer yielding an energy gap of 2.4 eV. At room temperature and upon irradiation with UV light, the material shows a weak fluorescence band at 15,870 cm(-1) (630 nm) with a quantum efficiency of 0.90(2) % and a lifetime of 131(2) ns. Upon lowering the temperature, the luminescence intensity strongly increases. Simultaneously, the band around 450 nm in the excitation spectrum decreases. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Application of a room temperature ionic liquid for nuclear spent fuel reprocessing: speciation of trivalent europium and solvatation effects; Application d'un liquide ionique basse temperature pour les procedes de separation: speciation de l'europium trivalent et effets solvatation

    Energy Technology Data Exchange (ETDEWEB)

    Moutiers, G.; Mekki, S. [CEA Saclay, Dept. de Physico-Chimie, Service de Chimie Physique, 91 - Gif sur Yvette (France); Billard, I. [IN2P3/CNRS, 69 - Villeurbanne (France)

    2007-07-01

    the electrochemical study. In the second chapter, we present the study of europium solvation in the ionic liquid media. In the third part, we expose the results concerning TTA solvation and its complexation with europium in bumimTf{sub 2}N under different conditions. Finally in the last chapter, we present the results obtained for the europium extraction in a three-stage extraction system: water/bumimTf{sub 2}N/supercritical CO{sub 2}. This work highlights the potential use of ionic liquids and particularly bumimTf{sub 2}N in the spent nuclear fuel reprocessing. The ability to extract quantitatively a trivalent lanthanide has been demonstrated. This fundamental study can be regarded as a feasibility demonstration to build an ionic liquid-containing extraction system, in the aim of possible large-scale application. (authors)

  1. A Compact Ionic Polymer Metal Composite (IPMC System with Inductive Sensor for Closed Loop Feedback

    Directory of Open Access Journals (Sweden)

    Jiaqi Wang

    2015-05-01

    Full Text Available Ionic polymer metal composite (IPMC, of which a low actuating voltage (<5 V, high power efficiency and biocompatibility makes it a proven candidate for low power devices. However, due to its inherent nonlinear behaviour and time-variance, feedback control, as well as reliable sensing means, are required for accurate operations. This paper presents an IPMC actuator implemented with an inductive sensor to enhance the reliability and compactness of the overall device. A practical, low cost and importantly, compact inductive sensor fabricated on a printed circuit board (PCB is proposed here. Target material selections and coil design considerations are discussed. It is experimentally determined that the inductive sensor has comparable performance to a laser sensor. Based on a proportional-integral-derivative (PID control results the inductive sensor has demonstrated to be an alternative to a laser sensor allowing devices using IPMC actuators to be compact.

  2. Underwater energy harvesting from a turbine hosting ionic polymer metal composites

    International Nuclear Information System (INIS)

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

    2014-01-01

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

  3. A biomimetic jellyfish robot based on ionic polymer metal composite actuators

    International Nuclear Information System (INIS)

    Yeom, Sung-Weon; Oh, Il-Kwon

    2009-01-01

    A biomimetic jellyfish robot based on ionic polymer metal composite actuators was fabricated and activated to mimic real locomotive behavior with pulse and recovery processes. To imitate the curved shape of the jellyfish, a thermal treatment was applied to obtain a permanent initial deformation of a hemispherical form. The bio-inspired input signal was generated for mimicking real locomotion of the jellyfish. The vertical floating displacement and the thrust force of the biomimetic jellyfish robot under various input signals were measured and compared. The present results show that the bio-inspired electrical input signal with pulse-recovery process generates much higher floating velocity of the biomimetic jellyfish robot in comparison with pure sinusoidal excitations. The curved shape of the IPMC actuator through thermal treatments can be successfully applied to mimic the real biomimetic robots with smooth curves

  4. Ionic polymer-metal composite torsional sensor: physics-based modeling and experimental validation

    Science.gov (United States)

    Aidi Sharif, Montassar; Lei, Hong; Khalid Al-Rubaiai, Mohammed; Tan, Xiaobo

    2018-07-01

    Ionic polymer-metal composites (IPMCs) have intrinsic sensing and actuation properties. Typical IPMC sensors are in the shape of beams and only respond to stimuli acting along beam-bending directions. Rod or tube-shaped IPMCs have been explored as omnidirectional bending actuators or sensors. In this paper, physics-based modeling is studied for a tubular IPMC sensor under pure torsional stimulus. The Poisson–Nernst–Planck model is used to describe the fundamental physics within the IPMC, where it is hypothesized that the anion concentration is coupled to the sum of shear strains induced by the torsional stimulus. Finite element simulation is conducted to solve for the torsional sensing response, where some of the key parameters are identified based on experimental measurements using an artificial neural network. Additional experimental results suggest that the proposed model is able to capture the torsional sensing dynamics for different amplitudes and rates of the torsional stimulus.

  5. Lithium polymer cell assembled by in situ chemical cross-linking of ionic liquid electrolyte with phosphazene-based cross-linking agent

    International Nuclear Information System (INIS)

    Choi, Ji-Ae; Kang, Yongku; Kim, Dong-Won

    2013-01-01

    Highlights: ► Ionic liquid-based cross-linked gel polymer electrolytes were synthesized and their electrochemical properties were investigated. ► Lithium polymer cells with in situ cross-linked gel polymer electrolytes exhibited reversible cycling behavior with good capacity retention. ► The use of ionic liquid-based cross-linked gel polymer electrolytes significantly improved the thermal stability of the cells. -- Abstract: Ionic liquid-based cross-linked gel polymer electrolytes were prepared with a phosphazene-based cross-linking agent, and their electrochemical properties were investigated. Lithium polymer cells composed of lithium anode and LiCoO 2 cathode were assembled with ionic liquid-based cross-linked gel polymer electrolyte and their cycling performance was evaluated. The interfacial adhesion between the electrodes and the electrolyte by in situ chemical cross-linking resulted in stable capacity retention of the cell. A reduction in the ionic mobility in both the electrolyte and the electrode adversely affected discharge capacity and high rate performance of the cell. DSC studies demonstrated that the use of ionic liquid-based cross-linked gel polymer electrolytes provided a significant improvement in the thermal stability of the cell

  6. A review on robotic fish enabled by ionic polymer-metal composite artificial muscles.

    Science.gov (United States)

    Chen, Zheng

    2017-01-01

    A novel actuating material, which is lightweight, soft, and capable of generating large flapping motion under electrical stimuli, is highly desirable to build energy-efficient and maneuverable bio-inspired underwater robots. Ionic polymer-metal composites are important category of electroactive polymers, since they can generate large bending motions under low actuation voltages. IPMCs are ideal artificial muscles for small-scale and bio-inspired robots. This paper takes a system perspective to review the recent work on IPMC-enabled underwater robots, from modeling, fabrication, and bio-inspired design perspectives. First, a physics-based and control-oriented model of IPMC actuator will be reviewed. Second, a bio-inspired robotic fish propelled by IPMC caudal fin will be presented and a steady-state speed model of the fish will be demonstrated. Third, a novel fabrication process for 3D actuating membrane will be introduced and a bio-inspired robotic manta ray propelled by two IPMC pectoral fins will be demonstrated. Fourth, a 2D maneuverable robotic fish propelled by multiple IPMC fin will be presented. Last, advantages and challenges of using IPMC artificial muscles in bio-inspired robots will be concluded.

  7. An Ionic-Polymer-Metallic Composite Actuator for Reconfigurable Antennas in Mobile Devices

    Directory of Open Access Journals (Sweden)

    Yi-Chen Lin

    2014-01-01

    Full Text Available In this paper, a new application of an electro-active-polymer for a radio frequency (RF switch is presented. We used an ionic polymer metallic composite (IPMC switch to change the operating frequency of an inverted-F antenna. This switch is light in weight, small in volume, and low in cost. In addition, the IPMC is suitable for mobile devices because of its driving voltage of 3 volts and thickness of 200 μm. The IPMC acts as a normally-on switch to control the operating frequency of a reconfigurable antenna in mobile phones. We experimentally demonstrated by network analysis that the IPMC switch could shift its operating frequency from 1.1 to 2.1 GHz, with return losses of than −10 dB at both frequencies. To minimize electrolysis and maximize the operation time in air, propylene carbonate electrolyte with lithium perchlorate (LiClO4 was applied inside the IPMC. The results showed that when the IPMC was actuated over three months at 3.5 V, the tip displacement fell by less than 10%. Therefore, an IPMC actuator is a promising choice for application to a reconfigurable antenna.

  8. Flexibility Matters: Cooperative Active Sites in Covalent Organic Framework and Threaded Ionic Polymer.

    Science.gov (United States)

    Sun, Qi; Aguila, Briana; Perman, Jason; Nguyen, Nicholas; Ma, Shengqian

    2016-12-07

    The combination of two or more reactive centers working in concert on a substrate to facilitate the reaction is now considered state of the art in catalysis, yet there still remains a tremendous challenge. Few heterogeneous systems of this sort have been exploited, as the active sites spatially separated within the rigid framework are usually difficult to cooperate. It is now shown that this roadblock can be surpassed. The underlying principle of the strategy presented here is the integration of catalytic components with excellent flexibility and porous heterogeneous catalysts, as demonstrated by the placement of linear ionic polymers in close proximity to surface Lewis acid active sites anchored on the walls of a covalent organic framework (COF). Using the cycloaddition of the epoxides and CO 2 as a model reaction, dramatic activity improvements have been achieved for the composite catalysts in relation to the individual catalytic component. Furthermore, they also clearly outperform the benchmark catalytic systems formed by the combination of the molecular organocatalysts and heterogeneous Lewis acid catalysts, while affording additional recyclability. The extraordinary flexibility and enriched concentration of the catalytically active moieties on linear polymers facilitate the concerted catalysis, thus leading to superior catalytic performance. This work therefore uncovers an entirely new strategy for designing bifunctional catalysts with double-activation behavior and opens a new avenue in the design of multicapable systems that mimic biocatalysis.

  9. Nonpolar solvation dynamics for a nonpolar solute in room ...

    Indian Academy of Sciences (India)

    Sandipa Indra

    2018-01-30

    Jan 30, 2018 ... Keywords. Solvation dynamics; nonpolar solvation; ionic liquid; molecular dynamics; linear response theory. 1. ... J. Chem. Sci. (2018) 130:3 spectrum of the excited probe molecule for imida- .... Therefore, the solute and the RTIL ions interact only ... interval of 30 ps from a long equilibrium trajectory of dura-.

  10. Interpenetrated polymer networks based on commercial silicone elastomers and ionic networks with high dielectric permittivity and self-healing properties

    DEFF Research Database (Denmark)

    Ogliani, Elisa; Yu, Liyun; Skov, Anne Ladegaard

    the applicability. One method used to avoid this limitation is to increase the dielectric permittivity of the material in order to improve the actuation response at a given field. Recently, interpenetrating polymer networks (IPNs) based on covalently cross-linked commercial silicone elastomers and ionic networks...... from amino- and carboxylic acid- functional silicones have been designed[2] (Figure 1). This novel system provides both the mechanical stability and the high breakdown strength given by the silicone part of the IPNs and the high permittivity and the softening effect of the ionic network. Thus......,1 Hz), and the commercial elastomers RT625 and LR3043/30 provide thebest viscoelastic properties to the systems, since they maintain low viscous losses upon addition of ionic network. The values ofthe breakdown strength in all cases remain higher than that of the reference pure PDMS network (ranging...

  11. Thermostable gel polymer electrolyte based on succinonitrile and ionic liquid for high-performance solid-state supercapacitors

    Science.gov (United States)

    Pandey, Gaind P.; Liu, Tao; Hancock, Cody; Li, Yonghui; Sun, Xiuzhi Susan; Li, Jun

    2016-10-01

    A flexible, free-standing, thermostable gel polymer electrolyte based on plastic crystalline succinonitrile (SN) and ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (BMImBF4) entrapped in copolymer poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) is prepared and optimized for application in solvent-free solid-state supercapacitors. The synthesized gel polymer electrolyte exhibits a high ionic conductivity over a wide temperature range (from ∼5 × 10-4 S cm-1 at -30 °C up to ∼1.5 × 10-2 S cm-1 at 80 °C) with good electrochemical stability window (-2.9 to 2.5 V). Thermal studies confirm that the SN containing gel polymer electrolyte remains stable in the same gel phase over a wide temperature range from -30 to 90 °C. The electric double layer capacitors (EDLCs) have been fabricated using activated carbon as active materials and new gel polymer electrolytes. Electrochemical performance of the EDLCs is assessed through cyclic voltammetry, galvanostatic charge-discharge cycling and impedance spectroscopy. The EDLC cells with the proper SN-containing gel polymer electrolyte has been found to give high specific capacitance 176 F g-1 at 0.18 A g-1 and 138 F g-1 at 8 A g-1. These solid-state EDLC cells show good cycling stability and the capability to retain ∼80% of the initial capacitance after 10,000 cycles.

  12. Effect of PVC on ionic conductivity, crystallographic structural, morphological and thermal characterizations in PMMA-PVC blend-based polymer electrolytes

    International Nuclear Information System (INIS)

    Ramesh, S.; Liew, Chiam-Wen; Morris, Ezra; Durairaj, R.

    2010-01-01

    In this paper, temperature dependence of ionic conductivity, crystallographic structural, morphological and thermal characteristics of polymer blends of PMMA and PVC with lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) as a dopant salt are investigated. The study on the temperature dependence of ionic conductivity shows that these polymer blends exhibit Arrhenius behavior. The highest ionic conductivity was achieved when 70 wt% of PMMA was blended with 30 wt% of PVC. X-ray diffraction (XRD) and scanning electron microscopy (SEM) reveal the amorphous nature and surface morphology of polymer electrolytes, respectively. In DSC analysis it was found that the glass transition temperature (T g ) and melting temperature (T m ) decreased, whereas the decomposition temperature (T d ) increased. In contrast, the shift towards higher decomposition temperature and decrease in weight loss of polymer electrolytes, in TGA studies, indicates that the thermal stability of polymer electrolytes improved.

  13. Effect of PVC on ionic conductivity, crystallographic structural, morphological and thermal characterizations in PMMA-PVC blend-based polymer electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Ramesh, S., E-mail: rameshtsubra@gmail.com [Centre for Ionics University Malaya, Department of Physics, Faculty of Science, University of Malaya, Lembah Pantai, 50603 Kuala Lumpur (Malaysia); Liew, Chiam-Wen; Morris, Ezra; Durairaj, R. [Faculty of Engineering and Science, Universiti Tunku Abdul Rahman, Setapak, 53300 Kuala Lumpur (Malaysia)

    2010-11-20

    In this paper, temperature dependence of ionic conductivity, crystallographic structural, morphological and thermal characteristics of polymer blends of PMMA and PVC with lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) as a dopant salt are investigated. The study on the temperature dependence of ionic conductivity shows that these polymer blends exhibit Arrhenius behavior. The highest ionic conductivity was achieved when 70 wt% of PMMA was blended with 30 wt% of PVC. X-ray diffraction (XRD) and scanning electron microscopy (SEM) reveal the amorphous nature and surface morphology of polymer electrolytes, respectively. In DSC analysis it was found that the glass transition temperature (T{sub g}) and melting temperature (T{sub m}) decreased, whereas the decomposition temperature (T{sub d}) increased. In contrast, the shift towards higher decomposition temperature and decrease in weight loss of polymer electrolytes, in TGA studies, indicates that the thermal stability of polymer electrolytes improved.

  14. Dynamic model of ion and water transport in ionic polymer-metal composites

    Directory of Open Access Journals (Sweden)

    Zicai Zhu

    2011-12-01

    Full Text Available In the process of electro-mechanical transduction of ionic polymer-metal composites (IPMCs, the transport of ion and water molecule plays an important role. In this paper, the theoretical transport models of IPMCs are critically reviewed, with particular emphasis on the recent developments in the latest decade. The models can be divided into three classes, thermodynamics of irreversible process model, frictional model and Nernst-Planck (NP equation model. To some extent the three models can be transformed into each other, but their differences are also obvious arising from the various mechanisms that considered in different models. The transport of ion and water molecule in IPMCs is compared with that in membrane electrode assembly and electrodialysis membrane to identify and clarify the fundamental transport mechanisms in IPMCs. And an improved transport model is proposed and simplified for numerical analysis. The model considers the convection effect rather than the diffusion as the major transport mechanism, and both the self-diffusion and the electroosmosis drag are accounted for in the water flux equation.

  15. Manufacturing of ionic polymer-metal composites (IPMCs) that can actuate into complex curves

    Science.gov (United States)

    Stoimenov, Boyko L.; Rossiter, Jonathan M.; Mukai, Toshiharu

    2007-04-01

    Ionic polymer-metal composites (IPMC) are soft actuators with potential applications in the fields of medicine and biologically inspired robotics. Typically, an IPMC bends with approximately constant curvature when voltage is applied to it. More complex shapes were achieved in the past by pre-shaping the actuator or by segmentation and separate actuation of each segment. There are many applications for which fully independent control of each segment of the IPMC is not required and the use of external wiring is objectionable. In this paper we propose two key elements needed to create an IPMC, which can actuate into a complex curve. The first is a connection between adjacent segments, which enables opposite curvature. This can be achieved by reversing the polarity applied on each side of the IPMC, for example by a through-hole connection. The second key element is a variable curvature segment. The segment is designed to bend with any fraction of its full bending ability under given electrical input by changing the overlap of opposite charge electrodes. We demonstrated the usefulness of these key elements in two devices. One is a bi-stable buckled IPMC beam, also used as a building block in a linear actuator device. The other one is an IPMC, actuating into an S-shaped curve with gradually increasing curvature near the ends. The proposed method of manufacturing holds promise for a wide range of new applications of IPMCs, including applications in which IPMCs are used for sensing.

  16. Flow measurement and thrust estimation of a vibrating ionic polymer metal composite

    International Nuclear Information System (INIS)

    Chae, Woojin; Cha, Youngsu; Peterson, Sean D; Porfiri, Maurizio

    2015-01-01

    Ionic polymer metal composites (IPMCs) are an emerging class of soft active materials that are finding growing application as underwater propulsors for miniature biomimetic swimmers. Understanding the hydrodynamics generated by an IPMC vibrating under water is central to the design of such biomimetic swimmers. In this paper, we propose the use of time-resolved particle image velocimetry to detail the fluid kinematics and kinetics in the vicinity of an IPMC vibrating along its fundamental structural mode. The reconstructed pressure field is ultimately used to estimate the thrust produced by the IPMC. The vibration frequency is systematically varied to elucidate the role of the Reynolds number on the flow physics and the thrust production. Experimental results indicate the formation and shedding of vortical structures from the IPMC tip during its vibration. Vorticity shedding is sustained by the pressure gradients along each side of the IPMC, which are most severe in the vicinity of the tip. The mean thrust is found to robustly increase with the Reynolds number, closely following a power law that has been derived from direct three-dimensional numerical simulations. A reduced order distributed model is proposed to describe IPMC underwater vibration and estimate thrust production, offering insight into the physics of underwater propulsion and aiding in the design of IPMC-based propulsors. (paper)

  17. Bias-dependent model of the electrical impedance of ionic polymer-metal composites.

    Science.gov (United States)

    Cha, Youngsu; Porfiri, Maurizio

    2013-02-01

    In this paper, we analyze the charge dynamics of ionic polymer-metal composites (IPMCs) in response to voltage inputs composed of a large dc bias and a small superimposed time-varying voltage. The IPMC chemoelectrical behavior is described through the modified Poisson-Nernst-Planck framework, in which steric effects are taken into consideration. The physics of charge build-up and mass transfer in the proximity of the high surface electrodes is modeled by schematizing the IPMC as the stacked sequence of five layers, in which the ionomeric membrane is separated from the metal electrodes by two composite layers. The method of matched asymptotic expansions is used to derive a semianalytical solution for the concentration of mobile counterions and the electric potential in the IPMC, which is, in turn, used to establish an equivalent circuit model for the IPMC electrical response. The circuit model consists of the series connection of a resistor and two complex elements, each constituted by the parallel connection of a capacitor and a Warburg impedance. The resistor is associated with ion transport in the ionomeric membrane and is independent of the dc bias. The capacitors and the Warburg impedance idealize charge build-up and mass transfer in the vicinity of the electrodes and their value is controlled by the dc bias. The proposed approach is validated against experimental results on in-house fabricated IPMCs and the accuracy of the equivalent circuit is assessed through comparison with finite element results.

  18. Solvation in supercritical water

    International Nuclear Information System (INIS)

    Cochran, H.D.; Cummings, P.T.; Karaborni, S.

    1991-01-01

    The aim of this work is to determine the solvation structure in supercritical water composed with that in ambient water and in simple supercritical solvents. Molecular dynamics studies have been undertaken of systems that model ionic sodium and chloride, atomic argon, and molecular methanol in supercritical aqueous solutions using the simple point charge model of Berendsen for water. Because of the strong interactions between water and ions, ionic solutes are strongly attractive in supercritical water, forming large clusters of water molecules around each ion. Methanol is found to be a weakly-attractive solute in supercritical water. The cluster of excess water molecules surrounding a dissolved ion or polar molecule in supercritical aqueous solutions is comparable to the solvent clusters surrounding attractive solutes in simple supercritical fluids. Likewise, the deficit of water molecules surrounding a dissolved argon atom in supercritical aqueous solutions is comparable to that surrounding repulsive solutes in simple supercritical fluids. The number of hydrogen bonds per water molecule in supercritical water was found to be about one third the number in ambient water. The number of hydrogen bonds per water molecule surrounding a central particle in supercritical water was only mildly affected by the identify of the central particle--atom, molecule, or ion. These results should be helpful in developing a qualitative understanding of important processes that occur in supercritical water. 29 refs., 6 figs

  19. High Ionic Conductivity of Composite Solid Polymer Electrolyte via In Situ Synthesis of Monodispersed SiO2 Nanospheres in Poly(ethylene oxide).

    Science.gov (United States)

    Lin, Dingchang; Liu, Wei; Liu, Yayuan; Lee, Hye Ryoung; Hsu, Po-Chun; Liu, Kai; Cui, Yi

    2016-01-13

    High ionic conductivity solid polymer electrolyte (SPE) has long been desired for the next generation high energy and safe rechargeable lithium batteries. Among all of the SPEs, composite polymer electrolyte (CPE) with ceramic fillers has garnered great interest due to the enhancement of ionic conductivity. However, the high degree of polymer crystallinity, agglomeration of ceramic fillers, and weak polymer-ceramic interaction limit the further improvement of ionic conductivity. Different from the existing methods of blending preformed ceramic particles with polymers, here we introduce an in situ synthesis of ceramic filler particles in polymer electrolyte. Much stronger chemical/mechanical interactions between monodispersed 12 nm diameter SiO2 nanospheres and poly(ethylene oxide) (PEO) chains were produced by in situ hydrolysis, which significantly suppresses the crystallization of PEO and thus facilitates polymer segmental motion for ionic conduction. In addition, an improved degree of LiClO4 dissociation can also be achieved. All of these lead to good ionic conductivity (1.2 × 10(-3) S cm(-1) at 60 °C, 4.4 × 10(-5) S cm(-1) at 30 °C). At the same time, largely extended electrochemical stability window up to 5.5 V can be observed. We further demonstrated all-solid-state lithium batteries showing excellent rate capability as well as good cycling performance.

  20. Solvation of ionic liquids based on N-alkyl-N-methylmorpholinium cations in N,N-dimethylformamide and dimethyl sulfoxide – A volumetric and acoustic study

    International Nuclear Information System (INIS)

    Marcinkowski, Łukasz; Szepiński, Emil; Kloskowski, Adam; Namieśnik, Jacek; Warmińska, Dorota

    2017-01-01

    Highlights: • V ϕ of DMSO and DMF solutions of [Mor1,R][BF 4 ] increase with increasing IL concentration at all investigated temperatures. • Ion–ion interaction are stronger for DMF solutions than corresponding for DMSO. • DMSO interacts more effectively with ionic liquids studied than DMF. • Obtained results are the consequence of the cation size of the ionic liquid. - Abstract: Apparent molar volumes and molar isentropic compressibilities for N-ethyl-N-methylmorpholinium and N-decyl-N-methylmorpholinium tetrafluoroborates in N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) have been determined from density and speed of sound measurements over the temperature range T = (298.15, 303.15, 308.15, 313.15, 318.15 and 328.15) K at experimental pressure p = 0.1 MPa. This data has been used to calculate partial molar volumes and partial molar isentropic compressibilities at infinite dilution. The partial molar expansion coefficients and their secondary derivative have been estimated as well. The obtained results indicate that dimethyl sulfoxide interacts more effectively with ionic liquids studied than N,N-dimetylformamide and ion–ion interaction are stronger for N,N-dimetylformamide solutions than corresponding in dimethyl sulfoxide. Moreover the temperature dependence of the limiting apparent molar volumes and compressibilities is a result of temperature influence on the electrostriction effect, the ordering of a bulk solvent and number solvent molecules in the nearest presence of the salt.

  1. Evolution of carboxymethyl cellulose layer morphology on hydrophobic mineral surfaces: variation of polymer concentration and ionic strength.

    Science.gov (United States)

    Beaussart, Audrey; Mierczynska-Vasilev, Agnieszka; Beattie, David A

    2010-06-15

    The adsorption of carboxymethyl cellulose (CMC) on the basal planes of talc and molybdenite has been studied using in situ atomic force microscope (AFM) imaging. These experiments were partnered with quantitative adsorption isotherm determinations on particulate samples. The isotherms revealed a clear increase of the CMC adsorbed amount upon increasing the solution ionic strength for adsorption on both minerals. In addition, the shapes of the isotherms changed in response to the change in the electrolyte concentration, with CMC on talc displaying stepped (10(-3) M KCl), Langmuir (10(-2) M KCl), then Freundlich isotherm shapes (10(-1) M KCl), and CMC on molybdenite displaying stepped (10(-3) M KCl), Freundlich (10(-2) M KCl), then Langmuir isotherm shapes (10(-1) M KCl). AFM imaging of the polymer layer on the mineral surfaces with varying solution conditions mirrored and confirmed the conclusions from the isotherms: as the polymer solution concentration increased, coverage on the basal plane increased; as the ionic strength increased, coverage on the basal plane increased and the morphology of the layer changed from isolated well-distributed polymer domains to extensive adsorption and formation of dense, uneven polymer domains/features. In addition, comparison of the talc and molybdenite datasets points toward the presence of different binding mechanisms for CMC adsorption on the talc and molybdenite basal plane surfaces. 2010 Elsevier Inc. All rights reserved.

  2. From Interfaces to Bulk: Experimental-Computational Studies Across Time and Length Scales of Multi-Functional Ionic Polymers

    Energy Technology Data Exchange (ETDEWEB)

    Perahia, Dvora [Clemson Univ., SC (United States); Grest, Gary S. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2017-01-25

    Neutron experiments coupled with computational components have resulted in unprecedented understanding of the factors that impact the behavior of ionic structured polymers. Additionally, new computational tools to study macromolecules, were developed. In parallel, this DOE funding have enabled the education of the next generation of material researchers who are able to take the advantage neutron tools offer to the understanding and design of advanced materials. Our research has provided unprecedented insight into one of the major factors that limits the use of ionizable polymers, combining the macroscopic view obtained from the experimental techniques with molecular insight extracted from computational studies leading to transformative knowledge that will impact the design of nano-structured, materials. With the focus on model systems, of broad interest to the scientific community and to industry, the research addressed challenges that cut across a large number of polymers, independent of the specific chemical structure or the transported species.

  3. Matrix-assisted laser desorption/ionization mass spectrometric analysis of aliphatic biodegradable photoluminescent polymers using new ionic liquid matrices.

    Science.gov (United States)

    Serrano, Carlos A; Zhang, Yi; Yang, Jian; Schug, Kevin A

    2011-05-15

    In this study, two novel ionic liquid matrices (ILMs), N,N-diisopropylethylammonium 3-oxocoumarate and N,N-diisopropylethylammonium dihydroxymonooxoacetophenoate, were tested for the structural elucidation of recently developed aliphatic biodegradable polymers by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). The polymers, formed by a condensation reaction of three components, citric acid, octane diol, and an amino acid, are fluorescent, but the exact mechanism behind their luminescent properties has not been fully elucidated. In the original studies, which introduced the polymer class (J. Yang et al., Proc. Natl. Acad. Sci. USA 2009, 106, 10086-10091), a hyper-conjugated cyclic structure was proposed as the source for the photoluminescent behavior. With the use of the two new ILMs, we present evidence that supports the presence of the proposed cyclization product. In addition, the new ILMs, when compared with a previously established ILM, N,N-diisopropylethylammonium α-cyano-3-hydroxycinnimate, provided similar signal intensities and maintained similar spectral profiles. This research also established that the new ILMs provided good spot-to-spot reproducibility and high ionization efficiency compared with corresponding crystalline matrix preparations. Many polymer features revealed through the use of the ILMs could not be observed with crystalline matrices. Ultimately, the new ILMs highlighted the composition of the synthetic polymers, as well as the loss of water that was expected for the formation of the proposed cyclic structure on the polymer backbone. Copyright © 2011 John Wiley & Sons, Ltd.

  4. Ionic Polymer-Metal Composites (IPMCs) as Biomimetic Sensors, Actuators and Artificial Muscles: A Review

    Science.gov (United States)

    Shahinpoor, M.; Bar-Cohen, Y.; Simpson, J. O.; Smith, J.

    1998-01-01

    This paper presents an introduction to ionic polymer-metal composites and some mathematical modeling pertaining to them. It further discusses a number of recent findings in connection with ion-exchange polymer-metal composites (IPMCS) as biomimetic sensors and actuators. Strips of these composites can undergo large bending and flapping displacement if an electric field is imposed across their thickness. Thus, in this sense they are large motion actuators. Conversely by bending the composite strip, either quasi-statically or dynamically, a voltage is produced across the thickness of the strip. Thus, they are also large motion sensors. The output voltage can be calibrated for a standard size sensor and correlated to the applied loads or stresses. They can be manufactured and cut in any size and shape. In this paper first the sensing capability of these materials is reported. The preliminary results show the existence of a linear relationship between the output voltage and the imposed displacement for almost all cases. Furthermore, the ability of these IPMCs as large motion actuators and robotic manipulators is presented. Several muscle configurations are constructed to demonstrate the capabilities of these IPMC actuators. This paper further identifies key parameters involving the vibrational and resonance characteristics of sensors and actuators made with IPMCS. When the applied signal frequency varies, so does the displacement up to a critical frequency called the resonant frequency where maximum deformation is observed, beyond which the actuator response is diminished. A data acquisition system was used to measure the parameters involved and record the results in real time basis. Also the load characterizations of the IPMCs were measured and it was shown that these actuators exhibit good force to weight characteristics in the presence of low applied voltages. Finally reported are the cryogenic properties of these muscles for potential utilization in an outer space

  5. Characterization of the harvesting capabilities of an ionic polymer metal composite device

    Science.gov (United States)

    Brufau-Penella, J.; Puig-Vidal, M.; Giannone, P.; Graziani, S.; Strazzeri, S.

    2008-02-01

    Harvesting systems capable of transforming dusty environmental energy into electrical energy have aroused considerable interest in the last two decades. Several research works have focused on the transformation of mechanical environmental vibrations into electrical energy. Most of the research activity refers to classic piezoelectric ceramic materials, but more recently piezoelectric polymer materials have been considered. In this paper, a novel point of view regarding harvesting systems is proposed: using ionic polymer metal composites (IPMCs) as generating materials. The goal of this paper is the development of a model able to predict the energy harvesting capabilities of an IPMC material working in air. The model is developed by using the vibration transmission theory of an Euler-Bernoulli cantilever IPMC beam. The IPMC is considered to work in its linear elastic region with a viscous damping contribution ranging from 0.1 to 100 Hz. An identification process based on experimental measurements performed on a Nafion® 117 membrane is used to estimate the material parameters. The model validation shows a good agreement between simulated and experimental results. The model is used to predict the optimal working region and the optimal geometrical parameters for the maximum power generation capacity of a specific membrane. The model takes into account two restrictions. The first is due to the beam theory, which imposes a maximum ratio of 0.5 between the cantilever width and length. The second restriction is to force the cantilever to oscillate with a specific strain; in this paper a 0.3% strain is considered. By considering these two assumptions as constraints on the model, it is seen that IPMC materials could be used as low-power generators in a low-frequency region. The optimal dimensions for the Nafion® 117 membrane are length = 12 cm and width = 6.2 cm, and the electric power generation is 3 nW at a vibrating frequency of 7.09 rad s-1. IPMC materials can sustain

  6. On the extraction of ion association data and transference numbers from ionic diffusivity and conductivity data in polymer electrolytes

    International Nuclear Information System (INIS)

    Stolwijk, Nicolaas A.; Kösters, Johannes; Wiencierz, Manfred; Schönhoff, Monika

    2013-01-01

    The degree of ion association in polymer electrolytes is often characterized by the Nernst–Einstein deviation parameter Δ, which quantifies the relative difference between the true ionic conductivity directly measured by electrical methods and the hypothetical maximum conductivity calculated from the individual ionic self-diffusion coefficients. Despite its unambiguous definition, the parameter Δ is a global quantity with limited explanatory power. Similar is true for the cation transport number t cat * , which relies on the same ionic diffusion coefficients usually measured by nuclear magnetic resonance or radiotracer methods. Particularly in cases when neutral ion pairs dominate over higher-order aggregates, more specific information can be extracted from the same body of experimental data that is used for the calculation of Δ and t cat * . This information concerns the pair contributions to the diffusion coefficient of cations and anions. Also the true cation transference number based on charged species only can be deduced. We present the basic theoretical framework and some pertinent examples dealing with ion pairing in polymer electrolytes

  7. Searching for a new ionomer for 3D printable ionic polymer-metal composites: Aquivion as a candidate

    Science.gov (United States)

    Trabia, Sarah; Olsen, Zakai; Kim, Kwang J.

    2017-11-01

    The work presented in this paper introduces Aquivion as a potential candidate for additive manufacturing of ionomeric polymers for the application of IPMCs. First, Aquivion was characterized and compared with Nafion to show that it has the similar qualities, with the major difference being the ionic conductivity. Ionic polymer-metal composites (IPMCs) were fabricated using off-the-shelf membranes of Nafion and Aquivion. The actuation tests showed improved performance for an IPMC with Aquivion as the base compared to an IPMC with a Nafion base. With these results in mind, additive manufacturing of unique shapes using Aquivion filament was studied. A 3D printer was modified to work with Aquivion filament and the polymer was printed into various shapes. Using the printed membranes, IPMCs were fabricated using an electroless plating process. Nafion-based and printed Aquivion-based IPMCs were tested for their performance in back relaxation, frequency driven actuation, blocking force, and mechano-electric sensing. The printed Aquivion-based IPMCs performed comparably to Nafion-based IPMC in back relaxation and showed significantly improved performance in frequency driven actuation, blocking force generation, and mechano-electric sensing.

  8. Extremely stretchable thermosensitive hydrogels by introducing slide-ring polyrotaxane cross-linkers and ionic groups into the polymer network

    Science.gov (United States)

    Bin Imran, Abu; Esaki, Kenta; Gotoh, Hiroaki; Seki, Takahiro; Ito, Kohzo; Sakai, Yasuhiro; Takeoka, Yukikazu

    2014-01-01

    Stimuli-sensitive hydrogels changing their volumes and shapes in response to various stimulations have potential applications in multiple fields. However, these hydrogels have not yet been commercialized due to some problems that need to be overcome. One of the most significant problems is that conventional stimuli-sensitive hydrogels are usually brittle. Here we prepare extremely stretchable thermosensitive hydrogels with good toughness by using polyrotaxane derivatives composed of α-cyclodextrin and polyethylene glycol as cross-linkers and introducing ionic groups into the polymer network. The ionic groups help the polyrotaxane cross-linkers to become well extended in the polymer network. The resulting hydrogels are surprisingly stretchable and tough because the cross-linked α-cyclodextrin molecules can move along the polyethylene glycol chains. In addition, the polyrotaxane cross-linkers can be used with a variety of vinyl monomers; the mechanical properties of the wide variety of polymer gels can be improved by using these cross-linkers. PMID:25296246

  9. Controlled Sol-Gel Transitions of a Thermoresponsive Polymer in a Photoswitchable Azobenzene Ionic Liquid as a Molecular Trigger.

    Science.gov (United States)

    Wang, Caihong; Hashimoto, Kei; Tamate, Ryota; Kokubo, Hisashi; Watanabe, Masayoshi

    2018-01-02

    Producing ionic liquids (ILs) that function as molecular trigger for macroscopic change is a challenging issue. Photoisomerization of an azobenzene IL at the molecular level evokes a macroscopic response (light-controlled mechanical sol-gel transitions) for ABA triblock copolymer solutions. The A endblocks, poly(2-phenylethyl methacrylate), show a lower critical solution temperature in the IL mixture containing azobenzene, while the B midblock, poly(methyl methacrylate), is compatible with the mixture. In a concentrated polymer solution, different gelation temperatures were observed in it under dark and UV conditions. Light-controlled sol-gel transitions were achieved by a photoresponsive solubility change of the A endblocks upon photoisomerization of the azobenzene IL. Therefore, an azobenzene IL as a molecular switch can tune the self-assembly of a thermoresponsive polymer, leading to macroscopic light-controlled sol-gel transitions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. The role of MgBr2 to enhance the ionic conductivity of PVA/PEDOT:PSS polymer composite

    Directory of Open Access Journals (Sweden)

    Eslam M. Sheha

    2015-07-01

    Full Text Available A solid polymer electrolyte system based on poly(vinyl alcohol (PVA and poly(3,4-Etylenedioxythiophene:poly(styrenesulfonate (PEDOT:PSS complexed with magnesium bromide (MgBr2 salt was prepared using solution cast technique. The ionic conductivity is observed to increase with increasing MgBr2 concentration. The maximum conductivity was found to be 9.89 × 10−6 S/cm for optimum polymer composite film (30 wt.% MgBr2 at room temperature. The increase in the conductivity is attributed to the increase in the number of ions as the salt concentration is increased. This has been proven by dielectric studies. The increase in conductivity is also attributable to the increase in the fraction of amorphous region in the electrolyte films as confirmed by their structural, thermal, electrical and optical properties.

  11. Thermotropic Ionic Liquid Crystals

    Science.gov (United States)

    Axenov, Kirill V.; Laschat, Sabine

    2011-01-01

    The last five years’ achievements in the synthesis and investigation of thermotropic ionic liquid crystals are reviewed. The present review describes the mesomorphic properties displayed by organic, as well as metal-containing ionic mesogens. In addition, a short overview on the ionic polymer and self-assembled liquid crystals is given. Potential and actual applications of ionic mesogens are also discussed. PMID:28879986

  12. Thermotropic Ionic Liquid Crystals.

    Science.gov (United States)

    Axenov, Kirill V; Laschat, Sabine

    2011-01-14

    The last five years' achievements in the synthesis and investigation of thermotropic ionic liquid crystals are reviewed. The present review describes the mesomorphic properties displayed by organic, as well as metal-containing ionic mesogens. In addition, a short overview on the ionic polymer and self-assembled liquid crystals is given. Potential and actual applications of ionic mesogens are also discussed.

  13. Thermotropic Ionic Liquid Crystals

    OpenAIRE

    Axenov, Kirill V.; Laschat, Sabine

    2011-01-01

    The last five years’ achievements in the synthesis and investigation of thermotropic ionic liquid crystals are reviewed. The present review describes the mesomorphic properties displayed by organic, as well as metal-containing ionic mesogens. In addition, a short overview on the ionic polymer and self-assembled liquid crystals is given. Potential and actual applications of ionic mesogens are also discussed.

  14. Solvation and stabilization of palladium nanoparticles in phosphonium-based ionic liquids: a combined infrared spectroscopic and density functional theory study.

    Science.gov (United States)

    Zvereva, Elena E; Grimme, Stefan; Katsyuba, Sergey A; Ermolaev, Vadim V; Arkhipova, Daria A; Yan, Ning; Miluykov, Vasili A; Sinyashin, Oleg G; Aleksandrov, Alexey

    2014-10-14

    Analysis of infrared spectra of palladium nanoparticles (NPs) immersed in the tri-tert-butyl-R-phosphonium-based ionic liquids (ILs) demonstrates that both cations and anions of the ILs interact with the NPs. According to quantum-chemical simulations of these interactions, the binding energy of anions to the Pd6 cluster, taken as a minimal-size model of the NPs, increases from ∼6 to ∼27 kcal mol(-1) in the order [PF6](-)≈ [BF4](-) < [Tf2N](-) < [OTf](-) < [Br](-)≪ [TFA](-). In contrast, the binding energy for all types of the [Bu(t)3PR](+) cations slightly varies at about ∼22 kcal mol(-1) only moderately depending on the choice of the R moiety (n-pentyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxy-2-oxoethyl). As a result, the energies of interaction between a Pd6 cluster and various ion pairs, formed by the abovementioned counter-ions, follow the order found for the anions and vary from ∼24 to ∼47 kcal mol(-1). These values are smaller than the energy of addition of a Pd atom to a Pdn cluster (∼58 kcal mol(-1)), which suggests kinetic stabilization of the NPs in phosphonium-based ILs rather than thermodynamic stabilization. The results are qualitatively similar to the trends found earlier for interactions between palladium clusters and components of imidazolium-based ILs, in spite of much larger contributions of the London dispersion forces to the binding of the [Bu(t)3PR](+) cations to the cluster (up to 80%) relative to the case of 1-R-3-methylimidazolium cations (up to 40%).

  15. Development and manufacture of printable next-generation gel polymer ionic liquid electrolyte for Zn/MnO2 batteries

    International Nuclear Information System (INIS)

    Winslow, R; Wang, Z; Wright, P; Wu, C H; Kim, B; Evans, J; Keif, M

    2013-01-01

    While much energy storage research focuses on the performance of individual components, such as the electrolyte or a single electrode, few investigate the electrochemical system as a whole. This research reports on the design, composition, and performance of a Zn/MnO 2 battery as affected by the manufacturing method and next-generation gel polymer electrolyte composed of the ionic liquid [BMIM][Otf], ZnOtf salt, and PVDF-HFP polymer binder. Materials and manufacturing tests are discussed with a focus on water concentration, surface features as produced by printing processes, and the effect of including a gel polymer phase. Cells produced for this research generated open circuit voltages from 1.0 to 1.3 V. A dry [BMIM][Otf] electrolyte was found to have 87.3 ppm of H 2 O, while an electrolyte produced in ambient conditions contained 12400 ppm of H 2 O. Cells produced in a dry, Ar environment had an average discharge capacity of 0.0137 mAh/cm 2 , while one produced in an ambient environment exhibited a discharge capacity at 0.05 mAh/cm 2 . Surface features varied significantly by printing method, where a doctor blade produced the most consistent features. The preliminary results herein suggest that water, surface roughness, and the gel polymer play important roles in affecting the performance of printed energy storage

  16. Development and manufacture of printable next-generation gel polymer ionic liquid electrolyte for Zn/MnO2 batteries

    Science.gov (United States)

    Winslow, R.; Wu, C. H.; Wang, Z.; Kim, B.; Keif, M.; Evans, J.; Wright, P.

    2013-12-01

    While much energy storage research focuses on the performance of individual components, such as the electrolyte or a single electrode, few investigate the electrochemical system as a whole. This research reports on the design, composition, and performance of a Zn/MnO2 battery as affected by the manufacturing method and next-generation gel polymer electrolyte composed of the ionic liquid [BMIM][Otf], ZnOtf salt, and PVDF-HFP polymer binder. Materials and manufacturing tests are discussed with a focus on water concentration, surface features as produced by printing processes, and the effect of including a gel polymer phase. Cells produced for this research generated open circuit voltages from 1.0 to 1.3 V. A dry [BMIM][Otf] electrolyte was found to have 87.3 ppm of H2O, while an electrolyte produced in ambient conditions contained 12400 ppm of H2O. Cells produced in a dry, Ar environment had an average discharge capacity of 0.0137 mAh/cm2, while one produced in an ambient environment exhibited a discharge capacity at 0.05 mAh/cm2. Surface features varied significantly by printing method, where a doctor blade produced the most consistent features. The preliminary results herein suggest that water, surface roughness, and the gel polymer play important roles in affecting the performance of printed energy storage.

  17. Physical Chemistry of Reaction Dynamics in Ionic Liquid

    Energy Technology Data Exchange (ETDEWEB)

    Maroncelli, Mark [Pennsylvania State Univ., University Park, PA (United States)

    2016-10-02

    Work completed over the past year mainly involves finishing studies related to solvation dynamics in ionic liquids, amplifying and extending our initial PFG-NMR work on solute diffusion, and learning how to probe rotational dynamics in ionic liquids.

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

    Science.gov (United States)

    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.

  19. Ionic relaxation in PEO/PVDF-HFP-LiClO4 blend polymer electrolytes: dependence on salt concentration

    Science.gov (United States)

    Das, S.; Ghosh, A.

    2016-06-01

    In this paper, we have studied the effect of LiClO4 salt concentration on the ionic conduction and relaxation in poly ethylene oxide (PEO) and poly (vinylidene fluoride hexafluoropropylene) (PVDF-HFP) blend polymer electrolytes, in which the molar ratio of ethylene oxide segments to lithium ions (R  =  EO: Li) has been varied between 3 and 35. We have observed two phases in the samples containing low salt concentrations (R  >  9) and single phase in the samples containing high salt concentrations (R  ⩽  9). The scanning electron microscopic images indicate that there exists no phase separation in the blend polymer electrolytes. The temperature dependence of the ionic conductivity shows two slopes corresponding to high and low temperatures and follows Arrhenius relation for the samples containing low salt concentrations (R  >  9). The conductivity relaxation as well as the structural relaxation has been clearly observed at around 104 Hz and 106 Hz for these concentrations of the blended electrolytes. However, a single conductivity relaxation peak has been observed for the compositions with R  ⩽  9. The scaling of the conductivity spectra shows that the relaxation mechanism is independent of temperature, but depends on salt concentration.

  20. Effect of epoxidation level on thermal properties and ionic conductivity of epoxidized natural rubber solid polymer nanocomposite electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Harun, Fatin; Chan, Chin Han; Winie, Tan [Faculty of Applied Sciences, UniversitiTeknologi MARA (UiTM), Shah Alam, 40450 Selangor Darul Ehsan (Malaysia); Sim, Lai Har; Zainal, Nurul Fatahah Asyqin [Center of Foundation Studies, PuncakAlam Campus, UniversitiTeknologi MARA, 40430 Selangor Darul Ehsan (Malaysia)

    2015-08-28

    Effect of epoxide content on the thermal and conductivity properties of epoxidized natural rubber (ENR) solid polymer nanocomposite electrolytes was investigated. Commercial available epoxidized natural rubber having 25 (ENR25) and 50 mole% (ENR50) epoxide, respectively were incorporated with lithium perchlorate (LiClO{sub 4}) salt and titanium dioxide (TiO{sub 2}) nanofiller via solution casting method. The solid polymer nanocomposite electrolytes were characterized by differential scanning calorimetry (DSC) and impedance spectroscopy (IS) for their thermal properties and conductivity, respectively. It was evident that introduction of LiClO{sub 4} causes a greater increase in glass transition temperature (T{sub g}) and ionic conductivity of ENR50 as compared to ENR25. Upon addition of TiO{sub 2} in ENR/LiClO{sub 4} system, a remarkable T{sub g} elevation was observed for both ENRs where ENR50 reveals a more pronounced changes. It is interesting to note that they exhibit different phenomenon in ionic conductivity with TiO{sub 2} loading where ENR25 shows enhancement of conductivity while ENR50 shows declination.

  1. Improvement of imprinting effect of ionic liquid molecularly imprinted polymers by use of a molecular crowding agent.

    Science.gov (United States)

    Jia, Man; Yang, Jian; Sun, Ya Kun; Bai, Xi; Wu, Tao; Liu, Zhao Sheng; Aisa, Haji Akber

    2018-01-01

    We aimed to improve the imprinting effect of ionic liquid molecularly imprinted polymers (MIPs) by use of a molecular crowding agent. The ionic liquid 1-vinyl-3-ethylimidazolium tetrafluoroborate ([VEIm][BF 4 ]) was used as the functional monomer and aesculetin was used as the template molecule in a crowding environment, which was made up of a tetrahydrofuran solution of polystyrene. The ionic liquid MIPs that were prepared in the crowding environment displayed an enhanced imprinting effect. NMR peak shifts of active hydrogen of aesculetin suggested that interaction between the functional monomer and the template could be increased by the use of a crowding agent in the self-assembly process. The retention and selectivity of aesculetin were affected greatly by high molecular crowding, the amount of high molecular weight crowding agent, and the ratio of [VEIm][BF 4 ] to aesculetin. The optimal MIPs were used as solid-phase extraction sorbents to extract aesculetin from Cichorium glandulosum. A calibration curve was obtained with aesculetin concentrations from 0.0005 to 0.05 mg mL -1 (correlation coefficient R 2 of 0.9999, y = 1519x + 0.0923). The limit of quantification was 0.12 μg mL -1 , and the limit of detection was 0.05 μg mL -1 . The absolute recovery of aesculetin was (80 ± 2)% (n = 3), and the purity of aesculetin was (92 ± 0.5)% (n = 5). As a conclusion, molecular crowding is an effective approach to obtain ionic liquid MIPs with high selectivity even in a polar solvent environment.

  2. Highly water-dispersible, mixed ionic-electronic conducting, polymer acid-doped polyanilines as ionomers for direct methanol fuel cells.

    Science.gov (United States)

    Murthy, Arun; Manthiram, Arumugam

    2011-06-28

    Highly water-dispersible polymer acid-doped polyanilines have been synthesized and evaluated as an alternative for expensive Nafion ionomers in the anode of direct methanol fuel cells (DMFC). These polymers as ionomers lead to higher performance in single cell DMFC compared to Nafion ionomers due to mixed ionic-electronic conduction, water dispersibility, and co-catalytic activity. This journal is © The Royal Society of Chemistry 2011

  3. The Impact of Template Types on Polyeugenol to the Adsorption Selectivity of Ionic Imprinted Polymer (IIP) Fe Metal Ion

    Science.gov (United States)

    Djunaidi, M. C.; Haris, A.; Pardoyo; Rosdiana, K.

    2018-04-01

    The synthesis of IIP was carried out by variation of Fe(III) ion templates from Fe(NO3)3, K3[Fe(CN)6] and NH4Fe(SO4)2 compounds which then tested IIP selectivity to the Fe metal ions through adsorption process. Ionic Imprinted Polymer (IIP) is a method of printing metal ions bound in a polymer, subsequently released from the polymer matrix to produce a suitable imprint for the target ion. The purposes of this study were to produce IIP from Fe(NO3)3, K3[Fe(CN)6] and NH4Fe(SO4)2 templates, to know the effect of templates on adsorption selectivity of IIP involving imprint cavity, and to know the impact of metal competitor on the selectivity adsorption of IIP to the Fe metals. The results obtained showed that IIP synthesized by variations of Fe(NO3)3, K3[Fe(CN)6] and NH4Fe(SO4)2 templates were successfully synthesized. The adsorption selectivity of Fe (III) metal ion in the Fe(NO3)3 template was greater than that of in the K3[Fe(CN)6] and NH4Fe(SO4)2 templates. The adsorption selectivity of Fe was greater on Fe-Cr compared to on Fe-Cd and Fe-Pb.

  4. Characterization of polymer-type ionic conductors using nuclear magnetic resonance and thermal analysis. Humidity sensor

    International Nuclear Information System (INIS)

    Cavalcante, Maria Goretti.

    1992-04-01

    We report a study using Nuclear Magnetic Resonance (NMR), Thermogravimetry Analysis, Differential Scanning Calorimetry and Infrared Spectroscopy in polymeric complexes formed poly(ethylene oxide), (PEO), and lithium salts. These complexes have have shown a large potential for technological applications in batteries, sensors, etc. We developed and characterized humidity sensors and discussed how the humidity affects the conformation of the complexes, the mobility of ionic species, and the polymeric chains. The results indicate that the hydration affects the conformation of polymeric complexes by plasticizing the water, which induces a volumetric expansion in the PEO chain. The processes was completely reversible for the level of hydration studied. NMR was used to distinguish the movement of polymeric chains from the movement of the ionic species. From the analysis of the second moment of resonance lines from the study of the nuclear relaxation we were able to estimate the average distance between the ionic species and the proton in the complexes chains. The behaviour of spin -lattice relaxation of hydrogen and fluorine in the P(EO) - Li B F, as a function of temperature and frequency reflects the nature of the disorder and the complexity of the ionic conduction process in these materials. (author). 91 refs., 69 figs., 2 tabs

  5. Facile preparation of polymer electrolytes based on the polymerized ionic liquid poly((4-vinylbenzyl)trimethylammonium bis(trifluoromethanesulfonylimide)) for lithium secondary batteries

    International Nuclear Information System (INIS)

    Li, Mingtao; Wang, Lu; Yang, Bolun; Du, Tingting; Zhang, Ying

    2014-01-01

    Graphical abstract: (A) The main components of PIL electrolytes, (B) A PIL electrolyte sample. - Highlights: • A new polymer electrolyte incorporating a DEME-TFSI liquid is prepared. • The ionic conductivity of the electrolytes reaches 7.58 × 10 −4 S cm −1 at 60 °C. • Batteries discharge 130 mAh g −1 at 0.1 C rates with good capacity retention. - Abstract: The polymer electrolytes based on a novel poly((4-vinylbenzyl)trimethylammonium bis(trifluoromethanesulfonylimide)) polymeric ionic liquid (PIL) as polymer host and containing DEME-TFSI ionic liquid, LiTFSI salt and nano silica are prepared. The polymer electrolyte is chemically stable even at a higher temperature of 60 °C in contact with lithium anode. Particularly, the electrolyte exhibits high lithium ion conductivity, wide electrochemical stability window and good lithium stripping/plating performance. When the IL content reaches 60% (the weight ratio of DEME-TFSI/PIL), the PIL electrolyte presents a higher ionic conductivity, and it is 7.58 × 10 −4 S cm −1 at 60 °C. Preliminary battery tests show that Li/LiFePO 4 cells with the PIL electrolytes are capable to deliver above 130 mAh g −1 at 60 °C with very good capacity retention

  6. Stimuli responsive ion gels based on polysaccharides and other polymers prepared using ionic liquids and deep eutectic solvents.

    Science.gov (United States)

    Prasad, Kamalesh; Mondal, Dibyendu; Sharma, Mukesh; Freire, Mara G; Mukesh, Chandrakant; Bhatt, Jitkumar

    2018-01-15

    Ion gels and self-healing gels prepared using ionic liquids (ILs) and deep eutectic solvents (DESs) have been largely investigated in the past years due to their remarkable applications in different research areas. Herewith we provide an overview on the ILs and DESs used for the preparation of ion gels, highlight the preparation and physicochemical characteristics of stimuli responsive gel materials based on co-polymers and biopolymers, with special emphasis on polysaccharides and discuss their applications. Overall, this review summarizes the fundamentals and advances in ion gels with switchable properties prepared using ILs or DESs, as well as their potential applications in electrochemistry, in sensing devices and as drug delivery vehicles. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Evaluation of circuit models for an IPMC (ionic polymer-metal composite) sensor using a parameter estimate method

    International Nuclear Information System (INIS)

    Park, Kiwon; Lee, Hyungki

    2012-01-01

    The present study investigated a sensor system to effectively detect the bending angles applied on an ionic polymer metal composite sensor. Firstly, the amount of net charge produced by the motion of cations was correlated to the bending angle based on the geometric relationship between a flat and a bent IPMC, and the relationship was represented by linear and nonlinear polynomial equations. Secondly, several existing and modified R and C circuit models with a linear charge model were evaluated using the experimental data. Thirdly, the nonlinear charge model was applied to a selected circuit model, and the effectivenesses of the linear and the nonlinear charge models were compared. Finally, the sensor output signal was fed into the inverse model of the identified circuit model to reproduce the bending angles. This paper presents a simple data processing procedure using the inverse transfer function of a selected circuit model that successfully monitored various bending motions of an IPMC sensor.

  8. Cross-linking of polymer and ionic liquid as high-performance gel electrolyte for flexible solid-state supercapacitors

    International Nuclear Information System (INIS)

    Zhong, Xiongwei; Tang, Jun; Cao, Lujie; Kong, Weiguang; Sun, Zheng; Cheng, Hua; Lu, Zhouguang; Pan, Hui; Xu, Baomin

    2017-01-01

    Highlights: •A facile method to prepare gel polymer electrolyte with high conductivity is proposed. •A flexible symmetric capacitor based on the prepared GPE shows ultra-flexibility. •The capacitor with high voltage can power up a 3.0 V LED even bended to a angle of 180°. -- Abstract: It is highly desirable to develop flexible solid-state electrochemical double-layer capacitors (EDLCs) with non-liquid electrolyte. However, it is still a great challenge to prepare gel polymer electrolyte (GPE) possessing high ionic conductivity and good mechanical property. In this work, a simple and novel method to improve the conductivity and mechanical properties of GPE film for their applications as electrolyte and separator in EDLC is presented. The GPE film is prepared by cross-linking ionic liquid (IL) with poly (ethylene oxide) (PEO) and benzophenone (Bp) followed by ultraviolet (UV) irradiation. Then, a non-woven cellulose separator (FPC) is used to absorb the GPE. By tuning the mass ratio (n) between IL and PEO, the flexible EDLC cooperated with low-cost active carbon and the electrolyte film with n = 10 has a high capacitance of 70.84 F∙g −1 , a wide and stable electrochemical window of 3.5 V, an energy density of 30.13 Wh∙kg −1 and a power density of 874.8 W∙kg −1 at a current density of 1 A∙g −1 , which can drive a 3.0 V light-emitting diode (LED). Importantly, the excellent performance of the flexible and low-cost EDLC can be maintained at a bending angle up to 180°, indicating the ultra-flexibility. It is expected that the IL-PEO-FPC electrolyte film is a promising candidate of GPE for flexible devices and energy storage systems.

  9. Synthesis and Characterization of β-Cyclodextrin Functionalized Ionic Liquid Polymer as a Macroporous Material for the Removal of Phenols and As(V

    Directory of Open Access Journals (Sweden)

    Muggundha Raoov

    2013-12-01

    Full Text Available β-Cyclodextrin-ionic liquid polymer (CD-ILP was first synthesized by functionalized β-cyclodextrin (CD with 1-benzylimidazole (BIM to form monofunctionalized CD (βCD-BIMOTs and was further polymerized using a toluene diisocyanate (TDI linker to form insoluble CD-ILP (βCD-BIMOTs-TDI. The βCD-BIMOTs-TDI polymer was characterized using various tools and the results obtained were compared with those derived from the native β-cyclodextrin polymer (βCD-TDI. The SEM result shows that the presence of ionic liquid (IL increases the pore size, while the thermo gravimetric analysis (TGA result shows that the presence of IL increases the stability of the polymer. Meanwhile, Brunauer-Emmett-Teller (BET results show that βCD-BIMOTs-TDI polymer has 1.254 m2/g surface areas and the Barret-Joyner-Halenda (BJH pore size distribution result reveals that the polymer exhibits macropores with a pore size of 77.66 nm. Preliminary sorption experiments were carried out and the βCD-BIMOTs-TDI polymer shows enhanced sorption capacity and high removal towards phenols and As(V.

  10. Composite polymer electrolyte containing ionic liquid and functionalized polyhedral oligomeric silsesquioxanes for anhydrous PEM applications.

    Science.gov (United States)

    Subianto, Surya; Mistry, Mayur K; Choudhury, Namita Roy; Dutta, Naba K; Knott, Robert

    2009-06-01

    A new type of supported liquid membrane was made by combining an ionic liquid (IL) with a Nafion membrane reinforced with multifunctional polyhedral oligomeric silsesquioxanes (POSSs) using a layer-by-layer strategy for anhydrous proton-exchange membrane (PEM) application. The POSS was functionalized by direct sulfonation, and the sulfonated POSS (S-POSS) was incorporated into Nafion 117 membranes by the infiltration method. The resultant hybrid membrane shows strong ionic interaction between the Nafion matrix and the multifunctional POSS, resulting in increased glass transition temperature and thermal stability at very low loadings of S-POSS (1%). The presence of S-POSS has also improved the proton conductivity especially at low humidities, where it shows a marked increase due to its confinement in the ionic domains and promotes water uptake by capillary condensation. In order to achieve anhydrous conductivity, the IL 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMI-BTSI) was incorporated into these membranes to provide proton conduction in the absence of water. Although the incorporation of an IL shows a plasticizing effect on the Nafion membrane, the S-POSS composite membrane with an IL shows a higher modulus at high temperatures compared to Nafion 117 and a Nafion-IL membrane, with significantly higher proton conductivity (5 mS/cm at 150 degrees C with 20% IL). This shows the ability of the multifunctional POSS and IL to work symbiotically to achieve the desirable proton conductivity and mechanical properties of such membranes by enhancing the ionic interaction within the material.

  11. Efficient and Stable Photovoltaic Characteristics of Quasi-Solid State DSSC using Polymer Gel Electrolyte Based on Ionic Liquid in Organosiloxane Polymer Gels

    Science.gov (United States)

    Pujiarti, H.; Arsyad, W. S.; Shobih; Muliani, L.; Hidayat, R.

    2018-04-01

    Dye-Sensitized Solar Cell (DSSC) is still one of the promising solar cell types among the third generation of solar cells because of easiness of fabrication and variety of available materials. In this type of solar cell, the electrolyte is one of the important components for regenerating excited dyes and transporting electric charge carriers to the counter electrode. Indeed, the power conversion efficiency of DSSC can be then significantly affected by the chemical and physical properties of the electrolyte. The simplest electrolyte system of an I-/I3 - redox couple in an organic solvent, however, has some drawbacks due to corrosive properties, volatile and leakage problem. Use of solid phase or gel phase electrolyte may overcome those problems, but it is often considered to suppress the efficiency due to low ion diffusion. Here, we report the photovoltaic characteristics of DSSC using polymer gel electrolyte (PGE), which is composed of ionic liquid and an organosiloxane polymer gel. The better cell performance with power conversion efficiency of about 6% has been obtained by optimizing the mesoporous size of the TiO2 layer and the PGE viscosity.

  12. Nanoparticle and gelation stabilized functional composites of an ionic salt in a hydrophobic polymer matrix.

    Directory of Open Access Journals (Sweden)

    Selin Kanyas

    Full Text Available Polymer composites consisted of small hydrophilic pockets homogeneously dispersed in a hydrophobic polymer matrix are important in many applications where controlled release of the functional agent from the hydrophilic phase is needed. As an example, a release of biomolecules or drugs from therapeutic formulations or release of salt in anti-icing application can be mentioned. Here, we report a method for preparation of such a composite material consisted of small KCOOH salt pockets distributed in the styrene-butadiene-styrene (SBS polymer matrix and demonstrate its effectiveness in anti-icing coatings. The mixtures of the aqueous KCOOH and SBS-cyclohexane solutions were firstly stabilized by adding silica nanoparticles to the emulsions and, even more, by gelation of the aqueous phase by agarose. The emulsions were observed in optical microscope to check its stability in time and characterized by rheological measurements. The dry composite materials were obtained via casting the emulsions onto the glass substrates and evaporations of the organic solvent. Composite polymer films were characterized by water contact angle (WCA measurements. The release of KCOOH salt into water and the freezing delay experiments of water droplets on dry composite films demonstrated their anti-icing properties. It has been concluded that hydrophobic and thermoplastic SBS polymer allows incorporation of the hydrophilic pockets/phases through our technique that opens the possibility for controlled delivering of anti-icing agents from the composite.

  13. Quantifying Contributions to Transport in Ionic Polymers Across Multiple Length Scales

    Science.gov (United States)

    Madsen, Louis

    Self-organized polymer membranes conduct mobile species (ions, water, alcohols, etc.) according to a hierarchy of structural motifs that span sub-nm to >10 μm in length scale. In order to comprehensively understand such materials, our group combines multiple types of NMR dynamics and transport measurements (spectroscopy, diffusometry, relaxometry, imaging) with structural information from scattering and microscopy as well as with theories of porous media,1 electrolytic transport, and oriented matter.2 In this presentation, I will discuss quantitative separation of the phenomena that govern transport in polymer membranes, from intermolecular interactions (<= 2 nm),3 to locally ordered polymer nanochannels (a few to 10s of nm),2 to larger polymer domain structures (10s of nm and larger).1 Using this multi-scale information, we seek to give informed feedback on the design of polymer membranes for use in, e . g . , efficient batteries, fuel cells, and mechanical actuators. References: [1] J. Hou, J. Li, D. Mountz, M. Hull, and L. A. Madsen. Journal of Membrane Science448, 292-298 (2013). [2] J. Li, J. K. Park, R. B. Moore, and L. A. Madsen. Nature Materials 10, 507-511 (2011). [3] M. D. Lingwood, Z. Zhang, B. E. Kidd, K. B. McCreary, J. Hou, and L. A. Madsen. Chemical Communications 49, 4283 - 4285 (2013).

  14. Optimization of PEDOT films in ionic liquid supercapacitors: demonstration as a power source for polymer electrochromic devices.

    Science.gov (United States)

    Österholm, Anna M; Shen, D Eric; Dyer, Aubrey L; Reynolds, John R

    2013-12-26

    We report on the optimization of the capacitive behavior of poly(3,4-ethylenedioxythiophene) (PEDOT) films as polymeric electrodes in flexible, Type I electrochemical supercapacitors (ESCs) utilizing ionic liquid (IL) and organic gel electrolytes. The device performance was assessed based on figures of merit that are critical to evaluating the practical utility of electroactive polymer ESCs. PEDOT/IL devices were found to be highly stable over hundreds of thousands of cycles and could be reversibly charged/discharged at scan rates between 500 mV/s and 2 V/s depending on the polymer loading. Furthermore, these devices exhibit leakage currents and self-discharge rates that are comparable to state of the art electrochemical double-layer ESCs. Using an IL as device electrolyte allowed an extension of the voltage window of Type I ESCs by 60%, resulting in a 2.5-fold increase in the energy density obtained. The efficacies of tjese PEDOT ESCs were assessed by using them as a power source for a high-contrast and fast-switching electrochromic device, demonstrating their applicability in small organic electronic-based devices.

  15. Fabrication and characterization of a micromachined swirl-shaped ionic polymer metal composite actuator with electrodes exhibiting asymmetric resistance.

    Science.gov (United States)

    Feng, Guo-Hua; Liu, Kim-Min

    2014-05-12

    This paper presents a swirl-shaped microfeatured ionic polymer-metal composite (IPMC) actuator. A novel micromachining process was developed to fabricate an array of IPMC actuators on a glass substrate and to ensure that no shortcircuits occur between the electrodes of the actuator. We demonstrated a microfluidic scheme in which surface tension was used to construct swirl-shaped planar IPMC devices of microfeature size and investigated the flow velocity of Nafion solutions, which formed the backbone polymer of the actuator, within the microchannel. The unique fabrication process yielded top and bottom electrodes that exhibited asymmetric surface resistance. A tool for measuring surface resistance was developed and used to characterize the resistances of the electrodes for the fabricated IPMC device. The actuator, which featured asymmetric electrode resistance, caused a nonzero-bias current when the device was driven using a zero-bias square wave, and we propose a circuit model to describe this phenomenon. Moreover, we discovered and characterized a bending and rotating motion when the IPMC actuator was driven using a square wave. We observed a strain rate of 14.6% and a displacement of 700 μm in the direction perpendicular to the electrode surfaces during 4.5-V actuation.

  16. Diffusion Control in the in Situ Synthesis of Iconic Metal-Organic Frameworks within an Ionic Polymer Matrix.

    Science.gov (United States)

    Lim, Jungho; Lee, Eun Ji; Choi, Jae Sun; Jeong, Nak Cheon

    2018-01-31

    Ionic polymers that possess ion-exchangeable sites have been shown to be a greatly useful platform to fabricate mixed matrices (MMs) where metal-organic frameworks (MOFs) can be in situ synthesized, although the in situ synthesis of MOF has been rarely studied. In this study, alginate (ALG), an anionic green polymer that possesses metal-ion-exchangeable sites, is employed as a platform of MMs for the in situ synthesis of iconic MOFs, HKUST-1, and MOF-74(Zn). We demonstrate for the first time that the sequential order of supplying MOF ingredients (metal ion and deprotonated ligand) into the alginate matrix leads to substantially different results because of a difference in the diffusion of the MOF components. For the examples examined, whereas the infusion of BTC 3- ligand into Cu 2+ -exchanged ALG engendered the eggshell-shaped HKUST-1 layers on the surface of MM spheres, the infusion of Cu 2+ ions into BTC 3- -included alginate engendered the high dispersivity and junction contact of HKUST-1 crystals in the alginate matrix. This fundamental property has been exploited to fabricate a flexible MOF-containing mixed matrix membrane by coincorporating poly(vinyl alcohol). Using two molecular dyes, namely, methylene blue and rhodamine 6G, further, we show that this in situ strategy is suitable for fabricating an MOF-MM that exhibits size-selective molecular uptake.

  17. Poly(vinylidene fluoride) modification induced by gamma irradiation for application as ionic polymer-metal composite

    International Nuclear Information System (INIS)

    Ferreira, Henrique Perez

    2011-01-01

    Gamma-radiation-induced grafting of styrene into poly(vinylidene fluoride) (PVDF) films with 0.125 mm thickness at doses from 1 to 100 kGy in the presence of a styrene/N,N- dimethylformamide (DMF) solution (1:1, v/v) and styrene/toluene (1:1, v/v) at dose rate of 5 kGy h-1 was carried out by simultaneous method under nitrogen atmosphere at room temperature, using gamma rays from a Co-60. After grafting reactions, the polymer was then sulfonated in chlorosulfonic acid/1,2-dichloroethane (2 and 10%) for 3 hours. The films were characterized before and after modification by calculating the degree of grafting (DOG), infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetry (TG/DTG). DOG results show that grafting increases with dose, and varies enormously depending on the solvent used, with DOGs about 20 times greater in DMF than in toluene. It was possible to confirm the grafting of styrene by FT-IR due to the appearance of the new characteristic peaks and by the TG and DSC which exhibited changes in the thermal behavior of the grafted/sulfonated material. Sulfonated material was also characterized by ion exchange capacity (IEC) showed that both DOG and sulfonic acid concentration increase IEC values. Results showed that it is possible to obtain materials with ion exchange capacity of possible application as ionic polymer-metal composites. (author)

  18. Experimental verification of displacement control on integrated ionic polymer-metal composite actuators with stochastic on/off controller

    Science.gov (United States)

    Kimura, Keishiro; Kamamichi, Norihiro

    2017-04-01

    An ionic polymer-metal composite (IPMC) actuator is one of polymer-based soft actuators. It is produced by chemically plating gold or platinum on both surface of a perfluorosulfonic acid membrane which is known as an ion-exchange membrane. It is able to be activated by a simple driving circuit and generate a large deformation under a low applied voltage (0.5-3 V). However, individual difference and characteristics changes from environmental conditions should be considered for realizing a stable or precise control. To solve these problems, we applied a stochastic ON/OFF controller to an integrated IPMC actuator with parallel connections. The controller consists of a central controller and distributed controllers. The central controller broadcasts a control signal such as an error signal to distributed controllers uniformly. The distributed controllers switch the ON/OFF states based on the broadcasted signal stochastically. The central controller dose not measure the states of each IPMC actuator, and the control signals is calculated by using the output signal of the integrated actuator and reference signal. The validity of the applied method was investigated through numerical simulations and experiments.

  19. Ionic conduction in 70-MeV C5+-ion-irradiated poly(vinylidenefluoride- co-hexafluoropropylene)-based gel polymer electrolytes

    International Nuclear Information System (INIS)

    Saikia, D.; Kumar, A.; Singh, F.; Avasthi, D.K.; Mishra, N.C.

    2005-01-01

    In an attempt to increase the Li + -ion diffusivity, poly(vinylidenefluoride-co-hexafluoropropylene)-(propylene carbonate+diethyl carbonate)-lithium perchlorate gel polymer electrolyte system has been irradiated with 70-MeV C 5+ -ion beam of nine different fluences. Swift heavy-ion irradiation shows enhancement in ionic conductivity at lower fluences and decrease in ionic conductivity at higher fluences with respect to unirradiated gel polymer electrolyte films. Maximum room-temperature (303 K) ionic conductivity is found to be 2x10 -2 S/cm after irradiation with a fluence of 10 11 ions/cm 2 . This interesting result could be attributed to the fact that for a particular ion beam with a given energy, a higher fluence provides critical activation energy for cross linking and crystallization to occur, which results in the decrease in ionic conductivity. X-ray-diffraction results show decrease in the degree of crystallinity upon ion irradiation at low fluences (≤10 11 ions/cm 2 ) and increase in crystallinity at higher fluences (>10 11 ions/cm 2 ). Analysis of Fourier-transform infrared spectroscopy results suggests the bond breaking at a fluence of 5x10 9 ions/cm 2 and cross linking at a fluence of 10 12 ions/cm 2 and corroborate conductivity and x-ray-diffraction results. Scanning electron micrographs exhibit increased porosity of the polymer electrolyte after ion irradiation

  20. Ionic conductivity in polyethylene-b-poly(ethylene oxide)/lithium perchlorate solid polymer electrolytes

    International Nuclear Information System (INIS)

    Guilherme, L.A.; Borges, R.S.; Moraes, E. Mara S.; Silva, G. Goulart; Pimenta, M.A.; Marletta, A.; Silva, R.A.

    2007-01-01

    The ionic conductivity and phase arrangement of solid polymeric electrolytes based on the block copolymer polyethylene-b-poly(ethylene oxide) (PE-b-PEO) and LiClO 4 have been investigated. One set of electrolytes was prepared from copolymers with 75% of PEO units and another set was based on a blend of copolymer with 50% PEO units and homopolymers. The differential scanning calorimetry (DSC) results, for electrolytes based on the copolymer with 75% of PEO units, were dominated by the PEO phase. The PEO block crystallinity dropped and the glass transition increased with salt addition due to the coordination of the cation by PEO oxygen. The conductivity for copolymers 75% PEO-based electrolyte with 15 wt% of salt was higher than 10 -5 S/cm at room temperature and reached to 10 -3 S/cm at 100 deg. C on a heating measurement. The blend of PE-b-PEO (50% PEO)/PEO/PE showed a complex thermal behavior with decoupled melting of the blocks and the homopolymers. Upon salt addition the endotherms associated with PEO domains disappeared and the PE crystals remained untouched. The conductivity results were limited at 100 deg. C to values close to 10 -4 S/cm and at room temperature values close to 3 x 10 -6 S/cm were obtained for the 15 wt% salt electrolyte. Raman study showed that the ionic association of the highly concentrated blend electrolytes at room temperature is not significant. Therefore, the lower values of conductivity in the case of the blend with 50% PEO can be assigned to the higher content of PE domains leading to a morphology with lower connectivity for ionic conduction both in the crystalline and melted state of the PE domains

  1. The material combining conducting polymer and ionic liquid: hydrogen bonding interactions between polyaniline and imidazolium salt

    Czech Academy of Sciences Publication Activity Database

    Stejskal, Jaroslav; Dybal, Jiří; Trchová, Miroslava

    2014-01-01

    Roč. 197, November (2014), s. 168-174 ISSN 0379-6779 R&D Projects: GA ČR(CZ) GA13-08944S Institutional support: RVO:61389013 Keywords : conducting polymer * conductivity * imidazolium salt Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.252, year: 2014

  2. Influence of Ionic Liquid Content on Properties of Dense Polymer Membranes

    Czech Academy of Sciences Publication Activity Database

    Kohoutová, Marie; Sikora, Antonín; Hovorka, Š.; Randová, A.; Schauer, Jan; Tišma, J.; Setničková, Kateřina; Petričkovič, Roman; Guernik, S.; Greenspoon, N.; Izák, Pavel

    2009-01-01

    Roč. 45, č. 3 (2009), s. 813-819 ISSN 0014-3057 R&D Projects: GA ČR GA104/08/0600; GA ČR GA203/08/0465 Grant - others:MERG(XE) CT/2006/44737 Institutional research plan: CEZ:AV0Z40720504; CEZ:AV0Z40500505 Keywords : dense polymer membranes * biofuel * fermentation Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.310, year: 2009

  3. Nanoporous Polymer Films of Cyanate Ester Resins Designed by Using Ionic Liquids as Porogens.

    Science.gov (United States)

    Fainleib, Alexander; Vashchuk, Alina; Starostenko, Olga; Grigoryeva, Olga; Rogalsky, Sergiy; Nguyen, Thi-Thanh-Tam; Grande, Daniel

    2017-12-01

    Novel nanoporous film materials of thermostable cyanate ester resins (CERs) were generated by polycyclotrimerization of dicyanate ester of bisphenol E in the presence of varying amounts (from 20 to 40 wt%) of an ionic liquid (IL), i.e., 1-heptylpyridinium tetrafluoroborate, followed by its quantitative extraction after complete CER network formation. The completion of CER formation and IL extraction was assessed using gel fraction content determination, FTIR, 1 H NMR, and energy-dispersive X-ray spectroscopy (EDX). SEM and DSC-based thermoporometry analyses demonstrated the formation of nanoporous structures after IL removal from CER networks, thus showing the effective role of IL as a porogen. Pore sizes varied from ~20 to ~180 nm with an average pore diameter of around 45-60 nm depending on the initial IL content. The thermal stability of nanoporous CER-based films was investigated by thermogravimetric analysis.

  4. Effect of degree of crosslinking and polymerization of 3D printable polymer/ionic liquid composites on performance of stretchable piezoresistive sensors

    Science.gov (United States)

    Lee, Jeongwoo; Faruk Emon, Md Omar; Vatani, Morteza; Choi, Jae-Won

    2017-03-01

    Ionic liquid (IL)/polymer composites (1-ethyl-3-methyl-imidazolium tetrafluoroborate (EMIMBF4)/2-[[(butylamino)carbonyl]oxy]ethyl acrylate (BACOEA)) were fabricated to use as sensing materials for stretchable piezoresistive tactile sensors. The detectability of the IL/polymer composites was enhanced because the ionic transport properties of EMIMBF4 in the composites were improved by the synergic actions between the coordinate sites generated by the local motion of BACOEA chain segments under enough activation energy. The performance of the piezoresistive sensors was investigated with the degree of crosslinking and polymerization of the IL/polymer composites. As the compressive strain was increased, the distance between two electrodes decreased, and the motion of polymer chains and IL occurred, resulting in a decrease in the electrical resistance of the sensors. We have confirmed that the sensitivity of the sensors are affected by the degree of crosslink and polymerization of the IL/polymer composites. In addition, all of the materials (skins, sensing material, and electrode) used in this study are photo-curable, and thus the stretchable piezoresistive tactile sensors can be successfully fabricated by 3D printing.

  5. Thermotropic Ionic Liquid Crystals

    Directory of Open Access Journals (Sweden)

    Sabine Laschat

    2011-01-01

    Full Text Available The last five years’ achievements in the synthesis and investigation of thermotropic ionic liquid crystals are reviewed. The present review describes the mesomorphic properties displayed by organic, as well as metal-containing ionic mesogens. In addition, a short overview on the ionic polymer and self-assembled liquid crystals is given. Potential and actual applications of ionic mesogens are also discussed.

  6. Analyses of ionic conductivity and dielectric behavior of solid polymer electrolyte based 2-hydroxyethyl cellulose doped ammonium nitrate plasticized with ethylene carbonate

    Science.gov (United States)

    Hafiza, M. N.; Isa, M. I. N.

    2017-09-01

    A solid polymer electrolyte (SPE) based 2-hydroxyethyl cellulose (2-HEC) doped ammonium nitrate (NH4NO3) plasticized with ethylene carbonate (EC) has been investigated using electrical impedance spectroscopy (EIS). The highest ionic conductivity of (1.17±0.01) × 10-3 Scm-1 was obtained for 2-HEC-NH4NO3 plasticized with 16 wt.% EC. Dielectric and modulus study showed non-Debye type of 2-HEC-NH4NO3-EC SPE.

  7. Biomimetic robotic Venus flytrap (Dionaea muscipula Ellis) made with ionic polymer metal composites

    Energy Technology Data Exchange (ETDEWEB)

    Shahinpoor, Mohsen, E-mail: mohsen.shahinpoor@maine.edu [Biomedical Engineering Laboratory, Department of Mechanical Engineering, University of Maine, Orono, ME 04469 (United States)

    2011-12-15

    The work described in this paper is a novel design of a robotic Venus flytrap (VFT) (Dionaea muscipula Ellis) by means of ionic polymeric metal composite (IPMC) artificial muscles as distributed nanosensors and nanoactuators. Rapid muscular movements in carnivorous plants, such as VFT, which are triggered by antenna-like sensors (trigger hair), present a golden key to study distributed biomolecular motors. Carnivorous plants, such as VFT, possess built-in intelligence (trigger hairs), as a strategy to capture prey, that can be turned on in a controlled manner. In the case of the VFT, the prey that is lured by the sweet nectar in the VFT pair of jaw-like lobes has to flip and move the trigger hairs, which are colorless, bristle-like and pointed. The dynamically moved trigger hairs then electro-elastically send an electric signal to the internal ions in the lobe to migrate outwardly for the jaw-like lobes to close rapidly to capture the prey. The manner in which the VFT lobes bend inward to capture the prey shows a remarkable similarity with typical IPMCs bending in an electric field. Furthermore, the mechano-electrical sensing characteristics of IPMCs also show a remarkable resemblance to mechano-electrical trigger hairs on the lobes of the VFT. The reader is referred to a number of papers in connection with sensing and actuation of IPMCs in particular. Thus, one can integrate IPMC lobes with a common electrode in the middle of one end of the lobes to act like a spine and use IPMC bristles as trigger finger to sense the intrusion of a fly or insect to send a sensing signal to a solid state relay which then triggers the actuation circuit of the IPMC lobes to rapidly bend toward each other and close. The two lobes, which form the trap, are attached to the midrib common electrode which is conveniently termed the spine. The upper surface of each lobe is dished, and spaced along the free margins of the lobes with some 15-20 prong-like teeth. These are tough and pointed

  8. Biomimetic robotic Venus flytrap (Dionaea muscipula Ellis) made with ionic polymer metal composites

    International Nuclear Information System (INIS)

    Shahinpoor, Mohsen

    2011-01-01

    The work described in this paper is a novel design of a robotic Venus flytrap (VFT) (Dionaea muscipula Ellis) by means of ionic polymeric metal composite (IPMC) artificial muscles as distributed nanosensors and nanoactuators. Rapid muscular movements in carnivorous plants, such as VFT, which are triggered by antenna-like sensors (trigger hair), present a golden key to study distributed biomolecular motors. Carnivorous plants, such as VFT, possess built-in intelligence (trigger hairs), as a strategy to capture prey, that can be turned on in a controlled manner. In the case of the VFT, the prey that is lured by the sweet nectar in the VFT pair of jaw-like lobes has to flip and move the trigger hairs, which are colorless, bristle-like and pointed. The dynamically moved trigger hairs then electro-elastically send an electric signal to the internal ions in the lobe to migrate outwardly for the jaw-like lobes to close rapidly to capture the prey. The manner in which the VFT lobes bend inward to capture the prey shows a remarkable similarity with typical IPMCs bending in an electric field. Furthermore, the mechano-electrical sensing characteristics of IPMCs also show a remarkable resemblance to mechano-electrical trigger hairs on the lobes of the VFT. The reader is referred to a number of papers in connection with sensing and actuation of IPMCs in particular. Thus, one can integrate IPMC lobes with a common electrode in the middle of one end of the lobes to act like a spine and use IPMC bristles as trigger finger to sense the intrusion of a fly or insect to send a sensing signal to a solid state relay which then triggers the actuation circuit of the IPMC lobes to rapidly bend toward each other and close. The two lobes, which form the trap, are attached to the midrib common electrode which is conveniently termed the spine. The upper surface of each lobe is dished, and spaced along the free margins of the lobes with some 15-20 prong-like teeth. These are tough and pointed

  9. Assimilation of NH₄Br in Polyvinyl Alcohol/Poly(N-vinyl pyrrolidone) Polymer Blend-Based Electrolyte and Its Effect on Ionic Conductivity.

    Science.gov (United States)

    Parameswaran, V; Nallamuthu, N; Devendran, P; Manikandan, A; Nagarajan, E R

    2018-06-01

    Biodegradable polymer blend electrolyte based on ammonium based salt in variation composition consisting of PVA:PVP were prepared by using solution casting technique. The obtained films have been analyzed by various technical methods like as XRD, FT-IR, TG-DSC, SEM analysis and impedance spectroscopy. The XRD and FT-IR analysis exposed the amorphous nature and structural properties of the complex formation between PVA/PVP/NH4Br. Impedance spectroscopy analysis revealed the ionic conductivity and the dielectric properties of PVA/PVP/NH4Br polymer blend electrolyte films. The maximum ionic conductivity was determined to be 6.14 × 10-5 Scm-1 for the composition of 50%PVA: 50%PVP: 10% NH4Br with low activation energy 0.3457 eV at room temperature. Solid state battery is fabricated using highest ionic conducting polymer blend as electrolyte with the configuration Zn/ZnSO4 · 7H2O (anode) ∥ 50%PVA: 50%PVP: 10% NH4Br ∥ Mn2O3 (cathode). The observed open circuit voltage is 1.2 V and its performance has been studied.

  10. Field enhanced charge carrier reconfiguration in electronic and ionic coupled dynamic polymer resistive memory

    International Nuclear Information System (INIS)

    Zhao Junhui; Thomson, Douglas J; Freund, Michael S; Pilapil, Matt; Pillai, Rajesh G; Aminur Rahman, G M

    2010-01-01

    Dynamic resistive memory devices based on a conjugated polymer composite (PPy 0 DBS - Li + (PPy: polypyrrole; DBS - : dodecylbenzenesulfonate)), with field-driven ion migration, have been demonstrated. In this work the dynamics of these systems has been investigated and it has been concluded that increasing the applied field can dramatically increase the rate at which information can be 'written' into these devices. A conductance model using space charge limited current coupled with an electric field induced ion reconfiguration has been successfully utilized to interpret the experimentally observed transient conducting behaviors. The memory devices use the rising and falling transient current states for the storage of digital states. The magnitude of these transient currents is controlled by the magnitude and width of the write/read pulse. For the 500 nm length devices used in this work an increase in 'write' potential from 2.5 to 5.5 V decreased the time required to create a transient conductance state that can be converted into the digital signal by 50 times. This work suggests that the scaling of these devices will be favorable and that 'write' times for the conjugated polymer composite memory devices will decrease rapidly as ion driving fields increase with decreasing device size.

  11. Understanding the Thermal Properties of Precursor-Ionomers to Optimize Fabrication Processes for Ionic Polymer-Metal Composites (IPMCs

    Directory of Open Access Journals (Sweden)

    Sarah Trabia

    2018-04-01

    Full Text Available Ionic polymer-metal composites (IPMCs are one of many smart materials and have ionomer bases with a noble metal plated on the surface. The ionomer is usually Nafion, but recently Aquivion has been shown to be a promising alternative. Ionomers are available in the form of precursor pellets. This is an un-activated form that is able to melt, unlike the activated form. However, there is little study on the thermal characteristics of these precursor ionomers. This lack of knowledge causes issues when trying to fabricate ionomer shapes using methods such as extrusion, hot-pressing, and more recently, injection molding and 3D printing. To understand the two precursor-ionomers, a set of tests were conducted to measure the thermal degradation temperature, viscosity, melting temperature, and glass transition. The results have shown that the precursor Aquivion has a higher melting temperature (240 °C than precursor Nafion (200 °C and a larger glass transition range (32–65°C compared with 21–45 °C. The two have the same thermal degradation temperature (~400 °C. Precursor Aquivion is more viscous than precursor Nafion as temperature increases. Based on the results gathered, it seems that the precursor Aquivion is more stable as temperature increases, facilitating the manufacturing processes. This paper presents the data collected to assist researchers in thermal-based fabrication processes.

  12. Effects of surface roughening on the mass transport and mechanical properties of ionic polymer-metal composite

    Science.gov (United States)

    Chang, Longfei; Asaka, Kinji; Zhu, Zicai; Wang, Yanjie; Chen, Hualing; Li, Dichen

    2014-06-01

    Ionic Polymer-Metal Composite (IPMC) has been well-documented of being a promising functional material in extensive applications. In its most popular and traditional manufacturing technique, roughening is a key process to ensure a satisfying performance. In this paper, based on a lately established multi-physical model, the effect of roughening process on the inner mass transportation and the electro-active output of IPMC were investigated. In the model, the electro-chemical field was monitored by Poisson equation and a properly simplified Nernst-Planck equation set, while the mechanical field was evaluated on the basis of volume strain effect. Furthermore, with Ramo-Shockley theorem, the out-circuit current and accumulated charge on the electrode were bridged with the inner cation distribution. Besides, nominal current and charge density as well as the curvature of the deformation were evaluated to characterize the performance of IPMC. The simulation was implemented by Finite Element Method with Comsol Multi-physics, based on two groups of geometrical models, those with various rough interface and those with different thickness. The results of how the roughening impact influences on the performance of IPMC were discussed progressively in three aspects, steady-state distribution of local potential and mass concentration, current response and charge accumulation, as well as the curvature of deformation. Detailed explanations for the performance improvement resulted from surface roughening were provided from the micro-distribution point of view, which can be further explored for the process optimization of IPMC.

  13. Anion Effects on the Ion Exchange Process and the Deformation Property of Ionic Polymer Metal Composite Actuators

    Directory of Open Access Journals (Sweden)

    Wataru Aoyagi

    2016-06-01

    Full Text Available An ionic polymer-metal composite (IPMC actuator composed of a thin perfluorinated ionomer membrane with electrodes plated on both surfaces undergoes a large bending motion when a low electric field is applied across its thickness. Such actuators are soft, lightweight, and able to operate in solutions and thus show promise with regard to a wide range of applications, including MEMS sensors, artificial muscles, biomimetic systems, and medical devices. However, the variations induced by changing the type of anion on the device deformation properties are not well understood; therefore, the present study investigated the effects of different anions on the ion exchange process and the deformation behavior of IPMC actuators with palladium electrodes. Ion exchange was carried out in solutions incorporating various anions and the actuator tip displacement in deionized water was subsequently measured while applying a step voltage. In the step voltage response measurements, larger anions such as nitrate or sulfate led to a more pronounced tip displacement compared to that obtained with smaller anions such as hydroxide or chloride. In AC impedance measurements, larger anions generated greater ion conductivity and a larger double-layer capacitance at the cathode. Based on these mechanical and electrochemical measurements, it is concluded that the presence of larger anions in the ion exchange solution induces a greater degree of double-layer capacitance at the cathode and results in enhanced tip deformation of the IPMC actuators.

  14. Fabrication of an ionic-liquid-based polymer monolithic column and its application in the fractionation of proteins from complex biosamples.

    Science.gov (United States)

    Zhang, Doudou; Zhang, Qian; Bai, Ligai; Han, Dandan; Liu, Haiyan; Yan, Hongyuan

    2018-05-01

    An ionic-liquid-based polymer monolithic column was synthesized by free radical polymerization within the confines of a stainless-steel column (50 mm × 4.6 mm id). In the processes, ionic liquid and stearyl methacrylate were used as dual monomers, ethylene glycol dimethacrylate as the cross-linking agent, and polyethylene glycol 200 and isopropanol as co-porogens. Effects of the prepolymerization solution components on the properties of the resulting monoliths were studied in detail. Scanning electron microscopy, nitrogen adsorption-desorption measurements, and mercury intrusion porosimetry were used to investigate the morphology and pore size distribution of the prepared monoliths, which showed that the homemade ionic-liquid-based monolith column possessed a relatively uniform macropore structure with a total macropore specific surface area of 44.72 m 2 /g. Compared to a non-ionic-liquid-based monolith prepared under the same conditions, the ionic-liquid-based monolith exhibited excellent selectivity and high performance for separating proteins from complex biosamples, such as egg white, snailase, bovine serum albumin digest solution, human plasma, etc., indicating promising applications in the fractionation and analysis of proteins from the complex biosamples in proteomics research. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Influence of hydrogen bond accepting ability of anions on the adsorption performance of ionic liquid surface molecularly imprinted polymers.

    Science.gov (United States)

    Zhu, Guifen; Gao, Xia; Wang, Xiaolong; Wang, Jianji; Fan, Jing

    2018-01-12

    To illuminate the influence mechanism of anionic structure of ionic liquids (ILs) on the adsorption performance of surface molecularly imprinted polymers (MIPs), in this work, six newly designed MIPs were prepared on the surface of amino-poly(styrene-divinylbenzene) particles by using imidazolium ILs with the same cation [C 4 mim] + but different anions (Cl, CH 3 SO 3 , PF 6 , BF 4 , C 4 F 7 O 2 , C 4 F 9 SO 3 ) as template molecules, methacrylic acid as functional monomer, and ethylene dimethacrylate as cross-linker. The resulting MIP materials were characterized by IR and SEM, and the influence of hydrogen bond accepting ability of anions on the adsorption performance of the MIPs for the ILs was investigated in acetonitrile. It was found that adsorption capacity of the MIPs towards the ILs decreased in the order MIP [C4mim][Cl]  > MIP [C4mim][C4F7O2]  ≥ MIP [C4mim][BF4] and MIP [C4mim][CH3SO3]  > MIP [C4mim][C4F9SO3]  > MIP [C4mim][PF6] , which is in good agreement with the ability of anions of the ILs to form hydrogen bonds. Ultraviolet, 1 H-NMR and 35 Cl-NMR spectroscopy was then used to study the interactions of anions of the ILs with the functional monomer. It was found that the hydrogen bond interaction between anions of the ILs and acidic proton of the functional monomer was the main driving force for the high adsorption selectivity of the imprinted polymers, and the stronger hydrogen bond interaction indicates higher binding capacity and higher selectivity of the polymers towards the ILs. It was also verified that the ILs with stronger hydrogen bond accepting ability of anions could be selectively extracted by the corresponding IL-MIPs. These results may provide new insight into the recognition mechanism of MIPs for ILs, and are also useful for the rational design of this new class of imprinting materials. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. An investigation of the structure–property relationships in ionic polymer polymer composites (IP2Cs) manufactured by polymerization in situ of PEDOT/PSS on Nafion®117

    International Nuclear Information System (INIS)

    Di Pasquale, G; Messina, F G; Pollicino, A; Puglisi, R; Graziani, S; Umana, E

    2014-01-01

    Ionic polymer polymer composites (IP 2 Cs) are all-organic electroactive polymers (EAPs) that show sensing and actuation capabilities when a deformation or a voltage is applied, respectively. They are fabricated starting from an ionic polymer coated on both sides with a conducting polymer as electrode element. In this work, poly(3,4-ethylendioxytiophene)–poly-(styrenesulfonate) (PEDOT/PSS) has been polymerized directly on Nafion ® 117 membrane and devices have been manufactured varying the polymerization time. Water and ethylene glycol (EG) have been used as solvents. The obtained IP 2 Cs have been characterized using thermal and mechanical analyses and electromechanically tested. The results have shown that in IP 2 Cs manufactured by polymerization in situ the PEDOT/PSS layer adheres very strongly on the Nafion ® 117 film, improving the possibility of rehydrating the devices after use. Moreover, taking into account that the different polymerization times influence the uniformity of the surface of the organic electrode and, consequently, both device stiffness and electrode conductivity, the structure–property relationships of the obtained devices have been investigated. The influence of the different solvents inside the devices has also been studied when IP 2 Cs have been used as actuators or sensors. Reported results show that it is possible to modulate the performances of IP 2 Cs by varying some manufacture parameters and the solvent. (paper)

  17. Supramolecular ionics: electric charge partition within polymers and other non-conducting solids

    Directory of Open Access Journals (Sweden)

    FERNANDO GALEMBECK

    2001-12-01

    Full Text Available Electrostatic phenomena in insulators have been known for the past four centuries, but many related questions are still unanswered, for instance: which are the charge-bearing species in an electrified organic polymer, how are the charges spatially distributed and which is the contribution of the electrically charged domains to the overall polymer properties? New scanning probe microscopies were recently introduced, and these are suitable for the mapping of electric potentials across a solid sample thus providing some answers for the previous questions. In this work, we report results obtained with two of these techniques: scanning electric potential (SEPM and electric force microscopy (EFM. These results were associated to images acquired by using analytical electron microscopy (energy-loss spectroscopy imaging in the transmission electron microscope, ESI-TEM for colloid polymer samples. Together, they show domains with excess electric charges (and potentials extending up to hundreds of nanometers and formed by large clusters of cations or anions, reaching supramolecular dimensions. Domains with excess electric charge were also observed in thermoplastics as well as in silica, polyphosphate and titanium oxide particles. In the case of thermoplastics, the origin of the charges is tentatively assigned to their tribochemistry, oxidation followed by segregation or the Mawell-Wagner-Sillars and Costa Ribeiro effects.A eletrificação de sólidos é conhecida há quatro séculos, mas há muitas questões importantes sobre este assunto, ainda não respondidas: por exemplo, quais são as espécies portadoras de cargas em um polímero isolante eletrificado, como estas cargas estão espacialmente distribuídas e qual é a contribuição destas cargas para as propriedades do polímero? Técnicas microscópicas introduzidas recentemente são apropriadas para o mapeamento de potenciais elétricos ao longo de uma superfície sólida, portanto podem responder a

  18. An ionic force-field study of monomers, dimers and higher polymers in pentafluoride vapors

    Energy Technology Data Exchange (ETDEWEB)

    Cicek Onem, Z. [Department of Physics, Istanbul University, Istanbul (Turkey); Akdeniz, Z. [Department of Physics, Istanbul University, Istanbul (Turkey); Classe di Scienze, Scuola Normale Superiore, I-56126 Pisa (Italy)], E-mail: zakdeniz@istanbul.edu.tr; Tosi, M.P. [Classe di Scienze, Scuola Normale Superiore, I-56126 Pisa (Italy)], E-mail: tosim@sns.it

    2008-08-01

    Pentafluoride compounds such as NbF{sub 5} and TaF{sub 5} have been reported in the literature to admit various states of polymerization coexisting with monomers in their vapor phase, in relative concentrations that vary with temperature and pressure. We construct a microscopic interionic force-field model for the molecular monomer of these compounds (including VF{sub 5}, SbF{sub 5} and MoF{sub 5} in addition to NbF{sub 5} and TaF{sub 5}), the stable form of the monomer being in the shape of a D{sub 3h} trigonal bipyramid in all cases. The model emulates chemical bonds by allowing for electrical and short-range overlap polarizabilities of the fluorines, and is used to evaluate the structure and the stability of (MF{sub 5}){sub n} molecules with n running from 2 to 6. The dimer is formed by two distorted edge-sharing octahedral, while the trimer and the higher polymers can form rings of distorted corner-sharing octahedra. A chain-like configuration is also found for the trimer of NbF{sub 5}, which consists of a seven-fold coordinated Nb bonded to two distorted octahedra via edge sharing. Comparison of calculated vibrational frequencies and bond lengths with experimental data is made whenever possible. We find that there is a small net gain of energy in the formation of a dimer, while otherwise the static energy of the n-mer is very close to that of n separated monomers. High sensitivity of the state of molecular aggregation to the thermodynamic conditions of the vapor is clearly indicated by our calculations.

  19. Modeling back-relaxation in ionic polymer metal composites: The role of steric effects and composite layers

    Science.gov (United States)

    Porfiri, Maurizio; Sharghi, Hesam; Zhang, Peng

    2018-01-01

    Ionic polymer metal composites (IPMCs) are a new class of active materials that are gaining traction as soft actuators in medical and industrial applications. IPMCs can undergo large deformations under modest voltage inputs, in dry and wet environments. Past studies have demonstrated that physical and geometric properties of all the IPMC constituents (ionomer, electrodes, and counterions) may all influence the time scales of the transient response and severity of the back-relaxation. In this study, we present a detailed mathematical model to investigate how the finite size of the counterions and the presence of metal particles in the vicinity of the electrodes modulate IPMC actuation. We build on previous work by our group on thermodynamically consistent modeling of IPMC mechanics and electrochemistry, which attributes IPMC actuation to the interplay between Maxwell stress and osmotic forces. To gain insight into the role of physical and geometric parameters, the resulting nonlinear partial differential equations are solved semianalytically using the method of matched asymptotic expansions, for the initial transient and the steady-state. A numerical solution in COMSOL Multiphysics® is developed to verify semianalytical findings and further explore IPMC actuation. Our model can successfully predict the entire response of IPMCs, from the initial bending toward the anode to the steady-state toward the cathode. We find that the steric effect can abolish the back-relaxation of IPMCs by restraining the counterions' concentration near the electrodes. We also find that increasing the thickness of the ionomer-metal composite layers may enhance IPMC actuation through increased osmotic forces and Maxwell stress.

  20. 60Co γ-irradiation induced polymerization of methyl methacrylate in imidazolium ionic liquids

    International Nuclear Information System (INIS)

    Qi Mingying; Wu Gongzhong; Liu Yaodong; Chen Shimou; Sha Maolin

    2006-01-01

    Room temperature ionic liquids (RTILs), as a class of novel environmental benign 'green solvents', have been used as reaction media for various polymerizations due to their unique properties of non-volatility, high polarity, ease of recycling and chirality. In radiation polymerization, the energetic photons or electrons result in the formation of solvated electron and radical ions in ionic liquids, which initiate polymerization of monomers without any chemical initiator. In this work, effects of gamma ray irradiation on pure ionic liquid [bmim][PF 6 ] was investigated in detail in a dose range of 5-400 kGy. The ionic liquids were quite stable under low dose irradiations, but underwent notable radiolysis with high doses. With the irradiated [bmim][PF 6 ], the UV-Vis absorbance increased and the fluorescence intensity decreased with increasing doses. Raman spectra proved that gamma radiation induced significant chemical scission of n-butyl group (e.g. C-H and C-C scission), along with damages to the [PF6] - anion. In cooled samples of the irradiated [bmim][PF 6 ] we found two coexist crystal structures, which had suffered a continuous destruction under high dose irradiation. After ensuring stability of the ionic liquids to low dose irradiation, radiation polymerization of methyl methacrylate (MMA) in ionic liquids and IL/organic solutions was performed. By adding the ionic liquids, the monomer conversion and molecular weight (Mw) of the polymer increased significant. Mw of PMMA in neat ionic liquid increased by about 60 times, from 3 x 10 4 with pure organic solvent to about 2 x 10 6 . Molecular weight of the polymer increased with the IL fraction in the IL/organic solutions, and it was dependent on ionic liquids and solvents used, too. It was also found that the polymer obtained in the existence of IL showed multi-modal broadened molecular weight distribution (MWD). A reasonable explanation is the inhomogeneous nature of the ionic liquid in micron scale and the

  1. Composites of ionic liquid and amine-modified SAPO 34 improve CO2 separation of CO2-selective polymer membranes

    Science.gov (United States)

    Hu, Leiqing; Cheng, Jun; Li, Yannan; Liu, Jianzhong; Zhang, Li; Zhou, Junhu; Cen, Kefa

    2017-07-01

    Mixed matrix membranes with ionic liquids and molecular sieve particles had high CO2 permeabilities, but CO2 separation from small gas molecules such as H2 was dissatisfied because of bad interfacial interaction between ionic liquid and molecular sieve particles. To solve that, amine groups were introduced to modify surface of molecular sieve particles before loading with ionic liquid. SAPO 34 was adopted as the original filler, and four mixed matrix membranes with different fillers were prepared on the outer surface of ceramic hollow fibers. Both surface voids and hard agglomerations disappeared, and the surface became smooth after SAPO 34 was modified by amine groups and ionic liquid [P66614][2-Op]. Mixed matrix membranes with composites of amine-modified SAPO 34 and ionic liquid exhibited excellent CO2 permeability (408.9 Barrers) and CO2/H2 selectivity (22.1).

  2. Selective solvation extraction of gold from alkaline cyanide solution by alkyl phosphorus esters

    Energy Technology Data Exchange (ETDEWEB)

    Miller, J.D.; Wan, R.Y.; Mooiman, M.B.; Sibrell, P.L.

    1987-01-01

    Research efforts have shown that solvation extraction of gold from alkaline cyanide solution is possible by alkyl phosphorus esters. Both tributyl phosphate (TBP) and dibutyl butyl phosphonate (DBBP) appear to be effective extractants for gold and exhibit high loading capacities exceeding 30 gpl. Selective solvation extraction of gold from alkaline cyanide solution can be achieved with selectivity factors relative to other cyanoanions as high as 1000 under certain circumstances. Variables influencing the selectivity such as ionic strength, temperature, and extractant structure, are discussed in terms of the extraction chemistry, which seems to involve the solvation of a M dot, dot, dot Au(CN)2 ion pair.

  3. Solid polymer electrolyte lithium batteries

    Science.gov (United States)

    Alamgir, Mohamed; Abraham, Kuzhikalail M.

    1993-01-01

    This invention pertains to Lithium batteries using Li ion (Li.sup.+) conductive solid polymer electrolytes composed of solvates of Li salts immobilized in a solid organic polymer matrix. In particular, this invention relates to Li batteries using solid polymer electrolytes derived by immobilizing solvates formed between a Li salt and an aprotic organic solvent (or mixture of such solvents) in poly(vinyl chloride).

  4. Improving accuracy of electrochemical capacitance and solvation energetics in first-principles calculations

    Science.gov (United States)

    Sundararaman, Ravishankar; Letchworth-Weaver, Kendra; Schwarz, Kathleen A.

    2018-04-01

    Reliable first-principles calculations of electrochemical processes require accurate prediction of the interfacial capacitance, a challenge for current computationally efficient continuum solvation methodologies. We develop a model for the double layer of a metallic electrode that reproduces the features of the experimental capacitance of Ag(100) in a non-adsorbing, aqueous electrolyte, including a broad hump in the capacitance near the potential of zero charge and a dip in the capacitance under conditions of low ionic strength. Using this model, we identify the necessary characteristics of a solvation model suitable for first-principles electrochemistry of metal surfaces in non-adsorbing, aqueous electrolytes: dielectric and ionic nonlinearity, and a dielectric-only region at the interface. The dielectric nonlinearity, caused by the saturation of dipole rotational response in water, creates the capacitance hump, while ionic nonlinearity, caused by the compactness of the diffuse layer, generates the capacitance dip seen at low ionic strength. We show that none of the previously developed solvation models simultaneously meet all these criteria. We design the nonlinear electrochemical soft-sphere solvation model which both captures the capacitance features observed experimentally and serves as a general-purpose continuum solvation model.

  5. First Principles Modeling of Structure and Transport in Solid Polymer Electrolytes, Ionic Liquids, and Methanol/Water Mixtures

    Science.gov (United States)

    2016-02-10

    chemical calculations of the magnesium battery electrolytes we were able to make all vibrational frequency assignments (measured in the IR and Raman ...electrolytes for magnesium batteries incorporating chloro- or iodo- ionic liquids. Much of this work was done in collaboration with the experimental group... magnesium batteries incorporating chloro- or iodo- ionic liquids. Much of this work was done in collaboration with the experimental group of Prof. Vito Di

  6. Ionic conduction studies in Li3+ ion irradiated P(VDF-HFP)-(PC + DEC)-LiCF3SO3 gel polymer electrolyte

    International Nuclear Information System (INIS)

    Saikia, D.; Hussain, A.M.P.; Kumar, A.; Singh, F.; Avasthi, D.K.

    2006-01-01

    In an attempt to increase the Li ion diffusivity in gel polymer electrolytes, the effects of Li 3+ ion irradiation in P(VDF-HFP)-(PC + DEC)-LiCF 3 SO 3 electrolyte system, with five different fluences, is studied. Irradiation with swift heavy ions shows enhancement in conductivity at low fluences and decreased in conductivity at higher fluences with respect to pristine polymer electrolyte films. Maximum room temperature ionic conductivity after irradiation is found to be 2.6 x 10 -3 S/cm. This interesting result could be attributed to the fact that, higher fluence provides critical activation energy for cross-linking and crystallization to occur, which results in decrease in ionic conductivity. XRD results show decrease in the degree of crystallinity upon ion irradiation at low fluences (≤10 11 ions/cm 2 ) and increase in crystallinity at high fluences (>10 11 ions/cm 2 ). In FTIR spectra the absorption band intensities around 3025 cm -1 and 2985 cm -1 decrease upon irradiation with a fluence of 5 x 10 1 ions/cm 2 suggesting chain scission and increase upon irradiation with a fluence of 5 x 10 12 ions/cm 2 indicating cross-linking. FTIR analyses corroborate the conductivity and XRD results

  7. A QuaternaryPoly(ethylene carbonate)-Lithium Bis(trifluoromethanesulfonyl)imide-Ionic Liquid-Silica Fiber Composite Polymer Electrolyte for Lithium Batteries

    International Nuclear Information System (INIS)

    Kimura, Kento; Matsumoto, Hidetoshi; Hassoun, Jusef; Panero, Stefania; Scrosati, Bruno; Tominaga, Yoichi

    2015-01-01

    Highlights: • A quaternary PEC-LiTFSI-Pyr 14 TFSI-Silica fiber electrolyte was prepared by a solvent casting method. • Both electrochemical and mechanical properties were improved by the presence of the Silica fiber. • The electrolyte showed a t Li+ value of 0.36 with an anodic stability extended up to 4.5 V vs. Li/Li + . • A prototype Li/LiFePO 4 polymer cell delivered a discharge capacity of about 100 mAh g −1 (75 °C, C/15). - Abstract: Poly(ethylene carbonate) (PEC) is known as an alternating copolymer derived from carbon dioxide (CO 2 ) and an epoxide as monomers. Here, we describe a new quaternary PEC-based composite electrolyte containing lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) salt, N-n-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide (Pyr 14 TFSI) ionic liquid, and an electrospun silica (SiO 2 ) fiber (SiF) with a submicron diameter in view of its possible applications in solid-state Li polymer batteries. A free-standing electrolyte membrane is prepared by a solvent casting method. The Pyr 14 TFSI ionic liquid enhances the ionic conductivity of the electrolyte as a result of its plasticizing effect. The electrochemical properties, such as ionic conductivity and Li transference number (t Li+ ), as well as mechanical strength of the electrolyte, are further improved by the SiF. We show that the quaternary electrolyte has a conductivity of the order of 10 −7 S cm −1 at ambient temperature and a high t Li+ value of 0.36 with an excellent flexibility. A prototype Li polymer cell using LiFePO 4 as a cathode material is assembled and tested. We demonstrate that this battery delivers a reversible charge-discharge capacity close to 100 mAh g −1 at 75 °C and C/15 rate. We believe that this work may pave the road to utilize CO 2 as a carbon source for highly-demanded, functional battery materials in future

  8. Interfacial solvation thermodynamics

    International Nuclear Information System (INIS)

    Ben-Amotz, Dor

    2016-01-01

    Previous studies have reached conflicting conclusions regarding the interplay of cavity formation, polarizability, desolvation, and surface capillary waves in driving the interfacial adsorptions of ions and molecules at air–water interfaces. Here we revisit these questions by combining exact potential distribution results with linear response theory and other physically motivated approximations. The results highlight both exact and approximate compensation relations pertaining to direct (solute–solvent) and indirect (solvent–solvent) contributions to adsorption thermodynamics, of relevance to solvation at air–water interfaces, as well as a broader class of processes linked to the mean force potential between ions, molecules, nanoparticles, proteins, and biological assemblies. (paper)

  9. Radiation Chemistry and Photochemistry of Ionic Liquids

    International Nuclear Information System (INIS)

    Wishart, J.F.; Takahaski, K.

    2010-01-01

    As our understanding of ionic liquids and their tunable properties has grown, it is possible to see many opportunities for ionic liquids to contribute to the sustainable use of energy. The potential safety and environmental benefits of ionic liquids, as compared to conventional solvents, have attracted interest in their use as processing media for the nuclear fuel cycle. Therefore, an understanding of the interactions of ionizing radiation and photons with ionic liquids is strongly needed. However, the radiation chemistry of ionic liquids is still a relatively unexplored topic although there has been a significant increase in the number of researchers in the field recently. This article provides a brief introduction to ionic liquids and their interesting properties, and recent advances in the radiation chemistry and photochemistry of ionic liquids. In this article, we will mainly focus on excess electron dynamics and radical reaction dynamics. Because solvation dynamics processes in ionic liquids are much slower than in molecular solvents, one of the distinguishing characteristics is that pre-solvated electrons play an important role in ionic liquid radiolysis. It will be also shown that the reaction dynamics of radical ions is significantly different from that observed in molecular solvents because of the Coulombic screening effects and electrostatic interactions in ionic liquids.

  10. Ionic conductivity and electrochemical properties of nanocomposite polymer electrolytes based on electrospun poly(vinylidene fluoride-co-hexafluoropropylene) with nano-sized ceramic fillers

    Energy Technology Data Exchange (ETDEWEB)

    Raghavan, Prasanth; Zhao Xiaohui; Kim, Jae-Kwang; Manuel, James; Chauhan, Ghanshyam S. [Department of Chemical and Biological Engineering and Engineering Research Institute, Gyeongsang National University, 900 Gajwa-dong, Jinju 660-701 (Korea, Republic of); Ahn, Jou-Hyeon [Department of Chemical and Biological Engineering and Engineering Research Institute, Gyeongsang National University, 900 Gajwa-dong, Jinju 660-701 (Korea, Republic of)], E-mail: jhahn@gnu.ac.kr; Nah, Changwoon [Department of Polymer-Nano Science and Technology, Chonbuk National University, 664-14 Duckjin-dong, Jeonju 561-756 (Korea, Republic of)

    2008-12-30

    A series of nanocomposite polymer electrolytes (NCPEs) comprising nanoparticles of BaTiO{sub 3}, Al{sub 2}O{sub 3} or SiO{sub 2} were prepared by electrospinning technique. The nano-sized ceramic fillers were incorporated into poly(vinylidene fluoride-co-hexafluoropropylene) [P(VdF-HEP)] membranes during the electrospinning process. The resultant porous membranes are good absorbent of the liquid electrolyte and exhibit high electrolyte retention capacity. The presence of the ceramic nanoparticles has positive effect on the mechanical properties of the membranes. The ionic conductivity and the electrochemical stability window of the electrospun P(VdF-HFP)-based polymer are enhanced by the presence of the fillers. The cell Li/LiFePO{sub 4} based on the NCPE containing BaTiO{sub 3} delivers a discharge capacity of 164 mAh/g, which corresponds to 96.5% utilization of the active material. In comparison, the performance of Li/LiFePO{sub 4} cells with NCPEs containing Al{sub 2}O{sub 3} and SiO{sub 2} was observed to be lower with respective discharge capacities of 153 and 156 mAh/g. The enhanced performance of the BaTiO{sub 3}-based-NCPE is attributed mainly to its better interaction with the host polymer and compatibility with lithium metal.

  11. Novel composite membranes based on PBI and dicationic ionic liquids for high temperature polymer electrolyte membrane fuel cells

    International Nuclear Information System (INIS)

    Hooshyari, Khadijeh; Javanbakht, Mehran; Adibi, Mina

    2016-01-01

    Two types of innovative composite membranes based on polybenzimidazole (PBI) containing dicationic ionic liquid 1,3-di(3-methylimidazolium) propane bis (trifluoromethylsulfonyl) imide (PDC 3 ) and monocationic ionic liquid 1-hexyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (PMC 6 ) are prepared as electrolyte for high temperature fuel cells applications under anhydrous conditions. The analyses of results display promising characteristics such as high proton conductivity and thermal stability. Moreover the fuel cell performance of PA doped PDC 3 composite membranes is enhanced in comparison with PA doped PMC 6 and PA doped PBI membranes at high temperatures. Dicationic ionic liquid with high number of charge carriers provides well-developed ionic channels which form facile pathways and considerably develop the anhydrous proton conductivity. The highest proton conductivity of 81 mS/cm is achieved for PA doped PDC 3 composite membranes with PBI/IL mole ratio: 4 at 180 °C. A power density of 0.44 W/cm 2 is obtained at 0.5 V and 180 °C for PA doped PDC 3 composite membranes, which proves that these developed composite membranes can be considered as most promising candidates for high temperature fuel cell applications with enhanced proton conductivity.

  12. A novel gel based on an ionic complex from a dendronized polymer and ciprofloxacin: Evaluation of its use for controlled topical drug release

    Energy Technology Data Exchange (ETDEWEB)

    García, Mónica C. [Unidad de Investigación y Desarrollo en Tecnología Farmacéutica (UNITEFA), CONICET and Departamento de Farmacia, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, X5000HUA Córdoba (Argentina); Cuggino, Julio C. [Instituto de Desarrollo Tecnológico para la Industria Química (INTEC), CONICET, Colectora Ruta Nac. N° 168, km. 0, Pje. El Pozo, 3000 Santa Fe (Argentina); Rosset, Clarisa I.; Páez, Paulina L. [Unidad de Investigación y Desarrollo en Tecnología Farmacéutica (UNITEFA), CONICET and Departamento de Farmacia, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, X5000HUA Córdoba (Argentina); Strumia, Miriam C. [Instituto Multidisciplinario de Biología Vegetal (IMBIV), CONICET and Laboratorio de Materiales Poliméricos (LAMAP), Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, X5000HUA Córdoba (Argentina); and others

    2016-12-01

    The development and characterization of a novel, gel-type material based on a dendronized polymer (DP) loaded with ciprofloxacin (CIP), and the evaluation of its possible use for controlled drug release, are presented in this work. DP showed biocompatible and non-toxic behaviors in cultured cells, both of which are considered optimal properties for the design of a final material for biomedical applications. These results were encouraging for the use of the polymer loaded with CIP (as a drug model), under gel form, in the development of a new controlled-release system to be evaluated for topical administration. First, DP-CIP ionic complexes were obtained by an acid-base reaction using the high density of carboxylic acid groups of the DP and the amine groups of the CIP. The complexes obtained in the solid state were broadly characterized using FTIR spectroscopy, XRP diffraction, DSC-TG analysis and optical microscopy techniques. Gels based on the DP-CIP complexes were easily prepared and presented excellent mechanical behaviors. In addition, optimal properties for application on mucosal membranes and skin were achieved due to their high biocompatibility and acute skin non-irritation. Slow and sustained release of CIP toward simulated physiological fluids was observed in the assays (in vitro), attributed to ion exchange phenomenon and to the drug reservoir effect. An in vitro bacterial growth inhibition assay showed significant CIP activity, corresponding to 38 and 58% of that exhibited by a CIP hydrochloride solution at similar CIP concentrations, against Staphylococcus aureus and Pseudomonas aeruginosa, respectively. However, CIP delivery was appropriate, both in terms of magnitude and velocity to allow for a bactericidal effect. In conclusion, the final product showed promising behavior, which could be exploited for the treatment of topical and mucosal opportunistic infections in human or veterinary applications. - Highlights: • A novel hydrogel based on

  13. A novel gel based on an ionic complex from a dendronized polymer and ciprofloxacin: Evaluation of its use for controlled topical drug release

    International Nuclear Information System (INIS)

    García, Mónica C.; Cuggino, Julio C.; Rosset, Clarisa I.; Páez, Paulina L.; Strumia, Miriam C.

    2016-01-01

    The development and characterization of a novel, gel-type material based on a dendronized polymer (DP) loaded with ciprofloxacin (CIP), and the evaluation of its possible use for controlled drug release, are presented in this work. DP showed biocompatible and non-toxic behaviors in cultured cells, both of which are considered optimal properties for the design of a final material for biomedical applications. These results were encouraging for the use of the polymer loaded with CIP (as a drug model), under gel form, in the development of a new controlled-release system to be evaluated for topical administration. First, DP-CIP ionic complexes were obtained by an acid-base reaction using the high density of carboxylic acid groups of the DP and the amine groups of the CIP. The complexes obtained in the solid state were broadly characterized using FTIR spectroscopy, XRP diffraction, DSC-TG analysis and optical microscopy techniques. Gels based on the DP-CIP complexes were easily prepared and presented excellent mechanical behaviors. In addition, optimal properties for application on mucosal membranes and skin were achieved due to their high biocompatibility and acute skin non-irritation. Slow and sustained release of CIP toward simulated physiological fluids was observed in the assays (in vitro), attributed to ion exchange phenomenon and to the drug reservoir effect. An in vitro bacterial growth inhibition assay showed significant CIP activity, corresponding to 38 and 58% of that exhibited by a CIP hydrochloride solution at similar CIP concentrations, against Staphylococcus aureus and Pseudomonas aeruginosa, respectively. However, CIP delivery was appropriate, both in terms of magnitude and velocity to allow for a bactericidal effect. In conclusion, the final product showed promising behavior, which could be exploited for the treatment of topical and mucosal opportunistic infections in human or veterinary applications. - Highlights: • A novel hydrogel based on

  14. [Verification of a decrease in the rigidity of the phage lambda DNA polymeric chain in low ionic strength aqueous solutions by testing the polymer-polymer interlink interactions].

    Science.gov (United States)

    Arutiunian, A V; Ivanova, M A; Kurliand, D I; Kapshin, Iu S; Landa, S B; Poshekhonov, S T; Drobchenko, E A; Shevelev, I V

    2011-01-01

    Changes in the rigidity of the polymetric chain of phage lambda double-strand DNA have been studied by laser correlation spectroscopy. It was shown that, as the ionic strength increases, the effect of the screening of the hydrodynamic interaction of the links of the polymeric chain specific for polymeric coils arises in a DNA solution. It is assumed that the screening occurs when the threshold of the overlapping of DNA coils is achieved. The overlapping of coils is the result of a previously observed significant rise of DNA coil size from abnormally small DNA coils in low ionic strength buffers (about 10(-2) M Na+ or less) to maximum possible large coils in the 5SSC and 5SSC-like buffers. Further analysis of the far interlink interactions in linear lambda phage DNA coils in similar buffers at pH 7 and 4 confirms the earlier proposal about the role of H+ ions in the appearance of abnormally small DNA coils. The abnormal decrease in the DNA coil size in low ionic strength buffers is not a specific feature of lambda phage DNA only.

  15. Solid-phase extraction of chlorophenols in seawater using a magnetic ionic liquid molecularly imprinted polymer with incorporated silicon dioxide as a sorbent.

    Science.gov (United States)

    Ma, Wanwan; Row, Kyung Ho

    2018-07-20

    A type of magnetic ionic liquid based molecularly imprinted polymer coated on SiO 2 (Fe 3 O 4 @SiO 2 @IL-MIPs) was prepared with 1-vinyl-3-ethylimidazole ionic liquid as functional monomer, and 1,4-butane-3,3'-bis-1-ethylimidazole ionic liquid as cross linker, 4-Chlorophenol as template was successfully applied as a selective adsorbent for selective extraction of 5 chlorophenols in seawater samples by using the magnetic solid-phase extraction (MSPE) method. 11 types of Fe 3 O 4 @SiO 2 @IL-MIPs were synthesized and investigated for their different compositions of functional monomer (such as [C 2 min][Br], [C 2 min][BF 4 ], [C 2 min][PF 6 ], acrylamide, methacrylic acid and 4-vinyl pyridine) and cross-linker (such as [C 4 min 2 ][Br], [C 4 min 2 ][BF 4 ], [C 4 min 2 ][PF 6 ], divinylbenzene, and ethylene glycol dimethacrylate), respectively. The [C 2 min][BF 4 ] and [C 4 min 2 ][PF 6 ] based Fe 3 O 4 @SiO 2 @IL-MIP with the highest extraction efficiencies was applied to the optimization experiment of MSPE process (including extraction time, adsorbent mass and desorption solvents). Good linearity was obtained with correlation coefficients (R 2 ) over 0.9990 and the relative standard deviations for the intra-day and inter-day determination were less than 3.10% with the extraction recoveries ranged from 85.0% to 98.4%. The results indicated that the proposed Fe 3 O 4 @SiO 2 @IL-MIPs possesses great identification and adsorption properties, and could be used as a good sorbent for selective extraction of CPs in environment waters. Copyright © 2018 Elsevier B.V. All rights reserved.

  16. Lipid processing in ionic liquids

    DEFF Research Database (Denmark)

    Lue, Bena-Marie; Guo, Zheng; Xu, Xuebing

    2007-01-01

    Ionic liquids (ILs) have been touted as “green” alternatives to traditional molecular solvents and have many unique properties which make them extremely desirable substitutes. Among their most attractive properties are their lack of vapour pressure, broad liquid range, strong solvating power and ...... and the ability to tailor properties of individual ILs to meet specific requirements. This article highlights current research as well as the vast potential of ILs for use as media for reactions, separation and processing in the lipid area....

  17. High-capacity hollow porous dummy molecular imprinted polymers using ionic liquid as functional monomer for selective recognition of salicylic acid.

    Science.gov (United States)

    Xiang, Haiyan; Peng, Mijun; Li, Hui; Peng, Sheng; Shi, Shuyun

    2017-01-30

    The existence of strong intramolecular hydrogen bond in salicylic acid (SA) weakens its intermolecular hydrogen bonding with functional monomer, then it is a challenge work to fabricate molecularly imprinted polymers (MIPs) for SA recognition with high capacity and good selectivity. Here, hollow porous dummy MIPs (HPDMIPs) were prepared using benzoic acid (BA) as dummy template, ionic liquid (i.e. 1-vinyl-3-methylimidazolium chloride) as functional monomer, and MCM-48 as sacrificial support. Factors that affected adsorption, such as type of template and porogen, mole ratio of template-functional monomer-cross-linker and type of binding solvent, were optimized in detail. Multiple strong interactions between SA and ionic liquid in HPDMIPs deduced higher binding capacity (29.75mg/g), imprinting factor (5.61) and selectivity than any previously reported MIPs by traditional or surface imprinting technology. The large surface area (543.9m 2 /g) with hollow porous structure resulted in faster kinetic binding (25min). The equilibrium data fitted well to Freundlich equation and the adsorption process could be described by pseudo-second order model. Finally, HPDMIPs were successfully applied to selectively extract and enrich SA from Actinidia chinensis with a relatively high recovery (84.6-94.5%). Copyright © 2016 Elsevier B.V. All rights reserved.

  18. Conductivity enhancement in K{sup +}-ion conducting dry Solid Polymer Electrolyte (SPE): [PEO: KNO{sub 3}]: A consequence of KI dispersal and nano-ionic effect

    Energy Technology Data Exchange (ETDEWEB)

    Kesharwani, Priyanka; Sahu, Dinesh K.; Mahipal, Y.K.; Agrawal, R.C., E-mail: rakesh_c_agrawal@yahoo.co.in

    2017-06-01

    Flexible films of dry Solid Polymer Electrolytes (SPEs): [PEO: KNO{sub 3}] in varying salt concentrations have been hot-press cast. Salt concentration dependent conductivity study revealed two SPE films: [95PEO: 5KNO{sub 3}] and [70PEO: 30KNO{sub 3}] exhibiting relatively higher room temperature conductivity (σ{sub rt}) ∼ 2.76 × 10{sup -7} S/cm and ∼4.31 × 10{sup -7} S/cm respectively. In order to increase σ{sub rt} further, two strategies have been adopted. Firstly, fractional amount of KI has been dispersed as IInd-phase active filler into above two SPE film compositions which acted as Ist-phase host and Composite Polymer Electrolyte (CPE) films were hot-press cast. Filler particle concentration dependent conductivity study identified CPE films: [(95PEO: 5KNO{sub 3}) + 7KI] and [(70PEO: 30KNO{sub 3}) + 10 KI] as optimum conducting films with σ{sub rt} ∼ 6.15 × 10{sup -6} S/cm and ∼3.98 × 10{sup -6} S/cm respectively. σ{sub rt}-enhancement of approximately an order of magnitude was achieved by this approach. In second approach, dry powder mixture of (KNO{sub 3} + KI), in ratio that of above two CPE films, were subjected to high energy ball-milling separately for different durations prior to casting the films again. The conductivity measurements as a function of milling time identified CPE films: [(95PEO: 5KNO{sub 3}) + 7KI] and [(70PEO: 30KNO{sub 3}) + 10 KI] in which two respective (KNO{sub 3} + KI) ratios milled for 4- and 6-h, exhibited almost similar value of σ{sub rt} ∼ 2.09 × 10{sup -5} S/cm. This approach increased σ{sub rt} further by ∼3–6 fold. The reason attributed for this has been Nano–ionic effect introduced at the interphase boundaries between KNO{sub 3} and KI, as a consequence of milling. These films have been referred to as milled CPE films. Subsequently, all the optimum conducting SPE and CPE (unmilled/milled) films were subjected to various characterization studies in order to evaluate their utility in potential All

  19. Ionic Conductivity and Cycling Stability Improvement of PVDF/Nano-Clay Using PVP as Polymer Electrolyte Membranes for LiFePO4 Batteries

    Directory of Open Access Journals (Sweden)

    Endah R. Dyartanti

    2018-07-01

    Full Text Available In this paper, we present the characteristics and performance of polymer electrolyte membranes (PEMs based on poly(vinylidene fluoride (PVDF. The membranes were prepared via a phase-inversion method (non-solvent-induced phase separation (NIPS. As separators for lithium battery systems, additive modified montmorillonite (MMT nano-clay served as a filler and poly(vinylpyrrolidone (PVP was used as a pore-forming agent. The membranes modified with an additive (8 wt % nano-clay and 7 wt % PVP showed an increased porosity (87% and an uptake of a large amount of electrolyte (801.69%, which generated a high level of ionic conductivity (5.61 mS cm−1 at room temperature. A graphite/PEMs/LiFePO4 coin cell CR2032 showed excellent stability in cycling performance (average discharge capacity 127 mA h g−1. Based on these results, PEMs are promising materials to be used in Polymer Electrolyte Membranes in lithium-ion batteries.

  20. Coordination Chemistry Inside Polymeric Nanoreactors: Interparticle Metal Exchange and Ionic Compound Vectorization in Phosphine-Functionalized Amphiphilic Polymer Latexes.

    Science.gov (United States)

    Chen, Si; Gayet, Florence; Manoury, Eric; Joumaa, Ahmad; Lansalot, Muriel; D'Agosto, Franck; Poli, Rinaldo

    2016-04-25

    Stable latexes of hierarchically organized core-cross-linked polymer micelles that are functionalized at the core with triphenylphosphine (TPP@CCM) have been investigated by NMR spectroscopic analysis at both natural (ca. pH 5) and strongly basic (pH 13.6) pH values after core swelling with toluene. The core-shell interface structuring forces part of the hydrophilic poly(ethylene oxide) (PEO) chains to reside inside the hydrophobic core at both pH values. Loading the particle cores with [Rh(acac)(CO)2 ] (acac=acetylacetonate) at various Rh/P ratios yielded polymer-supported [Rh(acac)(CO)(TPP)] (TPP=triphenylphosphine). The particle-to-particle rhodium migration is very fast at natural pH, but slows down dramatically at high pH, whereas the size distribution of the nanoreactors remains unchanged. The slow migration at pH 13.6 leads to the generation of polymer-anchored [Rh(OH)(CO)(TPP)2 ], which is also generated immediately upon the addition of NaOH to the particles with a [Rh(acac)(CO)] loading of 50 %. Similarly, treatment of the same particles with NaCl yielded polymer-anchored [RhCl(CO)(TPP)2 ]. Interparticle coupling occurs during these rapid processes. These experiments prove that the major contribution to metal migration is direct core-core contact. The slow migration at the high pH value, however, must result from a pathway that does not involve core-core contact. The facile penetration of the polymer cores by NaOH and NaCl results from the presence of shell-linked poly(ethylene oxide) methyl ether functions both outside and inside the polymer core-shell interface. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Design and Fabrication of a Large-Stroke Deformable Mirror Using a Gear-Shape Ionic-Conductive Polymer Metal Composite

    Directory of Open Access Journals (Sweden)

    Guo-Dung John Su

    2012-08-01

    Full Text Available Conventional camera modules with image sensors manipulate the focus or zoom by moving lenses. Although motors, such as voice-coil motors, can move the lens sets precisely, large volume, high power consumption, and long moving time are critical issues for motor-type camera modules. A deformable mirror (DM provides a good opportunity to improve these issues. The DM is a reflective type optical component which can alter the optical power to focus the lights on the two dimensional optical image sensors. It can make the camera system operate rapidly. Ionic polymer metal composite (IPMC is a promising electro-actuated polymer material that can be used in micromachining devices because of its large deformation with low actuation voltage. We developed a convenient simulation model based on Young’s modulus and Poisson’s ratio. We divided an ion exchange polymer, also known as Nafion®, into two virtual layers in the simulation model: one was expansive and the other was contractive, caused by opposite constant surface forces on each surface of the elements. Therefore, the deformation for different IPMC shapes can be described more easily. A standard experiment of voltage vs. tip displacement was used to verify the proposed modeling. Finally, a gear shaped IPMC actuator was designed and tested. Optical power of the IPMC deformable mirror is experimentally demonstrated to be 17 diopters with two volts. The needed voltage was about two orders lower than conventional silicon deformable mirrors and about one order lower than the liquid lens.

  2. Ion-Selective Ionic Polymer Metal Composite (IPMC) actuator based on crown ether containing sulfonated Poly(Arylene Ether Ketone)

    NARCIS (Netherlands)

    Tas, S.; Zoetebier, B.; Sukas, O.S.; Bayraktar, M.; Hempenius, M.; Vancso, G.J.; Nijmeijer, K.

    2017-01-01

    This study introduces the concept of ion selective actuation in polymer metal composite actuators, employing crown ether bearing aromatic polyether materials. For this purpose, sulfonated poly(arylene ether ketone) (SPAEK) and crown ether containing SPAEK with molar masses suitable for membrane

  3. Ionic liquid processing of cellulose.

    Science.gov (United States)

    Wang, Hui; Gurau, Gabriela; Rogers, Robin D

    2012-02-21

    Utilization of natural polymers has attracted increasing attention because of the consumption and over-exploitation of non-renewable resources, such as coal and oil. The development of green processing of cellulose, the most abundant biorenewable material on Earth, is urgent from the viewpoints of both sustainability and environmental protection. The discovery of the dissolution of cellulose in ionic liquids (ILs, salts which melt below 100 °C) provides new opportunities for the processing of this biopolymer, however, many fundamental and practical questions need to be answered in order to determine if this will ultimately be a green or sustainable strategy. In this critical review, the open fundamental questions regarding the interactions of cellulose with both the IL cations and anions in the dissolution process are discussed. Investigations have shown that the interactions between the anion and cellulose play an important role in the solvation of cellulose, however, opinions on the role of the cation are conflicting. Some researchers have concluded that the cations are hydrogen bonding to this biopolymer, while others suggest they are not. Our review of the available data has led us to urge the use of more chemical units of solubility, such as 'g cellulose per mole of IL' or 'mol IL per mol hydroxyl in cellulose' to provide more consistency in data reporting and more insight into the dissolution mechanism. This review will also assess the greenness and sustainability of IL processing of biomass, where it would seem that the choices of cation and anion are critical not only to the science of the dissolution, but to the ultimate 'greenness' of any process (142 references).

  4. Nanoscale Ionic Materials

    KAUST Repository

    Rodriguez, Robert; Herrera, Rafael; Archer, Lynden A.; Giannelis, Emmanuel P.

    2008-01-01

    Polymer nanocomposites (nanoparticles dispersed in a polymer matrix) have been the subject of intense research for almost two decades in both academic and industrial settings. This interest has been fueled by the ability of nanocomposites to not only improve the performance of polymers, but also by their ability to introduce new properties. Yet, there are still challenges that polymer nanocomposites must overcome to reach their full potential. In this Research News article we discuss a new class of hybrids termed nanoparticle ionic materials (NIMS). NIMS are organic-inorganic hybrid materials comprising a nanoparticle core functionalized with a covalently tethered ionic corona. They are facilely engineered to display flow properties that span the range from glassy solids to free flowing liquids. These new systems have unique properties that can overcome some of the challenges facing nanocomosite materials. © 2008 WILEY-VCH Verlag GmbH & Co. KGaA.

  5. Nanoscale Ionic Materials

    KAUST Repository

    Rodriguez, Robert

    2008-11-18

    Polymer nanocomposites (nanoparticles dispersed in a polymer matrix) have been the subject of intense research for almost two decades in both academic and industrial settings. This interest has been fueled by the ability of nanocomposites to not only improve the performance of polymers, but also by their ability to introduce new properties. Yet, there are still challenges that polymer nanocomposites must overcome to reach their full potential. In this Research News article we discuss a new class of hybrids termed nanoparticle ionic materials (NIMS). NIMS are organic-inorganic hybrid materials comprising a nanoparticle core functionalized with a covalently tethered ionic corona. They are facilely engineered to display flow properties that span the range from glassy solids to free flowing liquids. These new systems have unique properties that can overcome some of the challenges facing nanocomosite materials. © 2008 WILEY-VCH Verlag GmbH & Co. KGaA.

  6. Thermal stability, swelling behavior and CO 2 absorption properties of Nanoscale Ionic Materials (NIMs)

    KAUST Repository

    Andrew Lin, Kun-Yi; Park, Youngjune; Petit, Camille; Park, Ah-Hyung Alissa

    2014-01-01

    © The Royal Society of Chemistry 2015. Nanoscale Ionic Materials (NIMs) consist of a nanoscale core, a corona of charged brushes tethered on the surface of the core, and a canopy of the oppositely charged species linked to the corona. Unlike conventional polymeric nanocomposites, NIMs can display liquid-like behavior in the absence of solvents, have a negligible vapor pressure and exhibit unique solvation properties. These features enable NIMs to be a promising CO2 capture material. To optimize NIMs for CO2 capture, their structure-property relationships were examined by investigating the roles of the canopy and the core in their thermal stability, and thermally- and CO2-induced swelling behaviors. NIMs with different canopy sizes and core fractions were synthesized and their thermal stability as well as thermally- and CO2-induced swelling behaviors were determined using thermogravimetry, and ATR FT-IR and Raman spectroscopies. It was found that the ionic bonds between the canopy and the corona, as well as covalent bonds between the corona and the core significantly improved the thermal stability compared to pure polymer and polymer/nanofiller mixtures. A smaller canopy size and a larger core fraction led to a greater enhancement in thermal stability. This thermal stability enhancement was responsible for the long-term thermal stability of NIMs over 100 temperature swing cycles. Owing to their ordered structure, NIMs swelled less when heated or when they adsorbed CO2 compared to their corresponding polymers. This journal is

  7. Thermal stability, swelling behavior and CO 2 absorption properties of Nanoscale Ionic Materials (NIMs)

    KAUST Repository

    Andrew Lin, Kun-Yi

    2014-11-11

    © The Royal Society of Chemistry 2015. Nanoscale Ionic Materials (NIMs) consist of a nanoscale core, a corona of charged brushes tethered on the surface of the core, and a canopy of the oppositely charged species linked to the corona. Unlike conventional polymeric nanocomposites, NIMs can display liquid-like behavior in the absence of solvents, have a negligible vapor pressure and exhibit unique solvation properties. These features enable NIMs to be a promising CO2 capture material. To optimize NIMs for CO2 capture, their structure-property relationships were examined by investigating the roles of the canopy and the core in their thermal stability, and thermally- and CO2-induced swelling behaviors. NIMs with different canopy sizes and core fractions were synthesized and their thermal stability as well as thermally- and CO2-induced swelling behaviors were determined using thermogravimetry, and ATR FT-IR and Raman spectroscopies. It was found that the ionic bonds between the canopy and the corona, as well as covalent bonds between the corona and the core significantly improved the thermal stability compared to pure polymer and polymer/nanofiller mixtures. A smaller canopy size and a larger core fraction led to a greater enhancement in thermal stability. This thermal stability enhancement was responsible for the long-term thermal stability of NIMs over 100 temperature swing cycles. Owing to their ordered structure, NIMs swelled less when heated or when they adsorbed CO2 compared to their corresponding polymers. This journal is

  8. Modeling of an ionic polymer metal composite actuator based on an extended Kalman filter trained neural network

    International Nuclear Information System (INIS)

    Truong, Dinh Quang; Ahn, Kyoung Kwan

    2014-01-01

    An ion polymer metal composite (IPMC) is an electroactive polymer that bends in response to a small applied electric field as a result of mobility of cations in the polymer network and vice versa. This paper presents an innovative and accurate nonlinear black-box model (NBBM) for estimating the bending behavior of IPMC actuators. The model is constructed via a general multilayer perceptron neural network (GMLPNN) integrated with a smart learning mechanism (SLM) that is based on an extended Kalman filter with self-decoupling ability (SDEKF). Here the GMLPNN is built with an ability to autoadjust its structure based on its characteristic vector. Furthermore, by using the SLM based on the SDEKF, the GMLPNN parameters are optimized with small computational effort, and the modeling accuracy is improved. An apparatus employing an IPMC actuator is first set up to investigate the IPMC characteristics and to generate the data for training and validating the model. The advanced NBBM model for the IPMC system is then created with the proper inputs to estimate IPMC tip displacement. Next, the model is optimized using the SLM mechanism with the training data. Finally, the optimized NBBM model is verified with the validating data. A comparison between this model and the previously developed model is also carried out to prove the effectiveness of the proposed modeling technique. (paper)

  9. A novel ionic liquid-modified organic-polymer monolith as the sorbent for in-tube solid-phase microextraction of acidic food additives.

    Science.gov (United States)

    Wang, Ting-Ting; Chen, Yi-Hui; Ma, Jun-Feng; Hu, Min-Jie; Li, Ying; Fang, Jiang-Hua; Gao, Hao-Qi

    2014-08-01

    A novel ionic liquid-modified organic-polymer monolithic capillary column was prepared and used for in-tube solid-phase microextraction (SPME) of acidic food additives. The primary amino group of 1-aminopropyl-3-methylimidazolium chloride was reacted with the epoxide group of glycidyl methacrylate. The as-prepared new monomer was then copolymerized in situ with acrylamide and N,N'-methylenebisacrylamide in the presence of polyethylene glycol (PEG)-8000 and PEG-10,000 as porogens. The extraction performance of the developed monolithic sorbent was evaluated for benzoic acid, 3-hydroxybenzoic acid, cinnamic acid, 2,4-dichlorophenoxyacetic acid, and 3-(trifluoromethyl)-cinnamic acid. Such a sorbent, bearing hydrophobic and anion-exchange groups, had high extraction efficiency towards the test compounds. The adsorption capacities for the analytes dissolved in water ranged from 0.18 to 1.74 μg cm(-1). Good linear calibration curves (R(2) > 0.99) were obtained, and the limits of detection (S/N = 3) for the analytes were found to be in the range 1.2-13.5 ng mL(-1). The recoveries of five acidic food additives spiked in Coca-Cola beverage samples ranged from 85.4 % to 98.3 %, with RSD less than 6.9 %. The excellent applicability of the ionic liquid (IL)-modified monolithic column was further tested by the determination of benzoic acid content in Sprite samples, further illustrating its good potential for analyzing food additives in complex samples.

  10. Utilization of carbon dioxide for polymer electrolytes [I]: Effect of supercritical treatment conditions on ionic conduction in amorphous polyether/salt mixtures

    International Nuclear Information System (INIS)

    Oe, Yoshiyuki; Tominaga, Yoichi

    2011-01-01

    Highlights: ► Supercritical CO 2 treatment on amorphous polyether/salt mixtures improves ionic conductivity in the dry state. ► Suitable CO 2 condition for high conductivity exists in near the critical temperature and pressure. ► Conductivity decreases only 20% after 30 days. ► Dissociation of free ClO 4 − and interactions between ether chains and Li + increase in treated electrolytes. - Abstract: Supercritical carbon dioxide (scCO 2 ) as a treatment medium has a possibility to realize excellent room temperature conductivity more than 10 −4 S/cm for polymer electrolytes in the dry state. In this study, a typical high ion-conductive polyether-based electrolyte which consists of poly-[ethylene oxide-co-2-(2-methoxyethoxy)ethyl glycidyl ether] (P(EO/EM)) and lithium perchlorate (LiClO 4 ) was used as a model sample for the scCO 2 treatment. We found the suitable scCO 2 treatment conditions (pressure, temperature and time) for high conductivity. The conductivity of sample treated at 7.5 MPa and 40 °C for 40 min was more than 100-times higher than that of original without the treatment, and the value decreased only 20% after 30 days. DSC measurement revealed that the decrease in glass transition temperature (T g ) is caused by the scCO 2 -treatment. The change of ionic association in the scCO 2 -treated samples was confirmed using FT-IR measurement. The scCO 2 treatment gave rise to increase in peak fraction of free ClO 4 − anions (620–625 cm −1 ) and peak shift of ν(C–O–C) mode to lower frequency region (1060–1070 cm −1 ) depending on ether–Li + interactions.

  11. Theories of the solvated electron

    International Nuclear Information System (INIS)

    Kestner, N.R.

    1987-01-01

    In this chapter the authors address only the final state of the electron, that is, the solvated state, which, if no chemical reaction would occur, is a stable entity with well-defined characteristics. Except for some metal-ammonia solutions, and possible a few other cases, such stable species, in reality, exist but a short time (often as short as microseconds). Nevertheless, this chapter only deals with this final time-independent,'' completely solvated,'' equilibrium species. The last statement is added to indicate that the solvent around the electron has also come to thermal equilibrium with the field of the charge

  12. Studies on polymer electrolyte poly(vinyl) pyrrolidone (PVP) complexed with ionic liquid: Effect of complexation on thermal stability, conductivity and relaxation behaviour

    Energy Technology Data Exchange (ETDEWEB)

    Saroj, A.L. [Department of Physics, Banaras Hindu University, Varanasi, 221005 (India); Singh, R.K., E-mail: rksingh_17@rediffmail.com [Department of Physics, Banaras Hindu University, Varanasi, 221005 (India); Chandra, S. [Department of Physics, Banaras Hindu University, Varanasi, 221005 (India)

    2013-03-01

    Highlights: Black-Right-Pointing-Pointer PVP + IL based polymer electrolyte films have been prepared and studied. Black-Right-Pointing-Pointer The complexation/interaction of PVP with IL has been confirmed by FT-IR analysis. Black-Right-Pointing-Pointer The conductivity and relaxation frequency increases with increasing IL content. Black-Right-Pointing-Pointer Two relaxation peaks for complexed and uncomplexed PVP with IL have been observed. - Abstract: Polymer electrolyte films of PVP + x wt% ionic liquid (IL) (1-ethyl-3-methylimidazolium tetrafluoroborate [EMIM][BF{sub 4}]) for x = 0, 5, 10, 15, 20, 25 wt% have been prepared using solution cast technique. These films were characterized by TGA, DSC, FT-IR and ac impedance spectroscopy techniques. From XRD studies it is found that the inclusion of IL increases the amorphocity of polymeric membranes. DSC thermograms show that the glass transition (T{sub g}) and melting temperatures (T{sub m}) of PVP shift upon complexation with IL. FT-IR analysis shows the complexation of PVP with IL. Thermogravimetric studies show that PVP decomposes in a single step while PVP/IL membranes exhibit two step decomposition; lower value of decomposition temperature corresponds to the decomposition of PVP/IL complex while the higher decomposition temperature has been attributed to the decomposition of PVP. The decomposition temperature of PVP/IL complex decreases with the increasing amount of IL in the PVP membrane. Temperature dependence of conductivity and dielectric relaxation frequencies have also been studied for PVP and PVP/IL membranes. Both show thermally activated Arrhenius behaviour.

  13. Polímeros com condutividade iônica: desafios fundamentais e potencial tecnológico Polymers with ionic conductivity: fundamental challenges and technological potential

    Directory of Open Access Journals (Sweden)

    Virgínia P. R. Silva

    2005-11-01

    Full Text Available Polímeros condutores iônicos ou eletrólitos poliméricos constituídos por um sistema de sal dissolvido em uma matriz polimérica sólida são materiais que apresentam interesse científico e potencial tecnológico. A dissolução de sais em uma matriz polimérica amorfa ou semicristalina sólida leva a estudos sobre intrigantes aspectos estruturais, que podem ser abordados por técnicas físico-químicas diversas tais como RMN, Raman e Espectroscopia de Vida Média de Pósitrons. Os estudos estruturais são correlacionados com propriedades eletroquímicas visando à utilização desses materiais em dispositivos tais como baterias, supercapacitores e células solares. Grupos brasileiros têm gradativamente ampliado os estudos e aplicações de eletrólitos poliméricos sólidos.Ionic conducting polymers or polymer electrolytes prepared with the addition of a soluble salt in a solid polymeric matrix are very important materials, associated with an intense research activity and technological efforts. Structural studies in a system of salt dissolved in an amorphous or semicrystalline solid polymeric matrix can be done with various techniques, such as NMR, Raman and Positron Annihilation Spectroscopy. The structural studies are correlated with electrochemical properties in order to evaluate these materials for applications in batteries, supercapacitors and solar cells. Brazilian researchers are contributing to the fundamental research and development of new applications of polymeric electrolytes.

  14. Membrane separation of ionic liquid solutions

    Science.gov (United States)

    Campos, Daniel; Feiring, Andrew Edward; Majumdar, Sudipto; Nemser, Stuart

    2015-09-01

    A membrane separation process using a highly fluorinated polymer membrane that selectively permeates water of an aqueous ionic liquid solution to provide dry ionic liquid. Preferably the polymer is a polymer that includes polymerized perfluoro-2,2-dimethyl-1,3-dioxole (PDD). The process is also capable of removing small molecular compounds such as organic solvents that can be present in the solution. This membrane separation process is suitable for drying the aqueous ionic liquid byproduct from precipitating solutions of biomass dissolved in ionic liquid, and is thus instrumental to providing usable lignocellulosic products for energy consumption and other industrial uses in an environmentally benign manner.

  15. Solvation thermodynamics and heat capacity of polar and charged solutes in water

    Science.gov (United States)

    Sedlmeier, Felix; Netz, Roland R.

    2013-03-01

    The solvation thermodynamics and in particular the solvation heat capacity of polar and charged solutes in water is studied using atomistic molecular dynamics simulations. As ionic solutes we consider a F- and a Na+ ion, as an example for a polar molecule with vanishing net charge we take a SPC/E water molecule. The partial charges of all three solutes are varied in a wide range by a scaling factor. Using a recently introduced method for the accurate determination of the solvation free energy of polar solutes, we determine the free energy, entropy, enthalpy, and heat capacity of the three different solutes as a function of temperature and partial solute charge. We find that the sum of the solvation heat capacities of the Na+ and F- ions is negative, in agreement with experimental observations, but our results uncover a pronounced difference in the heat capacity between positively and negatively charged groups. While the solvation heat capacity ΔCp stays positive and even increases slightly upon charging the Na+ ion, it decreases upon charging the F- ion and becomes negative beyond an ion charge of q = -0.3e. On the other hand, the heat capacity of the overall charge-neutral polar solute derived from a SPC/E water molecule is positive for all charge scaling factors considered by us. This means that the heat capacity of a wide class of polar solutes with vanishing net charge is positive. The common ascription of negative heat capacities to polar chemical groups might arise from the neglect of non-additive interaction effects between polar and apolar groups. The reason behind this non-additivity is suggested to be related to the second solvation shell that significantly affects the solvation thermodynamics and due to its large spatial extent induces quite long-ranged interactions between solvated molecular parts and groups.

  16. Enthalpy-entropy compensation: the role of solvation.

    Science.gov (United States)

    Dragan, Anatoliy I; Read, Christopher M; Crane-Robinson, Colyn

    2017-05-01

    Structural modifications to interacting systems frequently lead to changes in both the enthalpy (heat) and entropy of the process that compensate each other, so that the Gibbs free energy is little changed: a major barrier to the development of lead compounds in drug discovery. The conventional explanation for such enthalpy-entropy compensation (EEC) is that tighter contacts lead to a more negative enthalpy but increased molecular constraints, i.e., a compensating conformational entropy reduction. Changes in solvation can also contribute to EEC but this contribution is infrequently discussed. We review long-established and recent cases of EEC and conclude that the large fluctuations in enthalpy and entropy observed are too great to be a result of only conformational changes and must result, to a considerable degree, from variations in the amounts of water immobilized or released on forming complexes. Two systems exhibiting EEC show a correlation between calorimetric entropies and local mobilities, interpreted to mean conformational control of the binding entropy/free energy. However, a substantial contribution from solvation gives the same effect, as a consequence of a structural link between the amount of bound water and the protein flexibility. Only by assuming substantial changes in solvation-an intrinsically compensatory process-can a more complete understanding of EEC be obtained. Faced with such large, and compensating, changes in the enthalpies and entropies of binding, the best approach to engineering elevated affinities must be through the addition of ionic links, as they generate increased entropy without affecting the enthalpy.

  17. Self-Sensing Control of Nafion-Based Ionic Polymer-Metal Composite (IPMC Actuator in the Extremely Low Humidity Environment

    Directory of Open Access Journals (Sweden)

    Minoru Sasaki

    2013-10-01

    Full Text Available This paper presents feedforward, feedback and two-degree-of-freedom control applied to an Ionic Polymer-Metal Composite (IPMC actuator. It presents a high potential for development of miniature robots and biomedical devices and artificial muscles. We have reported in the last few years that dehydration treatment improves the electrical controllability of bending in Selemion CMV-based IPMCs. We tried to replicate this controllability in Nafion-based IPMC. We found that the displacement of a Nafion-based IPMC was proportional to the total charge imposed, just as in the Selemion-CMV case. This property is the basis of self-sensing controllers for Nafion-based IPMC bending behavior: we perform bending curvature experiments on Nafion-based IPMCs, obtaining the actuator's dynamics and transfer function. From these, we implemented self-sensing controllers using feedforward, feedback and two-degree-of-freedom techniques. All three controllers performed very well with the Nafion-based IPMC actuator.

  18. Active Tube-Shaped Actuator with Embedded Square Rod-Shaped Ionic Polymer-Metal Composites for Robotic-Assisted Manipulation

    Directory of Open Access Journals (Sweden)

    Yanjie Wang

    2018-01-01

    Full Text Available This paper reports a new technique involving the design, fabrication, and characterization of an ionic polymer-metal composite- (IPMC- embedded active tube, which can achieve multidegree-of-freedom (MODF bending motions desirable in many applications, such as a manipulator and an active catheter. However, traditional strip-type IPMC actuators are limited in only being able to generate 1-dimensional bending motion. So, in this paper, we try to develop an approach which involves molding or integrating rod-shaped IPMC actuators into a soft silicone rubber structure to create an active tube. We modified the Nafion solution casting method and developed a complete sequence of a fabrication process for rod-shaped IPMCs with square cross sections and four insulated electrodes on the surface. The silicone gel was cured at a suitable temperature to form a flexible tube using molds fabricated by 3D printing technology. By applying differential voltages to the four electrodes of each IPMC rod-shaped actuator, MDOF bending motions of the active tube can be generated. Experimental results show that such IPMC-embedded tube designs can be used for developing robotic-assisted manipulation.

  19. A self-strain feedback tuning-fork-shaped ionic polymer metal composite clamping actuator with soft matter elasticity-detecting capability for biomedical applications.

    Science.gov (United States)

    Feng, Guo-Hua; Huang, Wei-Lun

    2014-12-01

    This paper presents a smart tuning-fork-shaped ionic polymer metal composite (IPMC) clamping actuator for biomedical applications. The two fingers of the actuator, which perform the clamping motion, can be electrically controlled through a unique electrode design on the IPMC material. The generated displacement or strain of the fingers can be sensed using an integrated soft strain-gage sensor. The IPMC actuator and associated soft strain gage were fabricated using a micromachining technique. A 13.5×4×2 mm(3) actuator was shaped from Nafion solution and a selectively grown metal electrode formed the active region. The strain gage consisted of patterned copper foil and polyethylene as a substrate. The relationship between the strain gage voltage output and the displacement at the front end of the actuator's fingers was characterized. The equivalent Young's modulus, 13.65 MPa, of the soft-strain-gage-integrated IPMC finger was analyzed. The produced clamping force exhibited a linear increasing rate of 1.07 mN/s, based on a dc driving voltage of 7 V. Using the developed actuator to clamp soft matter and simultaneously acquire its Young's modulus was achieved. This demonstrated the feasibility of the palpation function and the potential use of the actuator in minimally invasive surgery. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. Investigation on the Mechanical and Electrical Behavior of a Tuning Fork-Shaped Ionic Polymer Metal Composite Actuator with a Continuous Water Supply Mechanism.

    Science.gov (United States)

    Feng, Guo-Hua; Huang, Wei-Lun

    2016-03-25

    This paper presents an innovative tuning fork-shaped ionic polymer metal composite (IPMC) actuator. With an integrated soft strain gauge and water supply mechanism (WSM), the surface strain of the actuator can be sensed in situ, and providing a continuous water supply maintains the water content inside the IPMC for long-term operation in air. The actuator was fabricated using a micromachining technique and plated with a nickel electrode. The device performance was experimentally characterized and compared with an actuator without a WSM. A large displacement of 1.5 mm was achieved for a 6 mm-long prong with 7-V dc actuation applied for 30 s. The measured current was analyzed using an electrochemical model. The results revealed that the faradaic current plays a crucial role during operation, particularly after 10 s. The measured strain confirms both the bending and axial strain generation during the open-and-close motion of the actuator prongs. Most of the water loss during device operation was due to evaporation rather than hydrolysis. The constructed WSM effectively maintained the water content inside the IPMC for long-term continuous operation.

  1. Active Tube-Shaped Actuator with Embedded Square Rod-Shaped Ionic Polymer-Metal Composites for Robotic-Assisted Manipulation

    Science.gov (United States)

    Liu, Jiayu; Zhu, Denglin; Chen, Hualing

    2018-01-01

    This paper reports a new technique involving the design, fabrication, and characterization of an ionic polymer-metal composite- (IPMC-) embedded active tube, which can achieve multidegree-of-freedom (MODF) bending motions desirable in many applications, such as a manipulator and an active catheter. However, traditional strip-type IPMC actuators are limited in only being able to generate 1-dimensional bending motion. So, in this paper, we try to develop an approach which involves molding or integrating rod-shaped IPMC actuators into a soft silicone rubber structure to create an active tube. We modified the Nafion solution casting method and developed a complete sequence of a fabrication process for rod-shaped IPMCs with square cross sections and four insulated electrodes on the surface. The silicone gel was cured at a suitable temperature to form a flexible tube using molds fabricated by 3D printing technology. By applying differential voltages to the four electrodes of each IPMC rod-shaped actuator, MDOF bending motions of the active tube can be generated. Experimental results show that such IPMC-embedded tube designs can be used for developing robotic-assisted manipulation. PMID:29770160

  2. Effect of unsaturation on the absorption of ethane and ethylene in imidazolium-based ionic liquids.

    Science.gov (United States)

    Moura, Leila; Mishra, Manas; Bernales, Varinia; Fuentealba, Patricio; Padua, Agilio A H; Santini, Catherine C; Costa Gomes, Margarida F

    2013-06-20

    The influence of the presence of imidazolium side chain unsaturation on the solubility of ethane and ethylene was studied in three ionic liquids: 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide-saturated alkyl side-chain in the cation; 1-methyl-3-(buten-3-yl)imidazolium bis(trifluorosulfonyl)imide-double bond in the side-chain of the cation; and 1-methyl-3-benzylimidazolium bis(trifluorosulfonyl)imide-benzyl group in the side-chain of the cation. The solubility of both gases decreases when the side-chain of the cations is functionalized with an unsaturated group. This can be explained by a less favorable enthalpy of solvation. The difference of solubility between ethane and ethylene can be explained from a balance of enthalpic and entropic factors: for the ionic liquid with the saturated alkyl side-chain and the benzyl-substituted side-chain, it is the favorable entropy of solvation that explains the larger ethylene solubility, whereas in the case of the saturated side-chain, it is the more favorable enthalpy of solvation. Molecular simulation allowed the identification of the mechanisms of solvation and the preferential solvation sites for each gas in the different ionic liquids. Simulations have shown that the entropy of solvation is more favorable when the presence of the gas weakens the cation-anion interactions or when the gas can be solvated near different sites of the ionic liquid.

  3. Effect of Zirconium Oxide Nanofiller and Dibutyl Phthalate Plasticizer on Ionic Conductivity and Optical Properties of Solid Polymer Electrolyte

    Science.gov (United States)

    Yasin, Siti Mariah Mohd; Ibrahim, Suriani

    2014-01-01

    New solid polymer electrolytes (SPE) based on poly(ethylene oxide) (PEO) doped with lithium trifluoromethanesulfonate (LiCF3SO3), dibutyl phthalate (DBP) plasticizer, and zirconium oxide (ZrO2) nanoparticles were prepared by solution-casting technique. The conductivity was enhanced by addition of dibutyl phthalate (DBP) plasticizer and ZrO2 nanofiller with maximum conductivity (1.38 × 10−4 Scm−1). The absorption edge and band gap values showed decreases upon addition of LiSO3CF3, DBP, and ZrO2 due to the formation of localized states in the SPE and the degree of disorder in the films increased. PMID:25133244

  4. Effect of Zirconium Oxide Nanofiller and Dibutyl Phthalate Plasticizer on Ionic Conductivity and Optical Properties of Solid Polymer Electrolyte

    Directory of Open Access Journals (Sweden)

    Siti Mariah Mohd Yasin

    2014-01-01

    Full Text Available New solid polymer electrolytes (SPE based on poly(ethylene oxide (PEO doped with lithium trifluoromethanesulfonate (LiCF3SO3, dibutyl phthalate (DBP plasticizer, and zirconium oxide (ZrO2 nanoparticles were prepared by solution-casting technique. The conductivity was enhanced by addition of dibutyl phthalate (DBP plasticizer and ZrO2 nanofiller with maximum conductivity (1.38×10-4 Scm-1. The absorption edge and band gap values showed decreases upon addition of LiSO3CF3, DBP, and ZrO2 due to the formation of localized states in the SPE and the degree of disorder in the films increased.

  5. Ionic conductivity studies in crystalline PVA/NaAlg polymer blend electrolyte doped with alkali salt KCl

    Science.gov (United States)

    Sheela, T.; Bhajantri, R. F.; Ravindrachary, V.; Pujari, P. K.; Rathod, Sunil G.; Naik, Jagadish

    2014-04-01

    Potassium Chloride (KCl) doped poly(vinyl alcohol) (PVA)/sodium alginate (NaAlg) in 60:40 wt% polymer blend electrolytes were prepared by solution casting method. The complexation of KCl with host PVA/NaAlg blend is confirmed by FTIR and UV-Vis spectra. The XRD studies show that the crystallinity of the prepared blends increases with increase in doping. The dc conductivity increases with increase in dopant concentration. Temperature dependent dc conductivity shows an Arrhenius behavior. The dielectric properties show that both the dielectric constant and dielectric loss increases with increase in KCl doping concentration and decreases with frequency. The cole-cole plots show a decrease in bulk resistance, indicates the increase in ac conductivity, due to increase in charge carrier mobility. The doping of KCl enhances the mechanical properties of PVA/NaAlg, such as Young's modulus, tensile strength, stiffness.

  6. Desorption of Lipases Immobilized on Octyl-Agarose Beads and Coated with Ionic Polymers after Thermal Inactivation. Stronger Adsorption of Polymers/Unfolded Protein Composites

    Directory of Open Access Journals (Sweden)

    Jose J. Virgen-Ortíz

    2017-01-01

    Full Text Available Lipases from Candida antarctica (isoform B and Rhizomucor miehei (CALB and RML have been immobilized on octyl-agarose (OC and further coated with polyethylenimine (PEI and dextran sulfate (DS. The enzymes just immobilized on OC supports could be easily released from the support using 2% SDS at pH 7, both intact or after thermal inactivation (in fact, after inactivation most enzyme molecules were already desorbed. The coating with PEI and DS greatly reduced the enzyme release during thermal inactivation and improved enzyme stability. However, using OC-CALB/RML-PEI-DS, the full release of the immobilized enzyme to reuse the support required more drastic conditions: a pH value of 3, a buffer concentration over 2 M, and temperatures above 45 °C. However, even these conditions were not able to fully release the thermally inactivated enzyme molecules from the support, being necessary to increase the buffer concentration to 4 M sodium phosphate and decrease the pH to 2.5. The formation of unfolded protein/polymers composites seems to be responsible for this strong interaction between the octyl and some anionic groups of OC supports. The support could be reused five cycles using these conditions with similar loading capacity of the support and stability of the immobilized enzyme.

  7. Tensiometric investigation of the interaction and phase separation in a polymer mixture–ionic surfactant ternary system

    Directory of Open Access Journals (Sweden)

    JAROSLAV M. KATONA

    2010-06-01

    Full Text Available The interaction and phase separation in a ternary mixture composed of hydroxypropyl methyl cellulose (HPMC, sodium carboxymethyl cellulose (NaCMC, and sodium dodecylsulfate (SDS were investigated by tensiometry. Surface tension measurements of binary mixtures (0.7 % HPMC and 0.00–2.00 % SDS and of ternary mixtures (0.7 % HPMC, 0.3 % NaCMC, and 0.00–2.00 % SDS were performed. The measurements indicated interaction between HPMC and SDS, which resulted in HPMC–SDS complex formation. The critical association concentration, CAC, and polymer saturation point, PSP, were determined. Phase separation of ternary HPMC/SDS/NaCMC mixtures occurs at SDS concentration > CAC, i.e., when the HPMC–SDS complex is formed. The volume of the coacervate increases with increasing SDS concentration, and at SDS concentrations > 1.00 %, the coacervate vanishes. The surface tensions (s of ternary HPMC/SDS/NaCMC mixtures in the pre-coacervation region and at the onset of the coacervation region are similar to the σ of the corresponding binary HPMC–SDS mixtures, while in the coacervation and post coacervation region, they are close to the s of the corresponding SDS solutions

  8. Thermodynamics of ionic processes in solutions

    International Nuclear Information System (INIS)

    Krestov, G.A.

    1984-01-01

    The present nitions about the mechanism of solvation of atomic-molecular particles and the structure of electrolyte and non electrolyte solutions are given. From common positions a wide range of interrelated problems (general and thermodynamic characteristic of ions, thermodynamic characteristic of ion solvation and various ionic reactions in solutions, structural changes of the solvent in the above processes etc...) is considered. The latest scientific data including those on the effect on the thermodynamio properties of low temperatures, various impurities (air, water), large ions, peculiarities of the structure of solvent molecules reflected. Considerable attention is given to new conceptions definitions, structural notions as well as theoretical and experimental methods of obtaining quantitative characteristics of ion solvation

  9. Lignin Structure and Aggregation Behavior in a Two-Component Ionic Liquid Solvent System

    Directory of Open Access Journals (Sweden)

    Susanne Bylin

    2014-08-01

    Full Text Available Ionic liquids are of potential interest in the processing of lignocellulosic biomass. In this study, the ionic liquid co-solvent system of 1-methylimidazole (MIM and 1-ethyl-3-methyl-imidazolium acetate (EMIMAc was used to solvate LignoBoost lignin fractionated from black liquor obtained from a kraft paper mill. Lignin ethanol-precipitated (LEP and ethanol-soluble (LES fractions were characterized via gel permeation chromatography (GPC and 13C- and 31P-nuclear magnetic resonance spectroscopy (NMR to determine structural characteristics and their relationship to polymer solubility in the system. Polymer integrity and solubility were optimal at ~20% lignin loading (w/w. Results showed that LEPs were generally of higher apparent molecular weight (Mw and enriched with condensed/aliphatic ether linkages and aliphatic hydroxyls. The LESs had a lower apparent Mw and were enriched with carboxylic and phenolic groups. This newly gained knowledge on lignin fractionation and aggregation in the present solvent system provides future opportunities for tuning fractionation/extraction to suit a specific biomass-derived product, e.g., carbon fibers.

  10. Role of Dispersive Fluorous Interaction in the Solvation Dynamics of the Perfluoro Group Containing Molecules.

    Science.gov (United States)

    Mondal, Saptarsi; Chaterjee, Soumit; Halder, Ritaban; Jana, Biman; Singh, Prashant Chandra

    2017-08-17

    Perfluoro group containing molecules possess an important self-aggregation property through the fluorous (F···F) interaction which makes them useful for diverse applications such as medicinal chemistry, separation techniques, polymer technology, and biology. In this article, we have investigated the solvation dynamics of coumarin-153 (C153) and coumarin-6H (C6H) in ethanol (ETH), 2-fluoroethanol (MFE), and 2,2,2-trifluoroethanol (TFE) using the femtosecond upconversion technique and molecular dynamics (MD) simulation to understand the role of fluorous interaction between the solute and solvent molecules in the solvation dynamics of perfluoro group containing molecules. The femtosecond upconversion data show that the time scales of solvation dynamics of C6H in ETH, MFE, and TFE are approximately the same whereas the solvation dynamics of C153 in TFE is slow as compared to that of ETH and MFE. It has also been observed that the time scale of solvation dynamics of C6H in ETH and MFE is higher than that of C153 in the same solvents. MD simulation results show a qualitative agreement with the experimental data in terms of the time scale of the slow components of the solvation for all the systems. The experimental and simulation studies combined lead to the conclusion that the solvation dynamics of C6H in all solvents as well as C153 in ETH and MFE is mostly governed by the charge distribution of ester moieties (C═O and O) of dye molecules whereas the solvation of C153 in TFE is predominantly due to the dispersive fluorous interaction (F···F) between the perfluoro groups of the C153 and solvent molecules.

  11. Understanding Lithium Solvation and Diffusion through Topological Analysis of First-Principles Molecular Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Bhatia, Harsh [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Gyulassy, Attila [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Ong, Mitchell [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Lordi, Vincenzo [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Draeger, Erik [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Pask, John [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Pascucci, Valerio [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Bremer, Peer -Timo [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2016-09-27

    The performance of lithium-ion batteries is strongly influenced by the ionic conductivity of the electrolyte, which depends on the speed at which Li ions migrate across the cell and relates to their solvation structure. The choice of solvent can greatly impact, both, the solvation and diffusivity of Li ions. In this work, we present our application of the topological techniques to extract and predict such behavior in the data generated by the first-principles molecular dynamics simulation of Li ions in an important organic solvent -ethylene carbonate. More specifically, we use the scalar topology of the electron charge density field to analyze the evolution of the solvation structures. This allows us to derive a parameter-free bond definition for lithium-oxygen bonds, to provide a quantitative measure for bond strength, and to understand the regions of influence of each atom in the simulation. This has provided new insights into how and under what conditions certain bonds may form and break. As a result, we can identify and, more importantly, predict, unstable configurations in solvation structures. This can be very useful in understanding when small changes to the atoms' movements can cause significantly different bond structures to evolve. Ultimately, this promises to allow scientists to explore lithium ion solvation and diffusion more systematically, with the aim of new insights and potentially accelerating the calculations themselves.

  12. Ionic Liquid-Based Optical and Electrochemical Carbon Dioxide Sensors

    OpenAIRE

    Kamalakanta Behera; Shubha Pandey; Anu Kadyan; Siddharth Pandey

    2015-01-01

    Due to their unusual physicochemical properties (e.g., high thermal stability, low volatility, high intrinsic conductivity, wide electrochemical windows and good solvating ability), ionic liquids have shown immense application potential in many research areas. Applications of ionic liquid in developing various sensors, especially for the sensing of biomolecules, such as nucleic acids, proteins and enzymes, gas sensing and sensing of various important ions, among other chemosensing platforms, ...

  13. Solid-state supercapacitors with ionic liquid gel polymer electrolyte based on poly (3, 4-ethylenedioxythiophene), carbon nanotubes, and metal oxides nanocomposites for electrical energy storage

    Science.gov (United States)

    Obeidat, Amr M.

    Clean and renewable energy systems have emerged as an important area of research having diverse and significant new applications. These systems utilize different energy storage methods such as the batteries and supercapacitors. Supercapacitors are electrochemical energy storage devices that are designed to bridge the gap between batteries and conventional capacitors. Supercapacitors which store electrical energy by electrical double layer capacitance are based on large surface area structured carbons. The materials systems in which the Faradaic reversible redox reactions store electrical energy are the transition metal oxides and electronically conducting polymers. Among the different types of conducting polymers, poly (3, 4- ethylenedioxythiophene) (PEDOT) is extensively investigated owing to its chemical and mechanical stability. Due to instability of aqueous electrolytes at high voltages and toxicity of organic electrolytes, potential of supercapacitors has not been fully exploited. A novel aspect of this work is in utilizing the ionic liquid gel polymer electrolyte to design solid-state supercapacitors for energy storage. Various electrochemical systems were investigated including graphene, PEDOT, PEDOT-carbon nanotubes, PEDOT-manganese oxide, and PEDOT-iron oxide nanocomposites. The electrochemical performance of solid-state supercapacitor devices was evaluated based on cyclic voltammetry (CV), charge-discharge (CD), prolonged cyclic tests, and electrochemical impedance spectroscopy (EIS) techniques. Raman spectroscopy technique was also utilized to analyze the bonding structure of the electrode materials. The graphene solid-state supercapacitor system displayed areal capacitance density of 141.83 mF cm-2 based on high potential window up to 4V. The PEDOT solid-state supercapacitor system was synthesized in acetonitrile and aqueous mediums achieving areal capacitance density of 219.17 mF cm-2. The hybrid structure of solid-state supercapacitors was also

  14. Ion Transport and Structure in Polymer Electrolytes with Applications in Lithium Batteries

    Science.gov (United States)

    Chintapalli, Mahati

    When mixed with lithium salts, polymers that contain more than one chemical group, such as block copolymers and endgroup-functionalized polymers, are promising electrolyte materials for next-generation lithium batteries. One chemical group can provide good ion solvation and transport properties, while the other chemical group can provide secondary properties that improve the performance characteristics of the battery. Secondary properties of interest include non-flammability for safer lithium ion batteries and high mechanical modulus for dendrite resistance in high energy density lithium metal batteries. Block copolymers and other materials with multiple chemical groups tend to exhibit nanoscale heterogeneity and can undergo microphase separation, which impacts the ion transport properties. In block copolymers that microphase separate, ordered self-assembled structures occur on longer length scales. Understanding the interplay between structure at different length scales, salt concentration, and ion transport is important for improving the performance of multifunctional polymer electrolytes. In this dissertation, two electrolyte materials are characterized: mixtures of endgroup-functionalized, short chain perfluoropolyethers (PFPEs) and lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) salt, and mixtures of polystyrene-block-poly(ethylene oxide) (PS- b-PEO; SEO) and LiTFSI. The PFPE/LiTFSI electrolytes are liquids in which the PFPE backbone provides non-flammability, and the endgroups resemble small molecules that solvate ions. In these electrolytes, the ion transport properties and nanoscale heterogeneity (length scale 1 nm) are characterized as a function of endgroup using electrochemical techniques, nuclear magnetic resonance spectroscopy, and wide angle X-ray scattering. Endgroups, especially those containing PEO segments, have a large impact on ionic conductivity, in part because the salt distribution is not homogenous; we find that salt partitions

  15. Picosecond radiolysis of ionic liquids

    International Nuclear Information System (INIS)

    Funston, A.M.; Wishart, J.F.; Neta, P.; Lall, S.I.; Engel, R.

    2003-01-01

    Ionic liquids (ILs) are a rapidly expanding family of condensed-phase media with important applications in nuclear fuel and waste processing, energy production, improving the efficiency and safety of industrial chemical processes, and pollution prevention. Ionic liquids are completely nonvolatile, noncombustible, highly conductive, recyclable and capable of dissolving a wide variety of materials. An understanding of the radiation chemistry of ionic liquids is important for development of their applications in radioactive material processing and for the application of pulse radiolysis techniques to the general study of chemical reactivity in ionic liquids. Kinetic studies with a picosecond electron accelerator, such as the BNL Laser-Electron Accelerator Facility (LEAF), allow one to observe primary radiation products and their reactions on short time scales. For example, the solvated electron lifetime in neat methyltributylammonium bis(trifluoromethylsulfonyl)imide is ∼300 ns and its absorption maximum is ∼1400 nm. Kinetic studies of primary radiolytic products and their reactivities will be described for several types of ionic liquids. Supported in part by the U.S. Department of Energy, Division of Chemical Sciences, Office of Basic Energy Sciences, under contract DE-AC02-98-CH1088

  16. Synthesis and characterization of ion containing polymers

    Science.gov (United States)

    Dou, Shichen

    Two types of ion-containing polymers are included in this dissertation. The first was focused on the rheology, solvation, and correlation length of polyelectrolyte solutions in terms of charge density, solvent dielectric constant, and solvent quality. The second was focused on the PEO-based polyester ionomers as single ion conductors. A series of polyelectrolytes with varied charge density (0.03 residual salt significantly reduces the viscosity of polyelectrolyte solutions at concentrations c salt, with low residual salt, and with high residual salt concentration. PEO-based polyester ionomers were synthesized by melt polycondensation. Mn was determined using the 1H NMR of ionomers. No ion-cluster was observed from the DSC, SAXS, and rheology measurements. Ionic conductivity greatly depends on the Tg, T-T g and ion content of the ionomers. PEG600-PTMO650 (z)-Li copolyester ionomers show microphase separation and much lower ionic conductivity, compared to that of PE600-Li. PTMO650-Li shows nonconductor behavior.

  17. Ionic Liquid Epoxy Resin Monomers

    Science.gov (United States)

    Paley, Mark S. (Inventor)

    2013-01-01

    Ionic liquid epoxide monomers capable of reacting with cross-linking agents to form polymers with high tensile and adhesive strengths. Ionic liquid epoxide monomers comprising at least one bis(glycidyl) N-substituted nitrogen heterocyclic cation are made from nitrogen heterocycles corresponding to the bis(glycidyl) N-substituted nitrogen heterocyclic cations by a method involving a non-nucleophilic anion, an alkali metal cation, epichlorohydrin, and a strong base.

  18. Updated Abraham solvation parameters for polychlorinated biphenyls

    NARCIS (Netherlands)

    van Noort, P.C.M.; Haftka, J.J.H.; Parsons, J.R.

    2010-01-01

    This study shows that the recently published polychlorinated biphenyl (PCB) Abraham solvation parameters predict PCB air−n-hexadecane and n-octanol−water partition coefficients very poorly, especially for highly ortho-chlorinated congeners. Therefore, an updated set of PCB solvation parameters was

  19. Updated Abraham solvation parameters for polychlorinated biphenyls

    NARCIS (Netherlands)

    Noort, van P.C.M.; Haftka, J.J.H.; Parsons, J.R.

    2010-01-01

    This study shows that the recently published polychlorinated biphenyl (PCB) Abraham solvation parameters predict PCB air-n-hexadecane and n-octanol-water partition coefficients very poorly, especially for highly ortho-chlorinated congeners. Therefore, an updated set of PCB solvation parameters was

  20. Removal of 2,4-dichlorophenol using cyclodextrin-ionic liquid polymer as a macroporous material: Characterization, adsorption isotherm, kinetic study, thermodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Raoov, Muggundha [University of Malaya Centre for Ionic Liquids, Department of Chemistry, Faculty of Science, University of Malaya, Kuala Lumpur 50603 (Malaysia); Department of Chemistry, Faculty of Science, University of Malaya, Kuala Lumpur 50603 (Malaysia); Advanced Medical and Dental Institute, University of Science Malaysia, No. 1–8 (Lot 8), Persiaran Seksyen 4/1, Bandar Putra Bertam, Kepala Batas, Pulau Pinang 13200 (Malaysia); Mohamad, Sharifah, E-mail: sharifahm@um.edu.my [University of Malaya Centre for Ionic Liquids, Department of Chemistry, Faculty of Science, University of Malaya, Kuala Lumpur 50603 (Malaysia); Department of Chemistry, Faculty of Science, University of Malaya, Kuala Lumpur 50603 (Malaysia); Abas, Mohd Radzi [Department of Chemistry, Faculty of Science, University of Malaya, Kuala Lumpur 50603 (Malaysia)

    2013-12-15

    Highlights: • βCD-BIMOTs-TDI exhibits macropore size (77.66 nm) with 1.254 m{sup 2} g{sup −1} surface area. • Freundlich isotherm and pseudo-second order kinetics fit well the adsorption process. • Removal was optimum at pH 6 with 83% and reached equilibrium at 80 mg L{sup −1}. • Entropy (ΔS°) and heat of adsorption (ΔH°) estimated as −55.99 J/K mol and −18.10 J/mol. • Inclusion complex and π–π interaction were found to be dominant at pH 6. -- Abstract: Cyclodextrin-ionic liquid polymer (βCD-BIMOTs-TDI) was firstly synthesized using functionalized β-Cyclodextrin (CD) with 1-benzylimidazole (BIM) to form monofunctionalized CD (βCD-BIMOTs) and was further polymerized using toluene diisocyanate (TDI) linker to form insoluble βCD-BIMOTs-TDI. SEM characterization result shows that βCD-BIMOTs-TDI exhibits macropore size while the BET result shows low surface area (1.254 m{sup 2} g{sup −1}). The unique properties of the ILs allow us to produce materials with different morphologies. The adsorption isotherm and kinetics of 2,4-dichlorophenol (2,4-DCP) onto βCD-BIMOTs-TDI is studied. Freundlich isotherm and pseudo-second order kinetics are found to be the best to represent the data for 2,4-DCP adsorption on the βCD-BIMOTs-TDI. The presence of macropores decreases the mass transfer resistance and increases the adsorption process by reducing the diffusion distance. The change in entropy (ΔS°) and heat of adsorption (ΔH°) for 2,4-DCP on βCD-BIMOTs-TDI were estimated as −55.99 J/Kmol and −18.10 J/mol, respectively. The negative value of Gibbs free energy (ΔG°) indicates that the adsorption process is thermodynamically feasible, spontaneous and chemically controlled. Finally, the interactions between the cavity of βCD-BIMOTs and 2,4-DCP are investigated and the results shows that the inclusion of the complex formation and π–π interaction are the main processes involved in the adsorption process.

  1. Gel polymer electrolytes for batteries

    Science.gov (United States)

    Balsara, Nitash Pervez; Eitouni, Hany Basam; Gur, Ilan; Singh, Mohit; Hudson, William

    2014-11-18

    Nanostructured gel polymer electrolytes that have both high ionic conductivity and high mechanical strength are disclosed. The electrolytes have at least two domains--one domain contains an ionically-conductive gel polymer and the other domain contains a rigid polymer that provides structure for the electrolyte. The domains are formed by block copolymers. The first block provides a polymer matrix that may or may not be conductive on by itself, but that can soak up a liquid electrolyte, thereby making a gel. An exemplary nanostructured gel polymer electrolyte has an ionic conductivity of at least 1.times.10.sup.-4 S cm.sup.-1 at 25.degree. C.

  2. Ionic conducting poly-benzimidazoles

    International Nuclear Information System (INIS)

    Jouanneau, J.

    2006-11-01

    Over the last years, many research works have been focused on new clean energy systems. Hydrogen fuel cell seems to be the most promising one. However, the large scale development of this technology is still limited by some key elements. One of them is the polymer electrolyte membrane 'Nafion' currently used, for which the ratio performance/cost is too low. The investigations we carried out during this thesis work are related to a new class of ionic conducting polymer, the sulfonated poly-benzimidazoles (sPBI). Poly-benzimidazoles (PBI) are aromatic heterocyclic polymers well-known for their excellent thermal and chemical stability. Ionic conduction properties are obtained by having strong acid groups (sulfonic acid SO 3 H) on the macromolecular structure. For that purpose, we first synthesized sulfonated monomers. Their poly-condensation with an appropriate non-sulfonated co-monomer yields to sPBI with sulfonation range from 0 to 100 per cent. Three different sPBI structures were obtained, and verified by appropriate analytical techniques. We also showed that the protocol used for the synthesis resulted in high molecular weights polymers. We prepared ionic conducting membrane by casting sPBI solutions on glass plates. Their properties of stability, water swelling and ionic conductivity were investigated. Surprisingly, the behaviour of sPBI was quite different from the other sulfonated aromatic polymers with same amount of SO 3 H, their stability was much higher, but their water swelling and ionic conductivity were quite low. We attributed these differences to strong ionic interactions between the sulfonic acid groups and the basic benzimidazole groups of our polymers. However, we managed to solve this problem synthesizing very highly sulfonated PBI, obtaining membranes with a good balance between all the properties necessary. (author)

  3. Solvates of silico-12-molybdic acid with alcohols

    International Nuclear Information System (INIS)

    Punchuk, I.N.; Chuvaev, V.F.

    1984-01-01

    With the aim of investigating interaction processes of solid heteropolyacids and organic compounds, solvates are prepared. Solvates are products of adding gaseous methanol, ethanol and isopropanol to silico-12-molybdic acid. The compounds are studied by IR and PMR spectroscopy methods. Possible models for solvate structure are considered, as well as their connection with solvate properties and thermal decomposition

  4. Comparative Investigation of the Ionicity of Aprotic and Protic Ionic Liquids in Molecular Solvents by using Conductometry and NMR Spectroscopy.

    Science.gov (United States)

    Thawarkar, Sachin; Khupse, Nageshwar D; Kumar, Anil

    2016-04-04

    Electrical conductivity (σ), viscosity (η), and self-diffusion coefficient (D) measurements of binary mixtures of aprotic and protic imidazolium-based ionic liquids with water, dimethyl sulfoxide, and ethylene glycol were measured from 293.15 to 323.15 K. The temperature dependence study reveals typical Arrhenius behavior. The ionicities of aprotic ionic liquids were observed to be higher than those of protic ionic liquids in these solvents. The aprotic ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate, [bmIm][BF4 ], displays 100 % ionicity in both water and ethylene glycol. The protic ionic liquids in both water and ethylene glycol are classed as good ionic candidates, whereas in DMSO they are classed as having a poor ionic nature. The solvation dynamics of the ionic species of the ionic liquids are illustrated on the basis of the (1) H NMR chemical shifts of the ionic liquids. The self-diffusion coefficients D of the cation and anion of [HmIm][CH3 COO] in D2 O and in [D6 ]DMSO are determined by using (1) H nuclei with pulsed field gradient spin-echo NMR spectroscopy. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Learning Ionic

    CERN Document Server

    Ravulavaru, Arvind

    2015-01-01

    This book is intended for those who want to learn how to build hybrid mobile applications using Ionic. It is also ideal for people who want to explore theming for Ionic apps. Prior knowledge of AngularJS is essential to complete this book successfully.

  6. Electrode-Impregnable and Cross-Linkable Poly(ethylene oxide)-Poly(propylene oxide)-Poly(ethylene oxide) Triblock Polymer Electrolytes with High Ionic Conductivity and a Large Voltage Window for Flexible Solid-State Supercapacitors.

    Science.gov (United States)

    Han, Jae Hee; Lee, Jang Yong; Suh, Dong Hack; Hong, Young Taik; Kim, Tae-Ho

    2017-10-04

    We present cross-linkable precursor-type gel polymer electrolytes (GPEs) that have large ionic liquid uptake capability, can easily penetrate electrodes, have high ion conductivity, and are mechanically strong as high-performance, flexible all-solid-state supercapacitors (SC). Our polymer precursors feature a hydrophilic-hydrophobic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock main-chain structure and trifunctional silane end groups that can be multi-cross-linked with each other through a sol-gel process. The cross-linked solid-state electrolyte film with moderate IL content (200 wt %) shows a well-balanced combination of excellent ionic conductivity (5.0 × 10 -3 S cm -1 ) and good mechanical stability (maximum strain = 194%). Moreover, our polymer electrolytes have various advantages including high thermal stability (decomposition temperature > 330 °C) and the capability to impregnate electrodes to form an excellent electrode-electrolyte interface due to the very low viscosity of the precursors. By assembling our GPE-impregnated electrodes and solid-state GPE film, we demonstrate an all-solid-state SC that can operate at 3 V and provides an improved specific capacitance (112.3 F g -1 at 0.1 A g -1 ), better rate capability (64% capacity retention until 20 A g -1 ), and excellent cycle stability (95% capacitance decay over 10 000 charge/discharge cycles) compared with those of a reference SC using a conventional PEO electrolyte. Finally, flexible SCs with a high energy density (22.6 W h kg -1 at 1 A g -1 ) and an excellent flexibility (>93% capacitance retention after 5000 bending cycles) can successfully be obtained.

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

    Energy Technology Data Exchange (ETDEWEB)

    Rajput, Nav Nidhi; Murugesan, Vijayakumar; Shin, Yongwoo; Han, Kee Sung; Lau, Kah Chun; Chen, Junzheng; Liu, Jun; Curtiss, Larry A.; Mueller, Karl T.; Persson, Kristin A.

    2017-04-10

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

  8. 1 SUPPLEMENTARY INFORMATION Nonpolar Solvation Dynamics ...

    Indian Academy of Sciences (India)

    IITP

    . S. NP. ( t. ) ( )t. SNeqm. NP. (a). (b). Figure S2. (a) Nonequilibrium solvation response functions calculated after averaging over different number of nonequilibrium trajectories. The response function converges after averaging over more than ...

  9. Solvated electron structure in glassy matrices

    International Nuclear Information System (INIS)

    Kevan, L.

    1981-01-01

    Current knowledge of the detailed geometrical structure of solvated electrons in aqueous and organic media is summarized. The geometry of solvated electrons in glassy methanol, ethanol, and 2-methyltetrahydrofuran is discussed. Advanced electron magnetic resonance methods and development of new methods of analysis of electron spin echo modulation patterns, second moment line shapes, and forbidden photon spin-flip transitions for paramagnetic species in these disordered systems are discussed. 66 references are cited

  10. Synthesis, Characterization, and Impregnation of Some Ionic Liquids on Polymer Membrane for Separation of Carbon Dioxide from Its Mixture with Methane

    Directory of Open Access Journals (Sweden)

    T. T. L. Bui

    2018-03-01

    Full Text Available Some 1-alkyl-3-methylimidazolium-based ionic liquids were synthesized, characterized, and immobilized on membranes to form supported ionic liquid membranes. The supported ionic liquid membranes were characterized by SEM. The initial transmembrane pressures were investigated for each type of impregnated membrane. The CO2/CH4 single gas and mixed gas permeability (CO2 and CH4 have been investigated. The results showed that the CO2/CH4 ideal selectivities and mixed gas selectivities reached 15.45 – 23.9 and 13.91 – 22.82, respectively (equivalent to separation yields of 93.3 – 95.98 %.mThe 1-alkyl-3-methylimidazolium acetate impregnated membrane leads to a slightly lowermCO2/CH4 selectivity, however, this ionic liquid is stable, free of halogen and has a low price. The impregnated membranes prepared from polyvinylidene fluoride are more stablemthan those from polyethersulfone support, and have a higher affinity for CO2 compared to other gas. The obtained high CO2/CH4 selectivities indicate that immobilized membranes can be used for CO2 separation processes.

  11. Variation of the solvation number of Eu(III) in mixed system of methanol and water

    International Nuclear Information System (INIS)

    Suganuma, H.; Arisaka, M.; Omori, T.; Satoh, I.; Choppin, G.R.

    1999-01-01

    The stability constants (β 1 ) of the monofluoride complex of Eu(III) have been determined in mixed solvents of methanol and water at a 0.10 M ionic strength using a solvent extraction technique. The values of ln β 1 increase as the mole fraction of methanol in the mixed solvent system increases. The variation in the stability constants can be correlated with both the large effect due to the solvation of F and the small effect due to both (1) the solvation of cations in connection with complexation and (2) the electrostatic attraction between Eu 3+ and F - . Based on the variation in the sum of (1) and (2) in water and the mixed solvent solutions, it was determined that the coordination number (CN) of Eu(III) varied from a mixture of CN = 9 and 8 to CN = 8 at about a 0.03 mole fraction of methanol in the mixed solvent. (orig.)

  12. Polypyrrole for Artificial Muscles: Ionic Mechanisms

    DEFF Research Database (Denmark)

    Skaarup, Steen

    2006-01-01

    the matrix of a polymer electrode – thereby causing volume expansion which can be converted into work. Solvent molecules are able to penetrate the polymer too. A precise description of the nature of these ionic and solvent movements is therefore important for understanding and improving the performance....... This work examines the influence of solvent, ionic species and electrolyte concentration on the fundamental question about the ionic mechanism involved: Is the actuation process driven by anion motion, cation motion, or a mixture of the two? In addition: What is the extent of solvent motion? The discussion...... is centered on polypyrrole (PPy), which is the material most used and studied. The tetraethyl ammonium cation (TEA) is shown to be able to move in and out of PPy(DBS) polymer films, in contrast to expectations. There is a switching between ionic mechanisms during cycling in TEACl electrolyte....

  13. Solvation-based vapour pressure model for (solvent + salt) systems in conjunction with the Antoine equation

    International Nuclear Information System (INIS)

    Senol, Aynur

    2013-01-01

    Highlights: • Vapour pressures of (solvent + salt) systems have been estimated through a solvation-based model. • Two structural forms of the generalized solvation model using the Antoine equation have been performed. • A simplified concentration-dependent vapour pressure model has been also processed. • The model reliability analysis has been performed in terms of a log-ratio objective function. • The reliability of the models has been interpreted in terms of the statistical design factors. -- Abstract: This study deals with modelling the vapour pressure of a (solvent + salt) system on the basis of the principles of LSER. The solvation model framework clarifies the simultaneous impact of several physical variables such as the vapour pressure of a pure solvent estimated by the Antoine equation, the solubility and solvatochromic parameters of the solvent and the physical properties of the ionic salt. It has been analyzed independently the performance of two structural forms of the generalized model, i.e., a relation depending on an integration of the properties of the solvent and the ionic salt and a relation on a reduced property-basis. A simplified concentration-dependent vapour pressure model has been also explored and implemented on the relevant systems. The vapour pressure data of sixteen (solvent + salt) systems have been processed to analyze statistically the reliability of existing models in terms of a log–ratio objective function. The proposed vapour pressure models match relatively well the observed performance, yielding the overall design factors of 1.066 and 1.073 for the solvation-based models with the integrated and reduced properties, and 1.008 for the concentration-based model, respectively

  14. Understanding SO2 Capture by Ionic Liquids.

    Science.gov (United States)

    Mondal, Anirban; Balasubramanian, Sundaram

    2016-05-19

    Ionic liquids have generated interest for efficient SO2 absorption due to their low vapor pressure and versatility. In this work, a systematic investigation of the structure, thermodynamics, and dynamics of SO2 absorption by ionic liquids has been carried out through quantum chemical calculations and molecular dynamics (MD) simulations. MP2 level calculations of several ion pairs complexed with SO2 reveal its preferential interaction with the anion. Results of condensed phase MD simulations of SO2-IL mixtures manifested the essential role of both cations and anions in the solvation of SO2, where the solute is surrounded by the "cage" formed by the cations (primarily its alkyl tail) through dispersion interactions. These structural effects of gas absorption are substantiated by calculated Gibbs free energy of solvation; the dissolution is demonstrated to be enthalpy driven. The entropic loss of SO2 absorption in ionic liquids with a larger anion such as [NTf2](-) has been quantified and has been attributed to the conformational restriction of the anion imposed by its interaction with SO2. SO2 loading IL decreases its shear viscosity and enhances the electrical conductivity. This systematic study provides a molecular level understanding which can aid the design of task-specific ILs as electrolytes for efficient SO2 absorption.

  15. A novel polymer of Al2(SO43-poly(acrylamide-co-2-acrylamido-2-methyl-1-propanesulfonate ionic hybrid prepared by dispersion polymerization

    Directory of Open Access Journals (Sweden)

    2010-03-01

    Full Text Available A novel polymer Al2(SO43-poly(acrylamide-co-2-acrylamido-2-methyl-1-propanesulfonate (Al2(SO43-P(AM/AMPS had been synthesized by dispersion polymerization in an aqueous solution of ammonium sulfate and aluminum sulfate, using poly(2-acrylamido-2-methyl-1-propanesulfonate P(AMPS as stabilizer, acrylamide (AM and 2-acrylamido-2-methyl-1-propanesulfonate (AMPS as monomers, poly(2-acrylamido-2-methyl-1-propanesulfonate (PAMPS as stabilizer and [2-(2-imidazdino-2-ylpropane]dihydrochloride (VA-044 as initiator. The average particle size of polymer dispersion ranged from 0.2 to 0.3 µm, the molecular weight was from 4.3•106 to 5.7•106 g•mol-1. The polymer was characterized by infrared (IR spectroscopy, thermogravimetry (TGA and transmission electron microscopy (TEM. The swelling property of the dispersion polymer was studied by particle size distribution. When the polymer dispersion was diluted with deionized water, particle sizes decreased several times. When the polymer dispersion was diluted with salt water, the particle size increased with increasing concentration of salt. The effects of Al2(SO43 and stabilizer on the particle size and the relative molecular weight of the polymer were investigated, respectively. The optimum conditions for the stable Al2(SO43-P(AM/AMPS dispersion were that the concentration of Al2(SO43 was 1.12 wt%, the concentration of PAMPS stabilizer was 3 wt% and the concentration of initiator was 0.2 mol•l-1 and the monomers concentration was 14 wt%.

  16. Desolvation of polymers by ultrafast heating: Influence of hydrophilicity

    Science.gov (United States)

    Sun, Si Neng; Urbassek, Herbert M.

    2010-10-01

    Using molecular-dynamics simulation, we investigate the consequences of ultrafast laser-induced heating of a small water droplet containing a solvated polymer. Two polymers are studied: polyethylene as an example of a hydrophobic, and polyketone as an example of a hydrophilic polymer. In both cases, when the droplet is heated below the critical temperature of water, strong water evaporation is started, but the polymer remains in contact with a central water cluster. However, upon heating beyond the critical temperature, the hydrophilic polyethylene becomes completely desolvated, while polyketone still remains solvated. We analyze this behavior in terms of the intermolecular interactions and of the expansion dynamics of the heated droplet.

  17. Heterogeneous dynamics of ionic liquids: A four-point time correlation function approach

    Science.gov (United States)

    Liu, Jiannan; Willcox, Jon A. L.; Kim, Hyung J.

    2018-05-01

    Many ionic liquids show behavior similar to that of glassy systems, e.g., large and long-lasted deviations from Gaussian dynamics and clustering of "mobile" and "immobile" groups of ions. Herein a time-dependent four-point density correlation function—typically used to characterize glassy systems—is implemented for the ionic liquids, choline acetate, and 1-butyl-3-methylimidazolium acetate. Dynamic correlation beyond the first ionic solvation shell on the time scale of nanoseconds is found in the ionic liquids, revealing the cooperative nature of ion motions. The traditional solvent, acetonitrile, on the other hand, shows a much shorter length-scale that decays after a few picoseconds.

  18. Biomolecular electrostatics and solvation: a computational perspective.

    Science.gov (United States)

    Ren, Pengyu; Chun, Jaehun; Thomas, Dennis G; Schnieders, Michael J; Marucho, Marcelo; Zhang, Jiajing; Baker, Nathan A

    2012-11-01

    An understanding of molecular interactions is essential for insight into biological systems at the molecular scale. Among the various components of molecular interactions, electrostatics are of special importance because of their long-range nature and their influence on polar or charged molecules, including water, aqueous ions, proteins, nucleic acids, carbohydrates, and membrane lipids. In particular, robust models of electrostatic interactions are essential for understanding the solvation properties of biomolecules and the effects of solvation upon biomolecular folding, binding, enzyme catalysis, and dynamics. Electrostatics, therefore, are of central importance to understanding biomolecular structure and modeling interactions within and among biological molecules. This review discusses the solvation of biomolecules with a computational biophysics view toward describing the phenomenon. While our main focus lies on the computational aspect of the models, we provide an overview of the basic elements of biomolecular solvation (e.g. solvent structure, polarization, ion binding, and non-polar behavior) in order to provide a background to understand the different types of solvation models.

  19. Poly(vinylidene fluoride) modification induced by gamma irradiation for application as ionic polymer-metal composite; Modificacao de poli(fluoreto de vinilideno) induzida por radiacao gama para aplicacao como composito ionomerico de metal-polimero

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Henrique Perez

    2011-07-01

    Gamma-radiation-induced grafting of styrene into poly(vinylidene fluoride) (PVDF) films with 0.125 mm thickness at doses from 1 to 100 kGy in the presence of a styrene/N,N- dimethylformamide (DMF) solution (1:1, v/v) and styrene/toluene (1:1, v/v) at dose rate of 5 kGy h-1 was carried out by simultaneous method under nitrogen atmosphere at room temperature, using gamma rays from a Co-60. After grafting reactions, the polymer was then sulfonated in chlorosulfonic acid/1,2-dichloroethane (2 and 10%) for 3 hours. The films were characterized before and after modification by calculating the degree of grafting (DOG), infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetry (TG/DTG). DOG results show that grafting increases with dose, and varies enormously depending on the solvent used, with DOGs about 20 times greater in DMF than in toluene. It was possible to confirm the grafting of styrene by FT-IR due to the appearance of the new characteristic peaks and by the TG and DSC which exhibited changes in the thermal behavior of the grafted/sulfonated material. Sulfonated material was also characterized by ion exchange capacity (IEC) showed that both DOG and sulfonic acid concentration increase IEC values. Results showed that it is possible to obtain materials with ion exchange capacity of possible application as ionic polymer-metal composites. (author)

  20. Ionic Conductivity of Polyelectrolyte Hydrogels.

    Science.gov (United States)

    Lee, Chen-Jung; Wu, Haiyan; Hu, Yang; Young, Megan; Wang, Huifeng; Lynch, Dylan; Xu, Fujian; Cong, Hongbo; Cheng, Gang

    2018-02-14

    Polyelectrolytes have many important functions in both living organisms and man-made applications. One key property of polyelectrolytes is the ionic conductivity due to their porous networks that allow the transport of water and small molecular solutes. Among polyelectrolytes, zwitterionic polymers have attracted huge attention for applications that involve ion transport in a polyelectrolyte matrix; however, it is still unclear how the functional groups of zwitterionic polymer side chains affect their ion transport and swelling properties. In this study, zwitterionic poly(carboxybetaine acrylamide), poly(2-methacryloyloxyethyl phosphorylcholine), and poly(sulfobetaine methacrylate) hydrogels were synthesized and their ionic conductivity was studied and compared to cationic, anionic, and nonionic hydrogels. The change of the ionic conductivity of zwitterionic and nonionic hydrogels in different saline solutions was investigated in detail. Zwitterionic hydrogels showed much higher ionic conductivity than that of the widely used nonionic poly(ethylene glycol) methyl ether methacrylate hydrogel in all tested solutions. For both cationic and anionic hydrogels, the presence of mobile counterions led to high ionic conductivity in low salt solutions; however, the ionic conductivity of zwitterionic hydrogels surpassed that of cationic and ionic hydrogels in high salt solutions. Cationic and anionic hydrogels showed much higher water content than that of zwitterionic hydrogels in deionized water; however, the cationic hydrogels shrank significantly with increasing saline concentration. This work provides insight into the effects of polyelectrolyte side chains on ion transport. This can guide us in choosing better polyelectrolytes for a broad spectrum of applications, including bioelectronics, neural implants, battery, and so on.

  1. A solid-state dye-sensitized solar cell based on a novel ionic liquid gel and ZnO nanoparticles on a flexible polymer substrate

    Energy Technology Data Exchange (ETDEWEB)

    Wei Di; Ryhanen, Tapani [Nokia Research Centre c/o Nanoscience Centre, University of Cambridge, 11 JJ Thomson Avenue, CB3 0FF, Cambridge (United Kingdom); Unalan, Husnu Emrah; Amaratunga, Gehan [Centre of Advanced Photonics and Electronics, Department of Engineering, University of Cambridge, 9 JJ Thomson Avenue, CB3 0FA, Cambridge (United Kingdom); Han Dongxue; Zhang Qixian; Niu Li [Changchun Institute of Applied Chemistry, Chinese Academy of Science, 130000 Changchun (China)], E-mail: di.wei@nokia.com

    2008-10-22

    This paper describes a new strategy to make a full solid-state, flexible, dye-sensitized solar cell (DSSC) based on novel ionic liquid gel, organic dye, ZnO nanoparticles and carbon nanotube (CNT) thin film stamped onto a polyethylene terephthalate (PET) substrate. The CNTs serve both as the charge collector and as scaffolds for the growth of ZnO nanoparticles, where the black dye molecules are anchored. It opens up the possibility of developing a continuous roll to roll processing for THE mass production of DSSCs.

  2. Effect of plasticizer and fumed silica on ionic conductivity behaviour ...

    Indian Academy of Sciences (India)

    behaviour of proton conducting polymer electrolytes containing different concentrations of hexafluorophosphoric acid (HPF6) in polyethylene oxide ... Polymer electrolytes; ionic conductivity; polyethylene oxide; plasticizer; fumed silica. 1. Introduction ..... is a rapid weight loss which could be due to the degradation of polymer ...

  3. Ionic Liquid-Based Optical and Electrochemical Carbon Dioxide Sensors

    Science.gov (United States)

    Behera, Kamalakanta; Pandey, Shubha; Kadyan, Anu; Pandey, Siddharth

    2015-01-01

    Due to their unusual physicochemical properties (e.g., high thermal stability, low volatility, high intrinsic conductivity, wide electrochemical windows and good solvating ability), ionic liquids have shown immense application potential in many research areas. Applications of ionic liquid in developing various sensors, especially for the sensing of biomolecules, such as nucleic acids, proteins and enzymes, gas sensing and sensing of various important ions, among other chemosensing platforms, are currently being explored by researchers worldwide. The use of ionic liquids for the detection of carbon dioxide (CO2) gas is currently a major topic of research due to the associated importance of this gas with daily human life. This review focuses on the application of ionic liquids in optical and electrochemical CO2 sensors. The design, mechanism, sensitivity and detection limit of each type of sensor are highlighted in this review. PMID:26690155

  4. Ionic Liquid-Based Optical and Electrochemical Carbon Dioxide Sensors.

    Science.gov (United States)

    Behera, Kamalakanta; Pandey, Shubha; Kadyan, Anu; Pandey, Siddharth

    2015-12-04

    Due to their unusual physicochemical properties (e.g., high thermal stability, low volatility, high intrinsic conductivity, wide electrochemical windows and good solvating ability), ionic liquids have shown immense application potential in many research areas. Applications of ionic liquid in developing various sensors, especially for the sensing of biomolecules, such as nucleic acids, proteins and enzymes, gas sensing and sensing of various important ions, among other chemosensing platforms, are currently being explored by researchers worldwide. The use of ionic liquids for the detection of carbon dioxide (CO₂) gas is currently a major topic of research due to the associated importance of this gas with daily human life. This review focuses on the application of ionic liquids in optical and electrochemical CO₂ sensors. The design, mechanism, sensitivity and detection limit of each type of sensor are highlighted in this review.

  5. Ionic Liquid-Based Optical and Electrochemical Carbon Dioxide Sensors

    Directory of Open Access Journals (Sweden)

    Kamalakanta Behera

    2015-12-01

    Full Text Available Due to their unusual physicochemical properties (e.g., high thermal stability, low volatility, high intrinsic conductivity, wide electrochemical windows and good solvating ability, ionic liquids have shown immense application potential in many research areas. Applications of ionic liquid in developing various sensors, especially for the sensing of biomolecules, such as nucleic acids, proteins and enzymes, gas sensing and sensing of various important ions, among other chemosensing platforms, are currently being explored by researchers worldwide. The use of ionic liquids for the detection of carbon dioxide (CO2 gas is currently a major topic of research due to the associated importance of this gas with daily human life. This review focuses on the application of ionic liquids in optical and electrochemical CO2 sensors. The design, mechanism, sensitivity and detection limit of each type of sensor are highlighted in this review.

  6. Polymer anion-selective membranes for electrolytic splitting of water. Part II: enhancement of ionic conductivity and performance under conditions of alkaline water electrolysis

    Czech Academy of Sciences Publication Activity Database

    Hnát, J.; Paidar, M.; Schauer, Jan; Žitka, Jan; Bouzek, K.

    2012-01-01

    Roč. 42, č. 8 (2012), s. 545-554 ISSN 0021-891X R&D Projects: GA MŠk(CZ) 7E08005 EU Projects: European Commission(XE) 212903 - WELTEMP Institutional research plan: CEZ:AV0Z40500505 Keywords : water electrolysis * alkaline environment * polymer electrolyte Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.836, year: 2012

  7. Solvated protein-DNA docking using HADDOCK

    Energy Technology Data Exchange (ETDEWEB)

    Dijk, Marc van; Visscher, Koen M.; Kastritis, Panagiotis L.; Bonvin, Alexandre M. J. J., E-mail: a.m.j.j.bonvin@uu.nl [Utrecht University, Bijvoet Center for Biomolecular Research, Faculty of Science-Chemistry (Netherlands)

    2013-05-15

    Interfacial water molecules play an important role in many aspects of protein-DNA specificity and recognition. Yet they have been mostly neglected in the computational modeling of these complexes. We present here a solvated docking protocol that allows explicit inclusion of water molecules in the docking of protein-DNA complexes and demonstrate its feasibility on a benchmark of 30 high-resolution protein-DNA complexes containing crystallographically-determined water molecules at their interfaces. Our protocol is capable of reproducing the solvation pattern at the interface and recovers hydrogen-bonded water-mediated contacts in many of the benchmark cases. Solvated docking leads to an overall improvement in the quality of the generated protein-DNA models for cases with limited conformational change of the partners upon complex formation. The applicability of this approach is demonstrated on real cases by docking a representative set of 6 complexes using unbound protein coordinates, model-built DNA and knowledge-based restraints. As HADDOCK supports the inclusion of a variety of NMR restraints, solvated docking is also applicable for NMR-based structure calculations of protein-DNA complexes.

  8. Solvated protein–DNA docking using HADDOCK

    International Nuclear Information System (INIS)

    Dijk, Marc van; Visscher, Koen M.; Kastritis, Panagiotis L.; Bonvin, Alexandre M. J. J.

    2013-01-01

    Interfacial water molecules play an important role in many aspects of protein–DNA specificity and recognition. Yet they have been mostly neglected in the computational modeling of these complexes. We present here a solvated docking protocol that allows explicit inclusion of water molecules in the docking of protein–DNA complexes and demonstrate its feasibility on a benchmark of 30 high-resolution protein–DNA complexes containing crystallographically-determined water molecules at their interfaces. Our protocol is capable of reproducing the solvation pattern at the interface and recovers hydrogen-bonded water-mediated contacts in many of the benchmark cases. Solvated docking leads to an overall improvement in the quality of the generated protein–DNA models for cases with limited conformational change of the partners upon complex formation. The applicability of this approach is demonstrated on real cases by docking a representative set of 6 complexes using unbound protein coordinates, model-built DNA and knowledge-based restraints. As HADDOCK supports the inclusion of a variety of NMR restraints, solvated docking is also applicable for NMR-based structure calculations of protein–DNA complexes.

  9. Solvated protein-DNA docking using HADDOCK

    NARCIS (Netherlands)

    van Dijk, Marc; Visscher, Koen M; Bonvin, Alexandre M.J.J; Kastritis, Panagiotis L.

    2013-01-01

    Interfacial water molecules play an important role in many aspects of protein-DNA specificity and recognition. Yet they have been mostly neglected in the computational modeling of these complexes. We present here a solvated docking protocol that allows explicit inclusion of water molecules in the

  10. Synthesis, characterization, and application of novel Zn(II)-ionic imprinted polymer for preconcentration of Zn(II) ions from aqueous solution

    Science.gov (United States)

    Wirawan, T.; Supriyanto, G.; Soegianto, A.

    2018-04-01

    Preparation of a new Zn2+ ion-imprinted polymer (Zn-IIP) is presented in this report. The Zn-IIP are prepared by precipitation polymerization using 8-hydroxyquinoline (8HQ) as a ligand, methacrylic acid (MAA) as functional monomer, and ethylene glycol dimethacrylate (EGDMA) as a cross-linker has been prepared. The benzoyl peroxide and ethanol/acetonitrile (2:1) mixture were used as initiator and porogen, respectively. Precipitation polymerization was carried out by heating in a water bath at 60°C for 8 hours. After polymerization, cavities in the polymer particles corresponding to the Zn2+ ions were created by leaching the polymer with 2 mol L-1 HNO3. The polymer was washed with aquabidest and dried in an oven at the temperature of 60°C for 24 hours. The Zn-IIP was characterized by Fourier Transform Infrared Spectrophotometry (FT-IR) and Scanning Electron Microscopy (SEM). The synthesized Zn-IIP was used as a new adsorbent for solid phase extraction (SPE) of Zn(II) prior to Flame Atomic Absorption Spectrometry (FAAS) determination. The experimental parameters for SPE, such as pH of the sample, loading rate, and elution volume, have been optimized. The effect of pH of the sample on the extraction of analyte was studied in batch mode. The effects of loading rate and elution volume on the extraction of analyte were studied in dynamic mode by loading of the sample through IIP-SPE cartridge containing 100 mg of the synthesized Zn-IIP. The imprinted polymer (Zn-IIP) have bands at 3433.06 cm-1 (O-H), 1508.23 cm-1 (C=N aromatics), 1284.5 cm-1 (C-N aromatics), 1056.9 cm-1 (C-O phenol), 1724.24 cm-1 (C=O), and 1639.38 cm-1 (conjugated C=O with C=C). The Scanning Electron Microscopy (SEM) images of IIP and IIP show that the IIP is seen to have more cavities than NIP. The optimum pH for quantitative Zn(II) retention was 5.5, and the elution was completed with 2 mL of 1.0 mol L-1 nitric acid. The optimum loading rate was 0.5 mL min-1. The recovery of Zn(II) from solution

  11. Partial solvation parameters and LSER molecular descriptors

    International Nuclear Information System (INIS)

    Panayiotou, Costas

    2012-01-01

    Graphical abstract: The one-to-one correspondence of LSER molecular descriptors and partial solvation parameters (PSPs) for propionic acid. Highlights: ► Quantum-mechanics based development of a new QSPR predictive method. ► One-to-one correspondence of partial solvation parameters and LSER molecular descriptors. ► Development of alternative routes for the determination of partial solvation parameters and solubility parameters. ► Expansion and enhancement of solubility parameter approach. - Abstract: The partial solvation parameters (PSP) have been defined recently, on the basis of the insight derived from modern quantum chemical calculations, in an effort to overcome some of the inherent restrictions of the original definition of solubility parameter and expand its range of applications. The present work continues along these lines and introduces two new solvation parameters, the van der Waals and the polarity/refractivity ones, which may replace both of the former dispersion and polar PSPs. Thus, one may use either the former scheme of PSPs (dispersion, polar, acidic, and basic) or, equivalently, the new scheme (van der Waals, polarity/refractivity, acidic, basic). The new definitions are made in a simple and straightforward manner and, thus, the strength and appeal of the widely accepted concept of solubility parameter is preserved. The inter-relations of the various PSPs are critically discussed and their values are tabulated for a variety of common substances. The advantage of the new scheme of PSPs is the bridge that makes with the corresponding Abraham’s LSER descriptors. With this bridge, one may exchange information between PSPs, LSER experimental scales, and quantum mechanics calculations such as via the COSMO-RS theory. The proposed scheme is a predictive one and it is applicable to, both, homo-solvated and hetero-solvated compounds. The new scheme is tested for the calculation of activity coefficients at infinite dilution, for octanol

  12. Ionic liquids in the synthesis of nanoobjects

    International Nuclear Information System (INIS)

    Tarasova, Natalia P; Smetannikov, Yurii V; Zanin, A A

    2010-01-01

    Data on the usage of the novel green solvents, ionic liquids, in the synthesis of nanoobjects and their stabilization are considered. The information is structured according to the resulting products of the synthetic processes: nanoparticles of noble metals, nanoparticles of non-metals, nanoparticles of metal oxides and chalcogenides, nanocomposites, and highly dispersed polymers. The conclusion is made that the ionic liquids might determine the structure and the properties of the nanoobjects, thus opening new fundamental and technological horizons in nanochemistry.

  13. Advanced dielectric continuum model of preferential solvation

    Science.gov (United States)

    Basilevsky, Mikhail; Odinokov, Alexey; Nikitina, Ekaterina; Grigoriev, Fedor; Petrov, Nikolai; Alfimov, Mikhail

    2009-01-01

    A continuum model for solvation effects in binary solvent mixtures is formulated in terms of the density functional theory. The presence of two variables, namely, the dimensionless solvent composition y and the dimensionless total solvent density z, is an essential feature of binary systems. Their coupling, hidden in the structure of the local dielectric permittivity function, is postulated at the phenomenological level. Local equilibrium conditions are derived by a variation in the free energy functional expressed in terms of the composition and density variables. They appear as a pair of coupled equations defining y and z as spatial distributions. We consider the simplest spherically symmetric case of the Born-type ion immersed in the benzene/dimethylsulfoxide (DMSO) solvent mixture. The profiles of y(R ) and z(R ) along the radius R, which measures the distance from the ion center, are found in molecular dynamics (MD) simulations. It is shown that for a given solute ion z(R ) does not depend significantly on the composition variable y. A simplified solution is then obtained by inserting z(R ), found in the MD simulation for the pure DMSO, in the single equation which defines y(R ). In this way composition dependences of the main solvation effects are investigated. The local density augmentation appears as a peak of z(R ) at the ion boundary. It is responsible for the fine solvation effects missing when the ordinary solvation theories, in which z =1, are applied. These phenomena, studied for negative ions, reproduce consistently the simulation results. For positive ions the simulation shows that z ≫1 (z =5-6 at the maximum of the z peak), which means that an extremely dense solvation shell is formed. In such a situation the continuum description fails to be valid within a consistent parametrization.

  14. Ionic thermometers

    International Nuclear Information System (INIS)

    Strnad, M.

    1975-01-01

    An original method of temperature measurement based on conductivity changes near the phase transition point of ionic compounds and suitable for the range from 200 to 700 0 C according to the thermometric compound used, is given. By choosing between two approaches it is posible to evaluate either a discrete value of temperature or continuous measurement in a range to about 50 0 C below the phase transition point of thermometric compounds. The extreme nonlinearity of conductivity of the chosen group of ionic crystals used as well as the technical applications developed in the laboratories have not previously been published. The aim of the research is the application of this measuring method for temperature indication in nuclear reactors. Preliminary tests in radiation fields in an experimental reactor are yielding a real hope in this direction. (author)

  15. Ionic polarization

    International Nuclear Information System (INIS)

    Mahan, G.D.

    1992-01-01

    Ferroelectricity occurs in many different kinds of materials. Many of the technologically important solids, which are ferroelectric, can be classified as ionic. Any microscopic theory of ferroelectricity must contain a description of local polarization forces. We have collaborated in the development of a theory of ionic polarization which is quite successful. Its basic assumption is that the polarization is derived from the properties of the individual ions. We have applied this theory successfully to diverse subjects as linear and nonlinear optical response, phonon dispersion, and piezoelectricity. We have developed numerical methods using the local Density approximation to calculate the multipole polarizabilities of ions when subject to various fields. We have also developed methods of calculating the nonlinear hyperpolarizability, and showed that it can be used to explain light scattering experiments. This paper elaborates on this polarization theory

  16. Synergistic extraction of europium(III) in ammonium ionic liquid

    International Nuclear Information System (INIS)

    Rout, Alok; Venkatesan, K.A.; Antony, M.P.

    2016-01-01

    Room temperature ionic liquids have been receiving increased attention for possible applications in the area of nuclear fuel reprocessing and waste management due to their fascinating properties such as good ionicity, high solvation capability, properties tunable etc. Most of the studies in the literature on the extraction of metal ions with molecular extractants dissolved in ionic liquid diluents are making use of the hydrophobic ionic liquids containing imidazolium cations such as the 1-alkyl-3-methylimidazolium ion. From an environmental point of view, such ionic liquids are not suitable as the primary mode of the metal extraction is by cation exchange mechanism wherein ionic liquid cation is lost to the aqueous phase leading to aqueous contamination and issue of recyclability of organic phase. However, there are some hydrophobic ionic liquids such as trioctylmethylammonium chloride ((N 1888 )(Cl)), and trihexyl(tetradecyl)phoshonium chloride (Cyphos IL 101) that exhibit no cation exchange in the aqueous phase during extraction. In this context, the extraction behavior of europium(III) using a neutral extractant, octyl, phenyl-N.N-diisobutylmethylcarbamoylphophinoxide (CMPO) and/or an acidic extractant bis(ethylhexyl)phosphoric acid (D2EHPA) dissolved in the ammonium ionic liquid diluent, trioctylmethylammonium bis(trifluoromethanesulfonyl)imide, (N 1888 )(NTf 2 ). The extraction behavior of CMPO (or D2EHPA)/(N 1888 )((Tf 2 ) system was investigated as a function of different extraction parameters such as feed acidity, extractant concentration, equilibration time etc.

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

    Science.gov (United States)

    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.

  18. Polymer-ionic liquid ternary systems for Li-battery electrolytes: Molecular dynamics studies of LiTFSI in a EMIm-TFSI and PEO blend

    Energy Technology Data Exchange (ETDEWEB)

    Costa, Luciano T., E-mail: ltcosta@id.uff.br [Instituto de Química-Departamento de Físico-Química, Universidade Federal Fluminense, Outeiro de São João Batista s/n CEP, 24020-150 Niterói, Rio de Janeiro (Brazil); Sun, Bing; Jeschull, Fabian; Brandell, Daniel [Department of Chemistry—Ångström Laboratory, Uppsala University, P.O. Box 538, SE-751 21 Uppsala (Sweden)

    2015-07-14

    This paper presents atomistic molecular dynamics simulation studies of lithium bis(trifluoromethane)sulfonylimide (LiTFSI) in a blend of 1-ethyl-3-methylimidazolium (EMIm)-TFSI and poly(ethylene oxide) (PEO), which is a promising electrolyte material for Li- and Li-ion batteries. Simulations of 100 ns were performed for temperatures between 303 K and 423 K, for a Li:ether oxygen ratio of 1:16, and for PEO chains with 26 EO repeating units. Li{sup +} coordination and transportation were studied in the ternary electrolyte system, i.e., PEO{sub 16}LiTFSI⋅1.0 EMImTFSI, by applying three different force field models and are here compared to relevant simulation and experimental data. The force fields generated significantly different results, where a scaled charge model displayed the most reasonable comparisons with previous work and overall consistency. It is generally seen that the Li cations are primarily coordinated to polymer chains and less coupled to TFSI anion. The addition of EMImTFSI in the electrolyte system enhances Li diffusion, associated to the enhanced TFSI dynamics observed when increasing the overall TFSI anion concentration in the polymer matrix.

  19. Toward a Mesoscale Model for the Dynamics of Polymer Solutions

    Energy Technology Data Exchange (ETDEWEB)

    Miller, G H; Trebotich, D

    2006-10-02

    To model entire microfluidic systems containing solvated polymers we argue that it is necessary to have a numerical stability constraint governed only by the advective CFL condition. Advancements in the treatment of Kramers bead-rod polymer models are presented to enable tightly-coupled fluid-particle algorithms in the context of system-level modeling.

  20. Ionic conductivity and diffusion coefficient of barium-chloride-based ...

    Indian Academy of Sciences (India)

    styrenesulphonic acid) with bariumchloride dihydrate (BaCl 2 ·2H 2 O) salt complex has been synthesized following the usual solution casting. The ionic conductivity of polymer electrolyte was analysed by impedance spectroscopy. The highest room ...

  1. Poly (ether imide sulfone) membranes from solutions in ionic liquids

    KAUST Repository

    Kim, Dooli; Nunes, Suzana Pereira

    2017-01-01

    A membrane manufacture method based on non-volatile solvents and a high performance polymer, poly (ether imide sulfone) (EXTEM™), is proposed, as greener alternative to currently industrial process. We dissolved EXTEM™ in pure ionic liquids: 1-ethyl

  2. Relaxation dynamics following transition of solvated electrons

    International Nuclear Information System (INIS)

    Barnett, R.B.; Landman, U.; Nitzan, A.

    1989-01-01

    Relaxation dynamics following an electronic transition of an excess solvated electron in clusters and in bulk water is studied using an adiabatic simulation method. In this method the solvent evolves classically and the electron is constrained to a specified state. The coupling between the solvent and the excess electron is evaluated via the quantum expectation value of the electron--water molecule interaction potential. The relaxation following excitation (or deexcitation) is characterized by two time scales: (i) a very fast (/similar to/20--30 fs) one associated with molecular rotations in the first solvation shell about the electron, and (ii) a slower stage (/similar to/200 fs), which is of the order of the longitudinal dielectric relaxation time. The fast relaxation stage exhibits an isotope effect. The spectroscopical consequences of the relaxation dynamics are discussed

  3. Generalized Born Models of Macromolecular Solvation Effects

    Science.gov (United States)

    Bashford, Donald; Case, David A.

    2000-10-01

    It would often be useful in computer simulations to use a simple description of solvation effects, instead of explicitly representing the individual solvent molecules. Continuum dielectric models often work well in describing the thermodynamic aspects of aqueous solvation, and approximations to such models that avoid the need to solve the Poisson equation are attractive because of their computational efficiency. Here we give an overview of one such approximation, the generalized Born model, which is simple and fast enough to be used for molecular dynamics simulations of proteins and nucleic acids. We discuss its strengths and weaknesses, both for its fidelity to the underlying continuum model and for its ability to replace explicit consideration of solvent molecules in macromolecular simulations. We focus particularly on versions of the generalized Born model that have a pair-wise analytical form, and therefore fit most naturally into conventional molecular mechanics calculations.

  4. Differential solvation of intrinsically disordered linkers drives the formation of spatially organized droplets in ternary systems of linear multivalent proteins

    Science.gov (United States)

    Harmon, Tyler S.; Holehouse, Alex S.; Pappu, Rohit V.

    2018-04-01

    Intracellular biomolecular condensates are membraneless organelles that encompass large numbers of multivalent protein and nucleic acid molecules. The bodies assemble via a combination of liquid–liquid phase separation and gelation. A majority of condensates included multiple components and show multilayered organization as opposed to being well-mixed unitary liquids. Here, we put forward a simple thermodynamic framework to describe the emergence of spatially organized droplets in multicomponent systems comprising of linear multivalent polymers also known as associative polymers. These polymers, which mimic proteins and/or RNA have the architecture of domains or motifs known as stickers that are interspersed by flexible spacers known as linkers. Using a minimalist numerical model for a four-component system, we have identified features of linear multivalent molecules that are necessary and sufficient for generating spatially organized droplets. We show that differences in sequence-specific effective solvation volumes of disordered linkers between interaction domains enable the formation of spatially organized droplets. Molecules with linkers that are preferentially solvated are driven to the interface with the bulk solvent, whereas molecules that have linkers with negligible effective solvation volumes form cores in the core–shell architectures that emerge in the minimalist four-component systems. Our modeling has relevance for understanding the physical determinants of spatially organized membraneless organelles.

  5. Theory of optical spectra of solvated electrons

    International Nuclear Information System (INIS)

    Kestner, N.R.

    1975-01-01

    During the last few years better theoretical models of solvated electron have been developed. These models allow one to calculate a priori the observable properties of the trapped electron. One of the most important and most widely determined properties is the optical spectrum. In this paper we consider the predictions of the theories not only as to the band maximum but line shape and width. In addition we will review how the theories predict these will depend on the solvent, pressure, temperature, and solvent density. In all cases extensive comparisons will be made with experimental work. In addition four new areas will be explored and recent results will be presented. These concern electrons in dense polar gases, the time development of the solvated electron spectrum, solvated electrons in mixed solvents, and photoelectron emission spectra (PEE) as it relates to higher excited states. This paper will review all recent theoretical calculations and present a critical review of the present status and future developments which are anticipated. The best theories are quite successful in predicting trends, and qualitative agreement concerning band maximum. The theory is still weak in predicting line shape and line width

  6. Preferential solvation: dividing surface vs excess numbers.

    Science.gov (United States)

    Shimizu, Seishi; Matubayasi, Nobuyuki

    2014-04-10

    How do osmolytes affect the conformation and configuration of supramolecular assembly, such as ion channel opening and actin polymerization? The key to the answer lies in the excess solvation numbers of water and osmolyte molecules; these numbers are determinable solely from experimental data, as guaranteed by the phase rule, as we show through the exact solution theory of Kirkwood and Buff (KB). The osmotic stress technique (OST), in contrast, purposes to yield alternative hydration numbers through the use of the dividing surface borrowed from the adsorption theory. However, we show (i) OST is equivalent, when it becomes exact, to the crowding effect in which the osmolyte exclusion dominates over hydration; (ii) crowding is not the universal driving force of the osmolyte effect (e.g., actin polymerization); (iii) the dividing surface for solvation is useful only for crowding, unlike in the adsorption theory which necessitates its use due to the phase rule. KB thus clarifies the true meaning and limitations of the older perspectives on preferential solvation (such as solvent binding models, crowding, and OST), and enables excess number determination without any further assumptions.

  7. Preferential Solvation of an Asymmetric Redox Molecule

    Energy Technology Data Exchange (ETDEWEB)

    Han, Kee Sung; Rajput, Nav Nidhi; Vijayakumar, M.; Wei, Xiaoliang; Wang, Wei; Hu, Jian Z.; Persson, Kristin A.; Mueller, Karl T.

    2016-12-15

    The fundamental correlations between inter-molecular interactions, solvation structure and functionality of electrolytes are in many cases unknown, particularly for multi-component liquid systems. In this work, we explore such correlations by investigating the complex interplay between solubility and solvation structure for the electrolyte system comprising N-(ferrocenylmethyl)-N,N-dimethyl-N-ethylammonium bistrifluoromethylsulfonimide (Fc1N112-TFSI) dissolved in a ternary carbonate solvent mixture using combined NMR relaxation and computational analyses. Probing the evolution of the solvent-solvent, ion-solvent and ion-ion interactions with an increase in solute concentration provides a molecular level understanding of the solubility limit of the Fc1N112-TFSI system. An increase in solute con-centration leads to pronounced Fc1N112-TFSI contact-ion pair formation by diminishing solvent-solvent and ion-solvent type interactions. At the solubility limit, the precipitation of solute is initiated through agglomeration of contact-ion pairs due to overlapping solvation shells.

  8. Mode coupling theory analysis of electrolyte solutions: Time dependent diffusion, intermediate scattering function, and ion solvation dynamics.

    Science.gov (United States)

    Roy, Susmita; Yashonath, Subramanian; Bagchi, Biman

    2015-03-28

    A self-consistent mode coupling theory (MCT) with microscopic inputs of equilibrium pair correlation functions is developed to analyze electrolyte dynamics. We apply the theory to calculate concentration dependence of (i) time dependent ion diffusion, (ii) intermediate scattering function of the constituent ions, and (iii) ion solvation dynamics in electrolyte solution. Brownian dynamics with implicit water molecules and molecular dynamics method with explicit water are used to check the theoretical predictions. The time dependence of ionic self-diffusion coefficient and the corresponding intermediate scattering function evaluated from our MCT approach show quantitative agreement with early experimental and present Brownian dynamic simulation results. With increasing concentration, the dispersion of electrolyte friction is found to occur at increasingly higher frequency, due to the faster relaxation of the ion atmosphere. The wave number dependence of intermediate scattering function, F(k, t), exhibits markedly different relaxation dynamics at different length scales. At small wave numbers, we find the emergence of a step-like relaxation, indicating the presence of both fast and slow time scales in the system. Such behavior allows an intriguing analogy with temperature dependent relaxation dynamics of supercooled liquids. We find that solvation dynamics of a tagged ion exhibits a power law decay at long times-the decay can also be fitted to a stretched exponential form. The emergence of the power law in solvation dynamics has been tested by carrying out long Brownian dynamics simulations with varying ionic concentrations. The solvation time correlation and ion-ion intermediate scattering function indeed exhibit highly interesting, non-trivial dynamical behavior at intermediate to longer times that require further experimental and theoretical studies.

  9. Conductometric determination of solvation numbers of alkali metal cations

    International Nuclear Information System (INIS)

    Fialkov, Yu.Ya.; Gorbachev, V.Yu.; Chumak, V.L.

    1997-01-01

    Theories describing the interrelation of ion mobility with their effective radii in solutions are considered. Possibility of using these theories for determination the solvation numbers n s of some ions is estimated. According to conductometric data values of n s are calculated for alkali metal ions in propylene carbonate. The data obtained are compared with solvation numbers determined with the use of entropies of ions solvation. Change of n s values within temperature range 273.15-323.15 K is considered. Using literature data the effect of crystallographic radii of cations and medium permittivity on the the values of solvation numbers of cations are analyzed. (author)

  10. Electroactive polymers for sensing

    Science.gov (United States)

    2016-01-01

    Electromechanical coupling in electroactive polymers (EAPs) has been widely applied for actuation and is also being increasingly investigated for sensing chemical and mechanical stimuli. EAPs are a unique class of materials, with low-moduli high-strain capabilities and the ability to conform to surfaces of different shapes. These features make them attractive for applications such as wearable sensors and interfacing with soft tissues. Here, we review the major types of EAPs and their sensing mechanisms. These are divided into two classes depending on the main type of charge carrier: ionic EAPs (such as conducting polymers and ionic polymer–metal composites) and electronic EAPs (such as dielectric elastomers, liquid-crystal polymers and piezoelectric polymers). This review is intended to serve as an introduction to the mechanisms of these materials and as a first step in material selection for both researchers and designers of flexible/bendable devices, biocompatible sensors or even robotic tactile sensing units. PMID:27499846

  11. [Advances of poly (ionic liquid) materials in separation science].

    Science.gov (United States)

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

    2015-11-01

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

  12. Combined techniques for studying actinide complexes in room temperature ionic liquids

    International Nuclear Information System (INIS)

    Gaillard, C.; Billard, I.; Mekki, S.; Ouadi, A.; Hennig, Ch.; Denecke, M.A.

    2007-01-01

    Room temperature ionic liquids (RTILs) are a new class of solvents. Their main interest is related to their 'green' properties (non-volatile, non-flammable, etc.), but also from the variability of their physico-chemical properties (stability, hydrophobicity, viscosity) as a function of the RTIL cationic and anionic components. In the frame of the nuclear fuel reprocessing, RTILs are particularly attractive in order to improve existing processes or to develop new ones for actinide and lanthanide partitioning, in replacement of toxic solvents used nowadays, for metal electrodeposition or for liquid/liquid extraction by the use of task specific ionic liquids. However, despite the increasing number of publications devoted to ionic liquids, the solvation effects, the solute-solvent and solvent-solvent interactions are still hardly known. These fundamental aspects are of tremendous importance to the understanding of the solvating properties of these new solvents. In this frame, we have undertaken studies on the solvation and complexation of lanthanides (III) and actinides in RTILs, by the use of spectroscopic techniques. Experiments were led in various ionic liquids in order to highlight the role of the anionic part of the RTILs on the reactivity of the studied cations. Results have clearly shown that solvation phenomena in RTILs are not as 'simple' as in classical solvents. The dissolution of a Ln/An salt, even if complete, does not imply dissociation and solvation of the metal cation by the RTILs anions only. The nature of first co-ordination sphere of Ln/An depends on the competition between its counter-anions and the RTIL anions, which, in turn, influence the complexation reaction with other added anions such as chlorides. (authors)

  13. Green Imidazolium Ionics-From Truly Sustainable Reagents to Highly Functional Ionic Liquids.

    Science.gov (United States)

    Tröger-Müller, Steffen; Brandt, Jessica; Antonietti, Markus; Liedel, Clemens

    2017-09-04

    We report the synthesis of task-specific imidazolium ionic compounds and ionic liquids with key functionalities of organic molecules from electro-, polymer-, and coordination chemistry. Such products are highly functional and potentially suitable for technology applications even though they are formed without elaborate reactions and from cheap and potentially green reagents. We further demonstrate the versatility of the used synthetic approach by introducing different functional and green counterions to the formed ionic liquids directly during the synthesis or after metathesis reactions. The influence of different cation structures and different anions on the thermal and electrochemical properties of the resulting ionic liquids is discussed. Our goal is to make progress towards economically competitive and sustainable task-specific ionic liquids. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Magnetic Solid-phase Extraction with Fe3O4/Molecularly Imprinted Polymers Modified by Deep Eutectic Solvents and Ionic Liquids for the Rapid Purification of Alkaloid Isomers (Theobromine and Theophylline from Green Tea

    Directory of Open Access Journals (Sweden)

    Guizhen Li

    2017-06-01

    Full Text Available Different kinds of deep eutectic solvents (DES based on choline chloride (ChCl and ionic liquids (ILs based on 1-methylimidazole were used to modify Fe3O4/molecularly imprinted polymers (Fe3O4/MIPs, and the resulting materials were applied for the rapid purification of alkaloid isomers (theobromine and theophylline from green tea with magnetic solid-phase extraction (M-SPE. The M-SPE procedure was optimized using the response surface methodology (RSM to analyze the maximum conditions. The materials were characterized by Fourier transform infrared spectroscopy (FI-IR and field emission scanning electron microscopy (FE-SEM. Compared to the ILs-Fe3O4/MIPs, the DESs-Fe3O4/MIPs were developed for the stronger recognition and higher recoveries of the isomers (theophylline and theobromine from green tea, particularly DES-7-Fe3O4/MIPs. With RSM, the optimal recovery condition for theobromine and theophylline in the M-SPE were observed with ratio of methanol (80% as the washing solution, methanol/acetic acid (HAc (8:2 as the eluent at pH 3, and an eluent volume of 4 mL. The practical recoveries of theobromine and theophylline in green tea were 92.27% and 87.51%, respectively, with a corresponding actual extraction amount of 4.87 mg•g−1 and 5.07 mg•g−1. Overall, the proposed approach with the high affinity of Fe3O4/MIPs might offer a novel method for the purification of complex isomer samples.

  15. Magnetic Solid-phase Extraction with Fe₃O₄/Molecularly Imprinted Polymers Modified by Deep Eutectic Solvents and Ionic Liquids for the Rapid Purification of Alkaloid Isomers (Theobromine and Theophylline) from Green Tea.

    Science.gov (United States)

    Li, Guizhen; Wang, Xiaoqin; Row, Kyung Ho

    2017-06-25

    Different kinds of deep eutectic solvents (DES) based on choline chloride (ChCl) and ionic liquids (ILs) based on 1-methylimidazole were used to modify Fe3O4/molecularly imprinted polymers (Fe3O4/MIPs), and the resulting materials were applied for the rapid purification of alkaloid isomers (theobromine and theophylline) from green tea with magnetic solid-phase extraction (M-SPE). The M-SPE procedure was optimized using the response surface methodology (RSM) to analyze the maximum conditions. The materials were characterized by Fourier transform infrared spectroscopy (FI-IR) and field emission scanning electron microscopy (FE-SEM). Compared to the ILs-Fe3O4/MIPs, the DESs-Fe3O4/MIPs were developed for the stronger recognition and higher recoveries of the isomers (theophylline and theobromine) from green tea, particularly DES-7-Fe3O4/MIPs. With RSM, the optimal recovery condition for theobromine and theophylline in the M-SPE were observed with ratio of methanol (80%) as the washing solution, methanol/acetic acid (HAc) (8:2) as the eluent at pH 3, and an eluent volume of 4 mL. The practical recoveries of theobromine and theophylline in green tea were 92.27% and 87.51%, respectively, with a corresponding actual extraction amount of 4.87 mg•g-1 and 5.07 mg•g-1. Overall, the proposed approach with the high affinity of Fe3O4/MIPs might offer a novel method for the purification of complex isomer samples.

  16. Solid State Ionics Advanced Materials for Emerging Technologies

    Science.gov (United States)

    Chowdari, B. V. R.; Careem, M. A.; Dissanayake, M. A. K. L.; Rajapakse, R. M. G.; Seneviratne, V. A.

    2006-06-01

    spectroscopic analysis of thin film LiNiVO[symbol] prepared by pulsed laser deposition technique / S. Selvasekarapandian ... [et al.]. Synthesis and characterization of LiFePO[symbol] cathode materials by microwave processing / J. Zhou ... [et al.]. Characterization of Nd[symbol]Sr[symbol]CoO[symbol] including Pt second phase as the cathode material for low-temperature SOFCs / J. W. Choi ... [et al.]. Thermodynamic behavior of lithium intercalation into natural vein and synthetic graphite / N. W. B. Balasooriya, P. W. S. K. Bandaranayake, Ph. Touzain -- pt. III. Electroactive polymers. Invited papers. Organised or disorganised? looking at polymer electrolytes from both points of view / Y.-P. Liao ... [et al.]. Polymer electrolytes - simple low permittivity solutions? / I. Albinsson, B.-E. Mellander. Dependence of conductivity enhancement on the dielectric constant of the dispersoid in polymer-ferroelectric composite electrolytes / A. Chandra, P. K. Singh, S. Chandra. Design and application of boron compounds for high-performance polymer electrolytes / T. Fujinami. Structural, vibrational and AC impedance analysis of nano composite polymer electrolytes based on PVAC / S. Selvasekarapandian ... [et al.]. Absorption intensity variation with ion association in PEO based electrolytes / J. E. Furneaux ... [et al.]. Study of ion-polymer interactions in cationic and anionic ionomers from the dependence of conductivity on pressure and temperature / M. Duclot ... [et al.]. Triol based polyurethane gel electrolytes for electrochemical devices / A. R. Kulkarni. Contributed papers. Accurate conductivity measurements to solvation energies in nafion / M. Maréchal, J.-L Souquet. Ion conducting behaviour of composite polymer gel electrolyte: PEG-PVA-(NH[symbol]CH[symbol]CO[symbol])[symbol] system / S. L. Agrawal, A. Awadhia, S. K. Patel. Impedance spectroscopy and DSC studies of poly(vinylalcohol)/ silicotungstic acid crosslinked composite membranes / A. Anis, A. K. Banthia. (PEO

  17. High resolution scanning optical imaging of a frozen planar polymer light-emitting electrochemical cell: an experimental and modelling study

    Institute of Scientific and Technical Information of China (English)

    Faleh AlTal; Jun Gao

    2017-01-01

    Light-emitting electrochemical cells (LECs) are organic photonic devices based on a mixed electronic and ionic conductor.The active layer of a polymer-based LEC consists of a luminescent polymer,an ion-solvating/transport polymer,and a compatible salt.The LEC p-n or p-i-n junction is ultimately responsible for the LEC performance.The LEC junction,however,is still poorly understood due to the difficulties of characterizing a dynamic-junction LEC.In this paper,we present an experimental and modeling study of the LEC junction using scanning optical imaging techniques.Planar LECs with an interelectrode spacing of 560 μm have been fabricated,activated,frozen and scanned using a focused laser beam.The optical-beam-induced-current (OBIC) and photoluminescence (PL) data have been recorded as a function of beam location.The OBIC profile has been simulated in COMSOL that allowed for the determination of the doping concentration and the depletion width of the LEC junction.

  18. Theoretical Study of Renewable Ionic Liquids in the Pure State and with Graphene and Carbon Nanotubes.

    Science.gov (United States)

    García, Gregorio; Atilhan, Mert; Aparicio, Santiago

    2015-09-17

    The N-ethyl-N-(furan-2-ylmethyl)ethanaminium dihydrogen phosphate ionic liquid was studied as a model of ionic liquids which can be produced from totally renewable sources. A computational study using both molecular dynamics and density functional theory methods was carried out. The properties, structuring, and intermolecular interactions (hydrogen bonding) of this fluid in the pure state were studied as a function of pressure and temperature. Likewise, the adsorption on graphene and the confinement between graphene sheets was also studied. The solvation of single walled carbon nanotubes in the selected ionic liquid was analyzed together with the behavior of ions confined inside these nanotubes. The reported results show remarkable properties for this fluid, which show that many of the most relevant properties of ionic liquids and their ability to interact with carbon nanosystems may be maintained and even improved using new families of renewable compounds instead of classic types of ionic liquids with worse environmental, toxicological, and economical profiles.

  19. Abacavir methanol 2.5-solvate

    Directory of Open Access Journals (Sweden)

    Phuong-Truc T. Pham

    2009-08-01

    Full Text Available The structure of abacavir (systematic name: {(1S,4R-4-[2-amino-6-(cyclopropylamino-9H-purin-9-yl]cyclopent-2-en-1-yl}methanol, C14H18N6O·2.5CH3OH, consists of hydrogen-bonded ribbons which are further held together by additional hydrogen bonds involving the hydroxyl group and two N atoms on an adjacent purine. The asymmetric unit also contains 2.5 molecules of methanol solvate which were grossly disordered and were excluded using SQUEEZE subroutine in PLATON [Spek, (2009. Acta Cryst. D65, 148–155].

  20. Rotation and solvation of ammonium ion

    International Nuclear Information System (INIS)

    Perrin, C.L.; Gipe, R.K.

    1987-01-01

    From nitrogen-15 spin-lattice relaxation times and nuclear Overhauser enhancements, the rotational correlations time tau/sub c/ for 15 NH 4 + was determined in s series of solvents. Values of tau/sub c/ range from 0.46 to 20 picoseconds. The solvent dependent of tau/sub c/ cannot be explained in terms of solvent polarity, molecular dipole moment, solvent basicity, solvent dielectric relaxation, or solvent viscosity. The rapid rotation and the variation with solvent can be accounted for by a model that involves hydrogen bonding of an NH proton to more than one solvent molecule in a disordered solvation environment. 25 references, 1 table

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

    Science.gov (United States)

    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.

  2. Performance limitations of polymer electrolytes based on ethylene oxide polymers

    International Nuclear Information System (INIS)

    Buriez, Olivier; Han, Yong Bong; Hou, Jun; Kerr, John B.; Qiao, Jun; Sloop, Steven E.; Tian, Minmin; Wang, Shanger

    1999-01-01

    Studies of polymer electrolyte solutions for lithium-polymer batteries are described. Two different salts, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium trifluoromethanesulfonate (LiTf), were dissolved in a variety of polymers. The structures were all based upon the ethylene oxide unit for lithium ion solvation and both linear and comb-branch polymer architectures have been examined. Conductivity, salt diffusion coefficient and transference number measurements demonstrate the superior transport properties of the LiTFSI salt over LiTf. Data obtained on all of these polymers combined with LiTFSI salts suggest that there is a limit to the conductivity achievable at room temperature, at least for hosts containing ethylene oxide units. The apparent conductivity limit is 5 x 10-5 S/cm at 25 C. Providing that the polymer chain segment containing the ethylene oxide units is at least 5-6 units long there appears to be little influence of the polymer framework to which the solvating groups are attached. To provide adequate separator function, the mechanical properties may be disconnected from the transport properties by selection of an appropriate architecture combined with an adequately long ethylene oxide chain. For both bulk and interfacial transport of the lithium ions, conductivity data alone is insufficient to understand the processes that occur. Lithium ion transference numbers and salt diffusion coefficients also play a major role in the observed behavior and the transport properties of these polymer electrolyte solutions appear to be quite inadequate for ambient temperature performance. At present, this restricts the use of such systems to high temperature applications. Several suggestions are given to overcome these obstacles

  3. Solvation of hydrocarbons in aqueous-organic mixtures

    International Nuclear Information System (INIS)

    Sedov, I.A.; Magsumov, T.I.; Solomonov, B.N.

    2016-01-01

    Highlights: • Thermodynamic functions of solvation in mixtures of water with acetone and acetonitrile are measured at T = 298.15 K. • Solvation of n-octane and toluene in aqueous-organic mixtures is studied. • When increasing water content, Gibbs free energies grow up steadily, while enthalpies have a maximum. • Hydrocarbons are preferentially solvated with organic cosolvent even in mixtures with rather high water content. • Acetonitrile suppresses the hydrophobic effect less than acetone. - Abstract: We study the solvation of two hydrocarbons, n-octane and toluene, in binary mixtures of water with organic cosolvents. Two polar aprotic cosolvents that are miscible with water in any proportions, acetonitrile and acetone, were considered. We determine the magnitudes of thermodynamic functions of dissolution and solvation at T = 298.15 K in the mixtures with various compositions. Solution calorimetry was used to measure the enthalpies of solution, and GC headspace analysis was applied to obtain limiting activity coefficients of solutes in the studied systems. For the first time, the enthalpies of solution of alkane in the mixtures with high water content were measured directly. We observed well-pronounced maxima of the dependencies of enthalpies of solvation from the composition of solvent and no maxima for the Gibbs free energies of solvation. Two factors are concluded to be important to explain the observed tendencies: high energy cost of reorganization of binary solvent upon insertion of solute molecules and preferential surrounding of hydrocarbons with the molecules of organic cosolvent. Enthalpy-entropy compensation leads to a steady growth of the Gibbs free energies with increasing water content. On the other hand, consideration of the plots of the Gibbs free energy against enthalpy of solvation clearly shows that the solvation properties are changed dramatically after addition of a rather small amount of organic cosolvents. It is shown that they

  4. Radiation induced ionic polymerisation and grafting of vinyl monomers

    International Nuclear Information System (INIS)

    Stannett, V.T.

    1981-01-01

    Some special aspects of the radiation induced ionic polymerisation and grafting of vinyl monomers will be described. In particular the effects of solvents on the cationic polymerisation of the vinyl ethers will be discussed in detail. The unequivocal free ion nature of the polymerisation makes such information of considerable general interest. Estimates of the propagation rate constants with free cation polymerisation in solvents of different dielectric constants and solvation powers will be presented. Finally, some observations on the radiation induced graft polymerisation of ethyl vinyl ether to poly(vinyl chloride) and to polypropylene will be presented. (author)

  5. Ultrafast dynamics of hydrogen bond exchange in aqueous ionic solutions.

    Science.gov (United States)

    Park, Sungnam; Odelius, Michael; Gaffney, Kelly J

    2009-06-04

    The structural and dynamical properties of aqueous ionic solutions influence a wide range of natural and biological processes. In these solutions, water has the opportunity to form hydrogen bonds with other water molecules and anions. Knowing the time scale with which these configurations interconvert represents a key factor to understanding the influence of molecular scale heterogeneity on chemical events in aqueous ionic solutions. We have used ultrafast IR spectroscopy and Car-Parrinello molecular dynamics (CPMD) simulations to investigate the hydrogen bond (H-bond) structural dynamics in aqueous 6 M sodium perchlorate (NaClO4) solution. We have measured the H-bond exchange dynamics between spectrally distinct water-water and water-anion H-bond configurations with 2DIR spectroscopy and the orientational relaxation dynamics of water molecules in different H-bond configurations with polarization-selective IR pump-probe experiments. The experimental H-bond exchange time correlates strongly with the experimental orientational relaxation time of water molecules. This agrees with prior observations in water and aqueous halide solutions, and has been interpreted within the context of an orientational jump model for the H-bond exchange. The CPMD simulations performed on aqueous 6 M NaClO4 solution clearly demonstrate that water molecules organize into two radially and angularly distinct structural subshells within the first solvation shell of the perchlorate anion, with one subshell possessing the majority of the water molecules that donate H-bonds to perchlorate anions and the other subshell possessing predominantly water molecules that donate two H-bonds to other water molecules. Due to the high ionic concentration used in the simulations, essentially all water molecules reside in the first ionic solvation shells. The CPMD simulations also demonstrate that the molecular exchange between these two structurally distinct subshells proceeds more slowly than the H

  6. Concept of polymer alloy electrolytes: towards room temperature operation of lithium-polymer batteries

    International Nuclear Information System (INIS)

    Noda, Kazuhiro; Yasuda, Toshikazu; Nishi, Yoshio

    2004-01-01

    Polymer alloy technique is very powerful tool to tune the ionic conductivity and mechanical strength of polymer electrolyte. A semi-interpenetrating polymer network (semi-IPN) polymer alloy electrolyte, composed of non-cross-linkable siloxane-based polymer and cross-linked 3D network polymer, was prepared. Such polymer alloy electrolyte has quite high ionic conductivity (more than 10 -4 Scm -1 at 25 o C and 10 -5 Scm -1 at -10 o C) and mechanical strength as a separator film with a wide electrochemical stability window. A lithium metal/semi-IPN polymer alloy solid state electrolyte/LiCoO 2 cell demonstrated promising cycle performance with room temperature operation of the energy density of 300Wh/L and better rate performance than conventional PEO based lithium polymer battery ever reported

  7. The Effects of Lithium Triflate (LiCF3SO3) on the PMMA-based Solid Polymer Electrolytes

    International Nuclear Information System (INIS)

    Chew, K. W.; Chen, S. S.; Pang, W. L.; Tan, C. G.; Osman, Z.

    2010-01-01

    The effects of Lithium triflate salt (LiCF 3 SO 3 ), on the poly (methyl methacrylate)(PMMA)-based solid polymer electrolytes plasticized with propylene carbonate (PC) solvated in Tetrahydrofuran (THF) have been studied through a.c impedance spectroscopy and infrared spectroscopy. Lithium triflate was incorporated into the predetermined PMMA/PC system that has the highest value of ionic conductivity. In current investigations, four combination systems: Pure PMMA, (PMMA+PC) systems, (PMMA+LiCF 3 SO 3 ) and (PMMA+PC+LiCF 3 SO 3 ) systems were prepared using the solution cast method. Solutions were stirred for numerous hours to obtain a homogenous solution before it is poured into the petri dishes under ambient temperature to form the solid electrolyte thin film. The films were then removed from petri discs and transferred into the dessicator for further drying prior to the different tests. From the characterization done through the a.c impedance spectroscopy, the highest room temperature ionic conductivity in the pure PMMA sample, (PMMA+PC) system and (PMMA+LiCF 3 SO 3 ) system is 2.83x10 -12 Scm -1 , 4.39x10 -11 Scm -1 and 3.93x10 -6 Scm -1 respectively. The conductivity for (PMMA+PC+LiCF 3 SO 3 ) system was obtained with the 30 wt% of lithium triflate, which is 2.48x10 -5 Scm -1 . Infrared spectroscopy shows that complexation occurred between the polymer and the plasticizer, and the polymer and plasticizer and salt. The interactions have been studied in the C=O band, C-O-C band and the O-CH 3 band.

  8. Electroactive Ionic Soft Actuators with Monolithically Integrated Gold Nanocomposite Electrodes.

    Science.gov (United States)

    Yan, Yunsong; Santaniello, Tommaso; Bettini, Luca Giacomo; Minnai, Chloé; Bellacicca, Andrea; Porotti, Riccardo; Denti, Ilaria; Faraone, Gabriele; Merlini, Marco; Lenardi, Cristina; Milani, Paolo

    2017-06-01

    Electroactive ionic gel/metal nanocomposites are produced by implanting supersonically accelerated neutral gold nanoparticles into a novel chemically crosslinked ion conductive soft polymer. The ionic gel consists of chemically crosslinked poly(acrylic acid) and polyacrylonitrile networks, blended with halloysite nanoclays and imidazolium-based ionic liquid. The material exhibits mechanical properties similar to that of elastomers (Young's modulus ≈ 0.35 MPa) together with high ionic conductivity. The fabrication of thin (≈100 nm thick) nanostructured compliant electrodes by means of supersonic cluster beam implantation (SCBI) does not significantly alter the mechanical properties of the soft polymer and provides controlled electrical properties and large surface area for ions storage. SCBI is cost effective and suitable for the scaleup manufacturing of electroactive soft actuators. This study reports the high-strain electromechanical actuation performance of the novel ionic gel/metal nanocomposites in a low-voltage regime (from 0.1 to 5 V), with long-term stability up to 76 000 cycles with no electrode delamination or deterioration. The observed behavior is due to both the intrinsic features of the ionic gel (elasticity and ionic transport capability) and the electrical and morphological features of the electrodes, providing low specific resistance (<100 Ω cm -2 ), high electrochemical capacitance (≈mF g -1 ), and minimal mechanical stress at the polymer/metal composite interface upon deformation. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Acidic Ionic Liquids.

    Science.gov (United States)

    Amarasekara, Ananda S

    2016-05-25

    Ionic liquid with acidic properties is an important branch in the wide ionic liquid field and the aim of this article is to cover all aspects of these acidic ionic liquids, especially focusing on the developments in the last four years. The structural diversity and synthesis of acidic ionic liquids are discussed in the introduction sections of this review. In addition, an unambiguous classification system for various types of acidic ionic liquids is presented in the introduction. The physical properties including acidity, thermo-physical properties, ionic conductivity, spectroscopy, and computational studies on acidic ionic liquids are covered in the next sections. The final section provides a comprehensive review on applications of acidic ionic liquids in a wide array of fields including catalysis, CO2 fixation, ionogel, electrolyte, fuel-cell, membrane, biomass processing, biodiesel synthesis, desulfurization of gasoline/diesel, metal processing, and metal electrodeposition.

  10. Solvation of lithium ion in dimethoxyethane and propylene carbonate

    Science.gov (United States)

    Chaban, Vitaly

    2015-07-01

    Solvation of the lithium ion (Li+) in dimethoxyethane (DME) and propylene carbonate (PC) is of scientific significance and urgency in the context of lithium-ion batteries. I report PM7-MD simulations on the composition of Li+ solvation shells (SH) in a few DME/PC mixtures. The equimolar mixture features preferential solvation by PC, in agreement with classical MD studies. However, one DME molecule is always present in the first SH, supplementing the cage formed by five PC molecules. As PC molecules get removed, DME gradually substitutes vacant places. In the PC-poor mixtures, an entire SH is populated by five DME molecules.

  11. Ionic Liquids in Biomass Processing

    Science.gov (United States)

    Tan, Suzie Su Yin; Macfarlane, Douglas R.

    Ionic liquids have been studied for their special solvent properties in a wide range of processes, including reactions involving carbohydrates such as cellulose and glucose. Biomass is a widely available and renewable resource that is likely to become an economically viable source of starting materials for chemical and fuel production, especially with the price of petroleum set to increase as supplies are diminished. Biopolymers such as cellulose, hemicellulose and lignin may be converted to useful products, either by direct functionalisation of the polymers or depolymerisation to monomers, followed by microbial or chemical conversion to useful chemicals. Major barriers to the effective conversion of biomass currently include the high crystallinity of cellulose, high reactivity of carbohydrates and lignin, insolubility of cellulose in conventional solvents, as well as heterogeneity in the native lignocellulosic materials and in lignin itself. This combination of factors often results in highly heterogeneous depolymerisation products, which make efficient separation difficult. Thus the extraction, depolymerisation and conversion of biopolymers will require novel reaction systems in order to be both economically attractive and environmentally benign. The solubility of biopolymers in ionic liquids is a major advantage of their use, allowing homogeneous reaction conditions, and this has stimulated a growing research effort in this field. This review examines current research involving the use of ionic liquids in biomass reactions, with perspectives on how it relates to green chemistry, economic viability, and conventional biomass processes.

  12. Ionic conductivity studies of gel polyelectrolyte based on ionic liquid

    Energy Technology Data Exchange (ETDEWEB)

    Cha, E.H. [The Faculty of Liberal Arts (Chemistry), Hoseo University, Asan Choongnam 336-795 (Korea); Lim, S.A. [Functional Proteomics Center, Korea Institute of Science and Technology, Seoul 136-791 (Korea); Park, J.H. [Department of Herbal Medicine, Hoseo University, Asan Choongnam 336-795 (Korea); Kim, D.W. [Department of Chemical Technology, Han Bat National University, Daejon 305-719 (Korea); Macfarlane, D.R. [School of Chemistry, Monash University, Clayton, Vic. 3800 (Australia)

    2008-04-01

    Novel lithium polyelectrolyte-ionic liquids have been prepared and characterized of their properties. Poly(lithium 2-acrylamido-2-methyl propanesulfonate) (PAMPSLi) and its copolymer with N-vinyl formamide (VF) also has been prepared as a copolymer. 1-Ethyl-3-methylimidazolium tricyanomethanide (emImTCM) and N,N-dimethyl-N-propyl-N-butyl ammonium tricyanomethanide (N{sub 1134}TCM) which are chosen because of the same with the anion of ionic liquid were prepared. The ionic conductivity of copolymer system (PAMPSLi/PVF/emImTCM: 5.43 x 10{sup -3} S cm{sup -1} at 25 C) exhibits about over four times higher than that of homopolymer system (PAMPSLi/emImTCM: 1.28 x 10{sup -3} S cm{sup -1} at 25 C). Introduction of vinyl formamide into the copolymer type can increase the dissociation of the lithium cations from the polymer backbone. The ionic conductivity of copolymer with emImTCM (PAMPSLi/PVF/emImTCM) exhibits the higher conductivity than that of PAMPSLi/PVF/N{sub 1134}TCM (2.48 x 10{sup -3} S cm{sup -1}). Because of using the polymerizable anion it is seen to maintain high flexibility of imidazolium cation effectively to exhibit the higher conductivity. And also the viscosity of emImTCM (19.56 cP) is lower than that of N{sub 1134}TCM (28.61 cP). Low viscosity leads to a fast rate of diffusion of redox species. (author)

  13. Fullerol ionic fluids

    KAUST Repository

    Fernandes, Nikhil; Dallas, Panagiotis; Rodriguez, Robert; Bourlinos, Athanasios B.; Georgakilas, Vasilios; Giannelis, Emmanuel P.

    2010-01-01

    ®). The ionic fluid was compared to a control synthesized by mixing the partially protonated form (sodium form) of the fullerols with the same oligomeric amine in the same ratio as in the ionic fluids (20 wt% fullerol). In the fullerol fluid the ionic bonding

  14. High resolution scanning optical imaging of a frozen planar polymer light-emitting electrochemical cell:an experimental and modelling study

    Institute of Scientific and Technical Information of China (English)

    Faleh AlTal; Jun Gao

    2017-01-01

    Light-emitting electrochemical cells(LECs) are organic photonic devices based on a mixed electronic and ionic conductor.The active layer of a polymer-based LEC consists of a luminescent polymer,an ion-solvating/transport polymer,and a compatible salt.The LEC p-n or p-i-n junction is ultimately responsible for the LEC performance.The LEC junction,however,is still poorly understood due to the difficulties of characterizing a dynamic-junction LEC.In this paper,we present an experimental and modeling study of the LEC junction using scanning optical imaging techniques.Planar LECs with an interelectrode spacing of 560μm have been fabricated,activated,frozen and scanned using a focused laser beam.The optical-beam-induced-current(OBIC)and photoluminescence(PL) data have been recorded as a function of beam location.The OBIC profile has been simulated in COMSOL that allowed for the determination of the doping concentration and the depletion width of the LEC junction.

  15. Towards room-temperature performance for lithium-polymer batteries

    International Nuclear Information System (INIS)

    Kerr, J.B.; Liu, Gao; Curtiss, L.A.; Redfern, Paul C.

    2003-01-01

    Recent work on molecular simulations of the mechanisms of lithium ion conductance has pointed towards two types of limiting process. One has involved the commonly cited segmental motion while the other is related to energy barriers in the solvation shell of polymeric ether oxygens around the lithium ions. Calculations of the barriers to lithium ion migration have provided important indicators as to the best design of the polymer. The theoretical work has coincided with and guided some recent developments on polymer synthesis for lithium batteries. Structural change of the polymer solvation shell has been pursued by the introduction of trimethylene oxide (TMO) units into the polymer. The conductivity measurements on polymers containing TMO unit are encouraging. The architecture of the polymer networks has been varied upon which the solvating groups are attached and significant improvements in sub-ambient performance are observed as a result. However, the above-ambient temperature performance appears controlled by an Arrhenius process that is not completely consistent with the theoretical calculations described here and may indicate the operation of a different mechanism. The new polymers possess significantly lower T g values in the presence of lithium salts, which indicates weaker binding of the lithium ions by the polymers. These properties provide considerable improvement in the transport properties close to the electrode surfaces resulting in decreased impedances at the surfaces both at lithium metal and in composite electrodes. The greater flexibility of the solvation groups combined with appropriate architecture not only has applications in lithium metal-polymer batteries but also in lithium ion liquid and gel systems as well as in fuel cell electrodes

  16. Zero-point energy effects in anion solvation shells.

    Science.gov (United States)

    Habershon, Scott

    2014-05-21

    By comparing classical and quantum-mechanical (path-integral-based) molecular simulations of solvated halide anions X(-) [X = F, Cl, Br and I], we identify an ion-specific quantum contribution to anion-water hydrogen-bond dynamics; this effect has not been identified in previous simulation studies. For anions such as fluoride, which strongly bind water molecules in the first solvation shell, quantum simulations exhibit hydrogen-bond dynamics nearly 40% faster than the corresponding classical results, whereas those anions which form a weakly bound solvation shell, such as iodide, exhibit a quantum effect of around 10%. This observation can be rationalized by considering the different zero-point energy (ZPE) of the water vibrational modes in the first solvation shell; for strongly binding anions, the ZPE of bound water molecules is larger, giving rise to faster dynamics in quantum simulations. These results are consistent with experimental investigations of anion-bound water vibrational and reorientational motion.

  17. Proton solvation and proton transfer in chemical and electrochemical processes

    International Nuclear Information System (INIS)

    Lengyel, S.; Conway, B.E.

    1983-01-01

    This chapter examines the proton solvation and characterization of the H 3 O + ion, proton transfer in chemical ionization processes in solution, continuous proton transfer in conductance processes, and proton transfer in electrode processes. Topics considered include the condition of the proton in solution, the molecular structure of the H 3 O + ion, thermodynamics of proton solvation, overall hydration energy of the proton, hydration of H 3 O + , deuteron solvation, partial molal entropy and volume and the entropy of proton hydration, proton solvation in alcoholic solutions, analogies to electrons in semiconductors, continuous proton transfer in conductance, definition and phenomenology of the unusual mobility of the proton in solution, solvent structure changes in relation to anomalous proton mobility, the kinetics of the proton-transfer event, theories of abnormal proton conductance, and the general theory of the contribution of transfer reactions to overall transport processes

  18. Ultrafast transient-absorption of the solvated electron in water

    International Nuclear Information System (INIS)

    Kimura, Y.; Alfano, J.C.; Walhout, P.K.; Barbara, P.F.

    1994-01-01

    Ultrafast near infrared (NIR)-pump/variable wavelength probe transient-absorption spectroscopy has been performed on the aqueous solvated electron. The photodynamics of the solvated electron excited to its p-state are qualitatively similar to previous measurements of the dynamics of photoinjected electrons at high energy. This result confirms the previous interpretation of photoinjected electron dynamics as having a rate-limiting bottleneck at low energies presumably involving the p-state

  19. Solute partitioning between the ionic liquid 1-n-butyl-3-methylimidazolium tetrafluoroborate and supercritical CO.sub.2./sub. from capillary-column chromatography

    Czech Academy of Sciences Publication Activity Database

    Planeta, Josef; Roth, Michal

    2005-01-01

    Roč. 109, č. 31 (2005), s. 15165-15171 ISSN 1520-6106 R&D Projects: GA AV ČR(CZ) KJB400310504 Institutional research plan: CEZ:AV0Z40310501 Keywords : ionic liquid - supercritical CO2 system * solute partition coefficient * linear solvation energy relationship Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 4.033, year: 2005

  20. CO2 Solubilities in Amide-based Brφnsted Acidic Ionic Liquids

    International Nuclear Information System (INIS)

    Palgunadi, Jelliarko; Im, Jin Kyu; Kang, Je Eun; Kim, Hoon Sik; Cheong, Min Serk

    2010-01-01

    A distinguished class of hydrophobic ionic liquids bearing a Brφnsted acidic character derived from amide-like compounds were prepared by a neutralization reaction of N,N-diethylformamide, N,N-dibutylformamide, 1-formylpiperidine, and ε-caprolactam with trifluoroacetic acid and physical absorptions of CO 2 in these ionic liquids were demonstrated and evaluated. CO 2 solubilities in these ionic liquids were influenced by the molecular structure of the cation and were apparently increased with the molar volume. Comparison based on a volume unit reveals that CO 2 solubilities in these liquids are relatively higher than those in imidazolium-based ionic liquids. Henry's coefficients calculated from low-pressure solubility tests at 313 to 333 K were used to derive the thermodynamics quantities. Enthalpy and entropy of solvation may share equal contributions in solubility

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

    Science.gov (United States)

    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.

  2. Estimation of abraham solvation equation coefficients for hydrogen bond formation from abraham solvation parameters for solute activity and basicity

    NARCIS (Netherlands)

    Noort, van P.C.M.

    2013-01-01

    Abraham solvation equations find widespread use in environmental chemistry and pharmaco-chemistry. The coefficients in these equations, which are solvent (system) descriptors, are usually determined by fitting experimental data. To simplify the determination of these coefficients in Abraham

  3. Communication: Thermodynamic analysis of critical conditions of polymer adsorption

    International Nuclear Information System (INIS)

    Cimino, R.; Neimark, A. V.; Rasmussen, C. J.

    2013-01-01

    Polymer adsorption to solid surfaces is a ubiquitous phenomenon, which has attracted long-lasting attention. Dependent on the competition between the polymer-solid adsorption and polymer-solvent solvation interactions, a chain may assume either 3d solvated conformation when adsorption is weak or 2d adsorbed conformation when adsorption is strong. The transition between these conformations occurring upon variation of adsorption strength is quite sharp, and in the limit of “infinite” chain length, can be treated as a critical phenomenon. We suggest a novel thermodynamic definition of the critical conditions of polymer adsorption from the equality of incremental chemical potentials of adsorbed and free chains. We show with the example of freely jointed Lennard-Jones chains tethered to an adsorbing surface that this new definition provides a link between thermodynamic and geometrical features of adsorbed chains and is in line with classical scaling relationships for the fraction of adsorbed monomers, chain radii of gyration, and free energy

  4. Communication: Thermodynamic analysis of critical conditions of polymer adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Cimino, R.; Neimark, A. V., E-mail: aneimark@rutgers.edu [Department of Chemical and Biochemical Engineering, Rutgers, The State University of New Jersey, 98 Brett Road, Piscataway, New Jersey 08854 (United States); Rasmussen, C. J. [DuPont Central Research and Development, Corporate Center for Analytical Sciences, Macromolecular Characterization, Route 141 and Henry Clay, Wilmington, Delaware 19803 (United States)

    2013-11-28

    Polymer adsorption to solid surfaces is a ubiquitous phenomenon, which has attracted long-lasting attention. Dependent on the competition between the polymer-solid adsorption and polymer-solvent solvation interactions, a chain may assume either 3d solvated conformation when adsorption is weak or 2d adsorbed conformation when adsorption is strong. The transition between these conformations occurring upon variation of adsorption strength is quite sharp, and in the limit of “infinite” chain length, can be treated as a critical phenomenon. We suggest a novel thermodynamic definition of the critical conditions of polymer adsorption from the equality of incremental chemical potentials of adsorbed and free chains. We show with the example of freely jointed Lennard-Jones chains tethered to an adsorbing surface that this new definition provides a link between thermodynamic and geometrical features of adsorbed chains and is in line with classical scaling relationships for the fraction of adsorbed monomers, chain radii of gyration, and free energy.

  5. A classical density functional theory of ionic liquids.

    Science.gov (United States)

    Forsman, Jan; Woodward, Clifford E; Trulsson, Martin

    2011-04-28

    We present a simple, classical density functional approach to the study of simple models of room temperature ionic liquids. Dispersion attractions as well as ion correlation effects and excluded volume packing are taken into account. The oligomeric structure, common to many ionic liquid molecules, is handled by a polymer density functional treatment. The theory is evaluated by comparisons with simulations, with an emphasis on the differential capacitance, an experimentally measurable quantity of significant practical interest.

  6. Aerogels from Chitosan Solutions in Ionic Liquids

    Directory of Open Access Journals (Sweden)

    Gonzalo Santos-López

    2017-12-01

    Full Text Available Chitosan aerogels conjugates the characteristics of nanostructured porous materials, i.e., extended specific surface area and nano scale porosity, with the remarkable functional properties of chitosan. Aerogels were obtained from solutions of chitosan in ionic liquids (ILs, 1-butyl-3-methylimidazolium acetate (BMIMAc, and 1-ethyl-3-methyl-imidazolium acetate (EMIMAc, in order to observe the effect of the solvent in the structural characteristics of this type of materials. The process of elaboration of aerogels comprised the formation of physical gels through anti-solvent vapor diffusion, liquid phase exchange, and supercritical CO2 drying. The aerogels maintained the chemical identity of chitosan according to Fourier transform infrared spectrophotometer (FT-IR spectroscopy, indicating the presence of their characteristic functional groups. The internal structure of the obtained aerogels appears as porous aggregated networks in microscopy images. The obtained materials have specific surface areas over 350 m2/g and can be considered mesoporous. According to swelling experiments, the chitosan aerogels could absorb between three and six times their weight of water. However, the swelling and diffusion coefficient decreased at higher temperatures. The structural characteristics of chitosan aerogels that are obtained from ionic liquids are distinctive and could be related to solvation dynamic at the initial state.

  7. Water-enhanced solvation of organics

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Jane H. [Univ. of California, Berkeley, CA (United States)

    1993-07-01

    Water-enhanced solvation (WES) was explored for Lewis acid solutes in Lewis base organic solvents, to develop cheap extract regeneration processes. WES for solid solutes was determined from ratios of solubilities of solutes in water-sat. and low-water solvent; both were determined from solid-liquid equilibrium. Vapor-headspace analysis was used to determine solute activity coefficients as function of organic phase water concentration. WES magnitudes of volatile solutes were normalized, set equal to slope of log γs vs xw/xs curve. From graph shape Δ(log γs) represents relative change in solute activity coefficient. Solutes investigated by vapor-headspace analysis were acetic acid, propionic acid, ethanol, 1,2-propylene glycol, 2,3-butylene glycol. Monocarboxylic acids had largest decrease in activity coefficient with water addition followed by glycols and alcohols. Propionic acid in cyclohexanone showed greatest water-enhancement Δ(log γacid)/Δ(xw/xacid) = -0.25. In methylcyclohexanone, the decrease of the activity coefficient of propionic acid was -0.19. Activity coefficient of propionic acid in methylcyclohexanone stopped decreasing once the water reached a 2:1 water to acid mole ratio, implying a stoichiometric relation between water, ketone, and acid. Except for 2,3-butanediol, activity coefficients of the solutes studied decreased monotonically with water content. Activity coefficient curves of ethanol, 1,2-propanediol and 2,3-butanediol did not level off at large water/solute mole ratio. Solutes investigated by solid-liquid equilibrium were citric acid, gallic acid, phenol, xylenols, 2-naphthol. Saturation concentration of citric acid in anhydrous butyl acetate increased from 0.0009 to 0.087 mol/L after 1.3 % (g/g) water co-dissolved into organic phase. Effect of water-enhanced solvation for citric acid is very large but very small for phenol and its derivatives.

  8. Ionic conducting poly-benzimidazoles; Polybenzimidazoles conducteurs ioniques

    Energy Technology Data Exchange (ETDEWEB)

    Jouanneau, J

    2006-11-15

    Over the last years, many research works have been focused on new clean energy systems. Hydrogen fuel cell seems to be the most promising one. However, the large scale development of this technology is still limited by some key elements. One of them is the polymer electrolyte membrane 'Nafion' currently used, for which the ratio performance/cost is too low. The investigations we carried out during this thesis work are related to a new class of ionic conducting polymer, the sulfonated poly-benzimidazoles (sPBI). Poly-benzimidazoles (PBI) are aromatic heterocyclic polymers well-known for their excellent thermal and chemical stability. Ionic conduction properties are obtained by having strong acid groups (sulfonic acid SO{sub 3}H) on the macromolecular structure. For that purpose, we first synthesized sulfonated monomers. Their poly-condensation with an appropriate non-sulfonated co-monomer yields to sPBI with sulfonation range from 0 to 100 per cent. Three different sPBI structures were obtained, and verified by appropriate analytical techniques. We also showed that the protocol used for the synthesis resulted in high molecular weights polymers. We prepared ionic conducting membrane by casting sPBI solutions on glass plates. Their properties of stability, water swelling and ionic conductivity were investigated. Surprisingly, the behaviour of sPBI was quite different from the other sulfonated aromatic polymers with same amount of SO{sub 3}H, their stability was much higher, but their water swelling and ionic conductivity were quite low. We attributed these differences to strong ionic interactions between the sulfonic acid groups and the basic benzimidazole groups of our polymers. However, we managed to solve this problem synthesizing very highly sulfonated PBI, obtaining membranes with a good balance between all the properties necessary. (author)

  9. Preferential solvation of single ions in mixed solvents: Part 1. New experimental approach and solvation of monovalent ions in methanol-water and acetonitrile-water mixture. Part 2. Theoretical computation and comparison with experimental data

    International Nuclear Information System (INIS)

    Rege, Aarti C.; Venkataramani, B.; Gupta, A.R.

    1999-06-01

    Preferential solvation of single ion solutions has been studied with Li + , Na + , K + and Ag +- forms of Dowex 50W resins of different cross-linkings in methanol-water and acetonitrile (AN)- water mixtures. The solvent uptake by this alkali metal ionic forms of Dowex 50W resins was studied in an isopiestic set-up using 2,4,6 and 8 m LiCl solutions in 11.0, 20.8, 44.3 and 70.2 % (w/w) methanol-water mixtures and that of Na +- and Ag +- forms using 14.6 to 94.3 % (w/w) AN - water mixtures. The solvent sorbed in the resin phase was extracted by Rayleigh-type distillation and analysed gas chromatographically. The data were analysed by the N s (mole fraction of the organic solvent in the resin phase) vs n t au (total solvent content in the resin phase) plots and separation factor, alpha(ratio of mole fraction of the solvents in the resin and solution phases) or N s vs m (molality in the resin phase) plots. The limiting values of these plots gave the composition of the solvent in the primary solvation shell around the single ion. The compositions of the primary solvation shell around Li + , Na + , and K + in methanol-water mixtures and Na + and Ag + in acetonitrile (AN) - water mixtures have been computed using Franks equation and the approach of Marcus and compared with the experimental results obtained with the above mentioned ionic forms of Dowex 50W resins in different mixed solvents. The experimental results for Li + showed good agreement with the values computed using Franks equation for all methanol-water composition. However, in the case of Na + and K + in methanol-water mixtures and Na + in AN-water mixtures, there was agreement only at lower organic solvent content and the Franks equation predicted higher values for the organic solvent in the primary solvation shell around the cation at higher organic solvent content as compared to experimental results

  10. Rheology of Supramolecular Polymers

    DEFF Research Database (Denmark)

    Shabbir, Aamir

    Supramolecular polymers are a broad class of materials that include all polymerscapable of associating via secondary interactions. These materials represent an emerging class of systems with superior versatility compared to classical polymers with applications in food stuff, coatings, cost...... efficient processes or biomedical areas. Design and development of supramolecular polymers using ionic, hydrogen bonding or transition metal complexes with tailored properties requires deep understanding of dynamics both in linear and non-linear deformations. While linear rheology is important to understand...... the dynamics under equilibrium conditions, extensional rheology is relevant during the processing or in the usage of polymers utilizing supramolecular associations for example, acrylic based pressure sensitive adhesives are subjected to extensional deformations during the peeling where strain hardening...

  11. Concentration Fluctuations and Capacitive Response in Dense Ionic Solutions.

    Science.gov (United States)

    Uralcan, Betul; Aksay, Ilhan A; Debenedetti, Pablo G; Limmer, David T

    2016-07-07

    We use molecular dynamics simulations in a constant potential ensemble to study the effects of solution composition on the electrochemical response of a double layer capacitor. We find that the capacitance first increases with ion concentration following its expected ideal solution behavior but decreases upon approaching a pure ionic liquid in agreement with recent experimental observations. The nonmonotonic behavior of the capacitance as a function of ion concentration results from the competition between the independent motion of solvated ions in the dilute regime and solvation fluctuations in the concentrated regime. Mirroring the capacitance, we find that the characteristic decay length of charge density correlations away from the electrode is also nonmonotonic. The correlation length first decreases with ion concentration as a result of better electrostatic screening but increases with ion concentration as a result of enhanced steric interactions. When charge fluctuations induced by correlated ion-solvent fluctuations are large relative to those induced by the pure ionic liquid, such capacitive behavior is expected to be generic.

  12. (Liquid + liquid) equilibria of perfluorocarbons with fluorinated ionic liquids

    International Nuclear Information System (INIS)

    Martinho, S.; Araújo, J.M.M.; Rebelo, L.P.N.; Pereiro, A.B.; Marrucho, I.M.

    2013-01-01

    Highlights: • (Liquid + liquid) equilibria perfluorocarbons and fluorinated ionic liquids. • Non-Random Two Liquid model was successfully applied. • Thermodynamic functions that describe the solvation process were calculated. -- Abstract: In order to evaluate the feasibility of partially replace perfluorocarbons (PFCs) with fluorinated ionic liquids (FILs) in PFCs-in-water emulsions, usually used for biomedical purposes, herein the (liquid + liquid) phase equilibria of FILs containing fluorinated chains longer than four carbons with PFCs were carried out in a wide range of temperatures. With this goal in mind, two PFCs (perfluorooctane and perfluorodecalin) were selected and the (liquid + liquid) equilibria of the binary mixtures of these PFCs and FILs were studied at atmospheric pressure in a temperature range from T (293.15 to 343.15) K. For these studies, FILs containing ammonium, pyridinium and imidazolium cations and different anions with fluorocarbon alkyl chains between 4 and 8 were included. Additionally, Non-Random Two Liquid (NRTL) thermodynamic model was successfully applied to correlate the behaviour of the PFCs + FILs binary mixtures. Moreover, thermodynamic functions that describe the solvation process were calculated from the experimental data

  13. Theoretical studies of ionic conductivity of crosslinked chitosan membranes

    Energy Technology Data Exchange (ETDEWEB)

    Chavez, Ernesto Lopez [Programa de Ingenieria Molecular y Nuevos Materiales, Universidad Autonoma de la Ciudad de Mexico, Fray Servando Teresa de Mier 92, 1er. Piso, Col Centro, Mexico D.F. CP 06080 (Mexico); Oviedo-Roa, R.; Contreras-Perez, Gustavo; Martinez-Magadan, Jose Manuel [Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas Norte 152, Col. San Bartolo Atepehuacan, CP 07730 Mexico D.F. (Mexico); Castillo-Alvarado, F.L. [Escuela Superior de Fisica y Matematicas del Instituto Politecnico Nacional, Edificio 9 de la UPALM, Colonia Lindavista, Mexico D.F. CP 07738 (Mexico)

    2010-11-15

    Ionic conductivity of crosslinked chitosan membranes was studied using techniques of molecular modeling and simulation. The COMPASS force field was used. The simulation allows the description of the mechanism of ionic conductivity along the polymer matrix. The theoretical results obtained are compared with experimental results for chitosan membranes. The analysis suggests that the conduction mechanism is portrayed by the overlapping large Polaron tunneling model. In addition, when the chitosan membrane was crosslinked with an appropriate degree of crosslinking its ionic conductivity, at room temperature, was increased by about one order of magnitude. The chitosan membranes can be used as electrolytes in solid state batteries, electric double layer capacitors and fuel cells. (author)

  14. Polymer electrolytes—Some principles, cautions, and new practices

    International Nuclear Information System (INIS)

    Angell, C. Austen

    2017-01-01

    We give a short review of the basics of ionic dynamics in simple ionic liquids and their solutions (liquid fragility, conductivity-viscosity relations, limiting high conductivity, decoupling of conductivity from viscosity, conductivity maxima in solutions, and ionicity), and then summarize how these conceptual underpinnings must change when the ionic liquid becomes an ionic polymer or salt-in- polymer solution − the field of polymer electrolytes. We discuss the generation of rubbery plateaus, segmental relaxation and its control of thermodynamics, ionicity, and gelation), and revisit some of the key equations needed to provide quantitative accounts of the observed behavior. Finally we describe two alternative approaches to preparing flexible solid electrolytes, both higher-dimensional and one of them all-inorganic.

  15. Depleted depletion drives polymer swelling in poor solvent mixtures.

    Science.gov (United States)

    Mukherji, Debashish; Marques, Carlos M; Stuehn, Torsten; Kremer, Kurt

    2017-11-09

    Establishing a link between macromolecular conformation and microscopic interaction is a key to understand properties of polymer solutions and for designing technologically relevant "smart" polymers. Here, polymer solvation in solvent mixtures strike as paradoxical phenomena. For example, when adding polymers to a solvent, such that all particle interactions are repulsive, polymer chains can collapse due to increased monomer-solvent repulsion. This depletion induced monomer-monomer attraction is well known from colloidal stability. A typical example is poly(methyl methacrylate) (PMMA) in water or small alcohols. While polymer collapse in a single poor solvent is well understood, the observed polymer swelling in mixtures of two repulsive solvents is surprising. By combining simulations and theoretical concepts known from polymer physics and colloidal science, we unveil the microscopic, generic origin of this collapse-swelling-collapse behavior. We show that this phenomenon naturally emerges at constant pressure when an appropriate balance of entropically driven depletion interactions is achieved.

  16. Counterion-induced swelling of ionic microgels

    Science.gov (United States)

    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.

  17. Fullerol ionic fluids

    Science.gov (United States)

    Fernandes, Nikhil; Dallas, Panagiotis; Rodriguez, Robert; Bourlinos, Athanasios B.; Georgakilas, Vasilios; Giannelis, Emmanuel P.

    2010-09-01

    We report for the first time an ionic fluid based on hydroxylated fullerenes (fullerols). The ionic fluid was synthesized by neutralizing the fully protonated fullerol with an amine terminated polyethylene/polypropylene oxide oligomer (Jeffamine®). The ionic fluid was compared to a control synthesized by mixing the partially protonated form (sodium form) of the fullerols with the same oligomeric amine in the same ratio as in the ionic fluids (20 wt% fullerol). In the fullerol fluid the ionic bonding significantly perturbs the thermal transitions and melting/crystallization behavior of the amine. In contrast, both the normalized heat of fusion and crystallization of the amine in the control are similar to those of the neat amine consistent with a physical mixture of the fullerols/amine with minimal interactions. In addition to differences in thermal behavior, the fullerol ionic fluid exhibits a complex viscoelastic behavior intermediate between the neat Jeffamine® (liquid-like) and the control (solid-like).

  18. Nanoscale Ionic Liquids

    Science.gov (United States)

    2006-11-01

    Technical Report 11 December 2005 - 30 November 2006 4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER Nanoscale Ionic Liquids 5b. GRANT NUMBER FA9550-06-1-0012...Title: Nanoscale Ionic Liquids Principal Investigator: Emmanuel P. Giannelis Address: Materials Science and Engineering, Bard Hall, Cornell University...based fluids exhibit high ionic conductivity. The NFs are typically synthesized by grafting a charged, oligomeric corona onto the nanoparticle cores

  19. Cluster expansion of the solvation free energy difference: Systematic improvements in the solvation of single ions

    Science.gov (United States)

    Pliego, Josefredo R.

    2017-07-01

    The cluster expansion method has been used in the imperfect gas theory for several decades. This paper proposes a cluster expansion of the solvation free energy difference. This difference, which results from a change in the solute-solvent potential energy, can be written as the logarithm of a finite series. Similar to the Mayer function, the terms in the series are related to configurational integrals, which makes the integrand relevant only for configurations of the solvent molecules close to the solute. In addition, the terms involve interaction of solute with one, two, and so on solvent molecules. The approach could be used for hybrid quantum mechanical and molecular mechanics methods or mixed cluster-continuum approximation. A simple form of the theory was applied for prediction of pKa in methanol; the results indicated that three explicit methanol molecules and the dielectric continuum lead to a root of mean squared error (RMSE) of only 1.3 pKa units, whereas the pure continuum solvation model based on density method leads to a RMSE of 6.6 pKa units.

  20. Pulse radiolysis study of the intermediates formed in ionic liquids. Intermediate spectra in the p-terphenyl solution in the ionic liquid methyltributylammonium bis[(trifluoromethyl)sulfonyl]imide

    International Nuclear Information System (INIS)

    Grodkowski, J.; Kocia, R.; Mirkowski, J.

    2006-01-01

    Room temperature ionic liquids (Il) are non-volatile,and non-flammable and serve as good solvents for various reactions, mainly for g reen processing . To understand the effect of these solvents on the chemical reactions, the rate constants of several elementary reactions in ionic liquids have been studied by the pulse radiolysis technique. In this study, the formation of intermediates derived from p-terphenyl (Tp) in the ionic liquid methyl tributylammonium bis[(trifluoromethyl)sulfonyl] imide (R 4 NNTf 2 ) solutions have been studied by pulse radiolysis as a part of broader studies concerning CO 2 reduction. The registered spectra can be explained by CO 2 reaction with solvated and dry electrons thus eliminating one path of TP ·- formation. Some TP ·- are formed by reaction of excited TP *- states with Tea. Direct reactions involving Tp, TP ·- , CO 2 and CO 2 ·- are too slow to be observed in pulse radiolysis time scale

  1. Order and correlation contributions to the entropy of hydrophobic solvation

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Maoyuan; Besford, Quinn Alexander; Mulvaney, Thomas; Gray-Weale, Angus, E-mail: gusgw@gusgw.net [School of Chemistry, The University of Melbourne, Victoria 3010 (Australia)

    2015-03-21

    The entropy of hydrophobic solvation has been explained as the result of ordered solvation structures, of hydrogen bonds, of the small size of the water molecule, of dispersion forces, and of solvent density fluctuations. We report a new approach to the calculation of the entropy of hydrophobic solvation, along with tests of and comparisons to several other methods. The methods are assessed in the light of the available thermodynamic and spectroscopic information on the effects of temperature on hydrophobic solvation. Five model hydrophobes in SPC/E water give benchmark solvation entropies via Widom’s test-particle insertion method, and other methods and models are tested against these particle-insertion results. Entropies associated with distributions of tetrahedral order, of electric field, and of solvent dipole orientations are examined. We find these contributions are small compared to the benchmark particle-insertion entropy. Competitive with or better than other theories in accuracy, but with no free parameters, is the new estimate of the entropy contributed by correlations between dipole moments. Dipole correlations account for most of the hydrophobic solvation entropy for all models studied and capture the distinctive temperature dependence seen in thermodynamic and spectroscopic experiments. Entropies based on pair and many-body correlations in number density approach the correct magnitudes but fail to describe temperature and size dependences, respectively. Hydrogen-bond definitions and free energies that best reproduce entropies from simulations are reported, but it is difficult to choose one hydrogen bond model that fits a variety of experiments. The use of information theory, scaled-particle theory, and related methods is discussed briefly. Our results provide a test of the Frank-Evans hypothesis that the negative solvation entropy is due to structured water near the solute, complement the spectroscopic detection of that solvation structure by

  2. Characterization of polymer-type ionic conductors using nuclear magnetic resonance and thermal analysis. Humidity sensor; Caracterizacao de condutores ionicos de tipo polimerico por ressonancia magnetica nuclear (RMN) e analises termicas. Sensor de umidade

    Energy Technology Data Exchange (ETDEWEB)

    Cavalcante, Maria Goretti

    1992-04-01

    We report a study using Nuclear Magnetic Resonance (NMR), Thermogravimetry Analysis, Differential Scanning Calorimetry and Infrared Spectroscopy in polymeric complexes formed poly(ethylene oxide), (PEO), and lithium salts. These complexes have have shown a large potential for technological applications in batteries, sensors, etc. We developed and characterized humidity sensors and discussed how the humidity affects the conformation of the complexes, the mobility of ionic species, and the polymeric chains. The results indicate that the hydration affects the conformation of polymeric complexes by plasticizing the water, which induces a volumetric expansion in the PEO chain. The processes was completely reversible for the level of hydration studied. NMR was used to distinguish the movement of polymeric chains from the movement of the ionic species. From the analysis of the second moment of resonance lines from the study of the nuclear relaxation we were able to estimate the average distance between the ionic species and the proton in the complexes chains. The behaviour of spin -lattice relaxation of hydrogen and fluorine in the P(EO) - Li B F, as a function of temperature and frequency reflects the nature of the disorder and the complexity of the ionic conduction process in these materials. (author). 91 refs., 69 figs., 2 tabs.

  3. Standard electrode potential, Tafel equation, and the solvation thermodynamics.

    Science.gov (United States)

    Matyushov, Dmitry V

    2009-06-21

    Equilibrium in the electronic subsystem across the solution-metal interface is considered to connect the standard electrode potential to the statistics of localized electronic states in solution. We argue that a correct derivation of the Nernst equation for the electrode potential requires a careful separation of the relevant time scales. An equation for the standard metal potential is derived linking it to the thermodynamics of solvation. The Anderson-Newns model for electronic delocalization between the solution and the electrode is combined with a bilinear model of solute-solvent coupling introducing nonlinear solvation into the theory of heterogeneous electron transfer. We therefore are capable of addressing the question of how nonlinear solvation affects electrochemical observables. The transfer coefficient of electrode kinetics is shown to be equal to the derivative of the free energy, or generalized force, required to shift the unoccupied electronic level in the bulk. The transfer coefficient thus directly quantifies the extent of nonlinear solvation of the redox couple. The current model allows the transfer coefficient to deviate from the value of 0.5 of the linear solvation models at zero electrode overpotential. The electrode current curves become asymmetric in respect to the change in the sign of the electrode overpotential.

  4. Solvation structures of lithium halides in methanol–water mixtures

    International Nuclear Information System (INIS)

    Sarkar, Atanu; Dixit, Mayank Kumar; Tembe, B.L.

    2015-01-01

    Highlights: • Potentials of mean force for Li + -halides are calculated in methanol–water mixtures. • Stable CIP for x methanol = 1.0 becomes unstable at and below x methanol = 0.75. • The Li + ion is preferentially solvated by methanol molecules. • The halide ions are preferentially solvated by water molecules. - Abstract: The potentials of mean force (PMFs) for the ion pairs, Li + −Cl − , Li + −Br − and Li + −I − have been calculated in five methanol–water compositions. The results obtained are verified by trailing the trajectories and calculating the ion pair distance residence times. Local structures around the ions are studied using the radial distribution functions, density profiles, orientational correlation functions, running coordination numbers and excess coordination numbers. The major change in PMF is observed as the methanol mole fraction (x methanol ) is changed from 1.0 to 0.75. The stable contact ion pair occurring for x methanol = 1.0 becomes unstable at and below x methanol = 0.75. The preferential solvation data show that the halide ions are always preferentially solvated by water molecules. Although the lithium ion is preferentially solvated by methanol molecules, there is significant affinity towards water molecules as well

  5. Vibrational spectroscopy of bare and solvated ionic complexes of biological relevance

    NARCIS (Netherlands)

    Polfer, N. C.; Oomens, J.

    2009-01-01

    The low density of ions in mass spectrometers generally precludes direct infrared (IR) absorption measurements. The IR spectrum of an ion can nonetheless be obtained by inducing photodissociation of the ion using a high-intensity tunable laser The emergence of free electron lasers (FELs) and recent

  6. Semiconductor nanocrystals dispersed in imidazolium-based ionic liquids: a spectroscopic and morphological investigation

    International Nuclear Information System (INIS)

    Panniello, Annamaria; Binetti, Enrico; Ingrosso, Chiara; Curri, M. Lucia; Agostiano, Angela; Tommasi, Raffaele; Striccoli, Marinella

    2013-01-01

    A growing interest is devoted to the study of imidazolium-based ionic liquids as innovative materials to combine with functional elements for advanced technological applications. Materials based on semiconductor and oxide nanocrystals in ionic liquids can be promising for their integration in lithium batteries, as well as in innovative solar cells. Although the physical chemical properties and the solvation dynamics of bare ionic liquids have been extensively studied, their combination with colloidal nanocrystals still remains almost unexplored. Here, the optical properties of organic-capped luminescent cadmium selenide nanocrystals coated by a shell of zinc sulfide (CdSe(ZnS)) dispersed in 1,3-dialkyl imidazolium ionic liquids have been investigated, also in dependence of the alkyl chain length on the imidazolium ring and of the anion nature, by using both time-integrated and time-resolved optical spectroscopy. The observed variations in decay profiles of the ionic liquid in presence of colloidal nanocrystals suggest that the dispersion of the nanostructures induces modifications in the ionic liquid structural order. Finally, atomic force microscopy analysis has provided insight into the topography of the investigated dispersions deposited as film, confirming the organization of the ionic liquids in super-structures, also upon nanocrystal incorporation.

  7. Difference rule-a new thermodynamic principle: prediction of standard thermodynamic data for inorganic solvates.

    Science.gov (United States)

    Jenkins, H Donald Brooke; Glasser, Leslie

    2004-12-08

    We present a quite general thermodynamic "difference" rule, derived from thermochemical first principles, quantifying the difference between the standard thermodynamic properties, P, of a solid n-solvate (or n-hydrate), n-S, containing n molecules of solvate, S (water or other) and the corresponding solid parent (unsolvated) salt: [P[n-solvate] - P[parent

  8. Water Evaporation and Conformational Changes from Partially Solvated Ubiquitin

    Directory of Open Access Journals (Sweden)

    Saravana Prakash Thirumuruganandham

    2010-01-01

    Full Text Available Using molecular dynamics simulation, we study the evaporation of water molecules off partially solvated ubiquitin. The evaporation and cooling rates are determined for a molecule at the initial temperature of 300 K. The cooling rate is found to be around 3 K/ns, and decreases with water temperature in the course of the evaporation. The conformation changes are monitored by studying a variety of intermediate partially solvated ubiquitin structures. We find that ubiquitin shrinks with decreasing hydration shell and exposes more of its hydrophilic surface area to the surrounding.

  9. Dipole moments of molecules solvated in helium nanodroplets

    International Nuclear Information System (INIS)

    Stiles, Paul L.; Nauta, Klaas; Miller, Roger E.

    2003-01-01

    Stark spectra are reported for hydrogen cyanide and cyanoacetylene solvated in helium nanodroplets. The goal of this study is to understand the influence of the helium solvent on measurements of the permanent electric dipole moment of a molecule. We find that the dipole moments of the helium solvated molecules, calculated assuming the electric field is the same as in vacuum, are slightly smaller than the well-known gas-phase dipole moments of HCN and HCCCN. A simple elliptical cavity model quantitatively accounts for this difference, which arises from the dipole-induced polarization of the helium

  10. Polymer films

    Science.gov (United States)

    Granick, Steve; Sukhishvili, Svetlana A.

    2004-05-25

    A film contains a first polymer having a plurality of hydrogen bond donating moieties, and a second polymer having a plurality of hydrogen bond accepting moieties. The second polymer is hydrogen bonded to the first polymer.

  11. Differential geometry based solvation model II: Lagrangian formulation.

    Science.gov (United States)

    Chen, Zhan; Baker, Nathan A; Wei, G W

    2011-12-01

    Solvation is an elementary process in nature and is of paramount importance to more sophisticated chemical, biological and biomolecular processes. The understanding of solvation is an essential prerequisite for the quantitative description and analysis of biomolecular systems. This work presents a Lagrangian formulation of our differential geometry based solvation models. The Lagrangian representation of biomolecular surfaces has a few utilities/advantages. First, it provides an essential basis for biomolecular visualization, surface electrostatic potential map and visual perception of biomolecules. Additionally, it is consistent with the conventional setting of implicit solvent theories and thus, many existing theoretical algorithms and computational software packages can be directly employed. Finally, the Lagrangian representation does not need to resort to artificially enlarged van der Waals radii as often required by the Eulerian representation in solvation analysis. The main goal of the present work is to analyze the connection, similarity and difference between the Eulerian and Lagrangian formalisms of the solvation model. Such analysis is important to the understanding of the differential geometry based solvation model. The present model extends the scaled particle theory of nonpolar solvation model with a solvent-solute interaction potential. The nonpolar solvation model is completed with a Poisson-Boltzmann (PB) theory based polar solvation model. The differential geometry theory of surfaces is employed to provide a natural description of solvent-solute interfaces. The optimization of the total free energy functional, which encompasses the polar and nonpolar contributions, leads to coupled potential driven geometric flow and PB equations. Due to the development of singularities and nonsmooth manifolds in the Lagrangian representation, the resulting potential-driven geometric flow equation is embedded into the Eulerian representation for the purpose of

  12. Ionic conductivity and diffusion coefficient of barium-chloride-based ...

    Indian Academy of Sciences (India)

    2017-07-26

    Jul 26, 2017 ... the present research is to reveal the effect of BaCl2 on the ionic conductivity ... pared polymer electrolyte was recorded and energy band gap was evaluated from ... The XRD analysis is useful to determine the structural and.

  13. Shape-Memory Behavior of Polylactide/Silica Ionic Hybrids

    KAUST Repository

    Odent, Jérémy

    2017-03-27

    Commercial polylactide (PLA) was converted and endowed with shape-memory properties by synthesizing ionic hybrids based on blends of PLA with imidazolium-terminated PLA and poly[ε-caprolactone-co-d,l-lactide] (P[CL-co-LA]) and surface-modified silica nanoparticles. The electrostatic interactions assist with the silica nanoparticle dispersion in the polymer matrix. Since nanoparticle dispersion in polymers is a perennial challenge and has prevented nanocomposites from reaching their full potential in terms of performance we expect this new design will be exploited in other polymers systems to synthesize well-dispersed nanocomposites. Rheological measurements of the ionic hybrids are consistent with the formation of a network. The ionic hybrids are also much more deformable compared to the neat PLA. More importantly, they exhibit shape-memory behavior with fixity ratio Rf ≈ 100% and recovery ratio Rr = 79%, for the blend containing 25 wt % im-PLA and 25 wt % im-P[CL-co-LA] and 5 wt % of SiO2–SO3Na. Dielectric spectroscopy and dynamic mechanical analysis show a second, low-frequency relaxation attributed to strongly immobilized polymer chains on silica due to electrostatic interactions. Creep compliance tests further suggest that the ionic interactions prevent permanent slippage in the hybrids which is most likely responsible for the significant shape-memory behavior observed.

  14. Shape-Memory Behavior of Polylactide/Silica Ionic Hybrids

    KAUST Repository

    Odent, Jé ré my; Raquez, Jean-Marie; Samuel, Cé dric; Barrau, Sophie; Enotiadis, Apostolos; Dubois, Philippe; Giannelis, Emmanuel P.

    2017-01-01

    Commercial polylactide (PLA) was converted and endowed with shape-memory properties by synthesizing ionic hybrids based on blends of PLA with imidazolium-terminated PLA and poly[ε-caprolactone-co-d,l-lactide] (P[CL-co-LA]) and surface-modified silica nanoparticles. The electrostatic interactions assist with the silica nanoparticle dispersion in the polymer matrix. Since nanoparticle dispersion in polymers is a perennial challenge and has prevented nanocomposites from reaching their full potential in terms of performance we expect this new design will be exploited in other polymers systems to synthesize well-dispersed nanocomposites. Rheological measurements of the ionic hybrids are consistent with the formation of a network. The ionic hybrids are also much more deformable compared to the neat PLA. More importantly, they exhibit shape-memory behavior with fixity ratio Rf ≈ 100% and recovery ratio Rr = 79%, for the blend containing 25 wt % im-PLA and 25 wt % im-P[CL-co-LA] and 5 wt % of SiO2–SO3Na. Dielectric spectroscopy and dynamic mechanical analysis show a second, low-frequency relaxation attributed to strongly immobilized polymer chains on silica due to electrostatic interactions. Creep compliance tests further suggest that the ionic interactions prevent permanent slippage in the hybrids which is most likely responsible for the significant shape-memory behavior observed.

  15. Effect of plasticizer and fumed silica on ionic conductivity behaviour

    Indian Academy of Sciences (India)

    The effect of addition of propylene carbonate (PC) and nano-sized fumed silica on the ionic conductivity behaviour of proton conducting polymer electrolytes containing different concentrations of hexafluorophosphoric acid (HPF6) in polyethylene oxide (PEO) has been studied. The addition of PC results in an increase in ...

  16. Amphiphile Meets Amphiphile: Beyond the Polar-Apolar Dualism in Ionic Liquid/Alcohol Mixtures.

    Science.gov (United States)

    Russina, Olga; Sferrazza, Alessio; Caminiti, Ruggero; Triolo, Alessandro

    2014-05-15

    The mesoscopic morphology of binary mixtures of ethylammonium nitrate (EAN), the protic ionic liquid par excellence, and methanol is explored using neutron/X-ray diffraction and computational techniques. Both compounds are amphiphilic and characterized by an extended hydrogen bonding network: surprisingly, though macroscopically homogeneous, these mixtures turn out to be mesoscopically highly heterogeneous. Our study reveals that even in methanol-rich mixtures, a wide distribution of clusters exists where EAN preserves its bulk, sponge-like morphology. Accordingly methanol does not succeed in fully dissociating the ionic liquid that keeps on organizing in a bulk-like fashion. This behavior represents the premises to the more dramatic phenomenology observed with longer alcohols that eventually phase separate from EAN. These results challenge the commonly accepted polar and apolar moieties segregation in ionic liquids/molecular liquids mixtures and the current understanding of technologically relevant solvation processes.

  17. Investigation of a nanoconfined, ceramic composite, solid polymer electrolyte

    International Nuclear Information System (INIS)

    Jayasekara, Indumini; Poyner, Mark; Teeters, Dale

    2017-01-01

    The challenges for further development of lithium rechargeable batteries are finding electrolyte materials that are safe, have mechanical and thermal stability and have sufficiently high ionic conduction. Polymer electrolytes have many of these advantages, but suffer with low ionic conduction. This study involves the use of anodic aluminum oxide (AAO) membranes having nanochannels filled with polymer electrolyte to make composite solid electrolytes having ionic conductivity several orders of magnitude higher (10 −4 Ω ‐1 cm −1 ) than non-confined polymer. SEM, ac impedance spectroscopy, temperature dependence studies, XRD, ATR- FTIR and DSC studies were done in order to characterize and understand the behavior of nanoconfined polymer electrolytes. The composite polymer electrolyte was found to be more amorphous with polymer chains aligned in the direction of the nanochannels, which is felt to promote ion conduction. The electrolyte systems, confined in nanoporous membranes, can be used as electrolytes for the fabrication of a room temperature all solid state battery.

  18. Ionic liquids as electrolytes

    International Nuclear Information System (INIS)

    Galinski, Maciej; Lewandowski, Andrzej; Stepniak, Izabela

    2006-01-01

    Salts having a low melting point are liquid at room temperature, or even below, and form a new class of liquids usually called room temperature ionic liquids (RTIL). Information about RTILs can be found in the literature with such key words as: room temperature molten salt, low-temperature molten salt, ambient-temperature molten salt, liquid organic salt or simply ionic liquid. Their physicochemical properties are the same as high temperature ionic liquids, but the practical aspects of their maintenance or handling are different enough to merit a distinction. The class of ionic liquids, based on tetraalkylammonium cation and chloroaluminate anion, has been extensively studied since late 1970s of the XX century, following the works of Osteryoung. Systematic research on the application of chloroaluminate ionic liquids as solvents was performed in 1980s. However, ionic liquids based on aluminium halides are moisture sensitive. During the last decade an increasing number of new ionic liquids have been prepared and used as solvents. The general aim of this paper was to review the physical and chemical properties of RTILs from the point of view of their possible application as electrolytes in electrochemical processes and devices. The following points are discussed: melting and freezing, conductivity, viscosity, temperature dependence of conductivity, transport and transference numbers, electrochemical stability, possible application in aluminium electroplating, lithium batteries and in electrochemical capacitors

  19. Canopy Dynamics in Nanoscale Ionic Materials Probed by NMR

    Science.gov (United States)

    Mirau, Peter

    2013-03-01

    Nanoscale ionic materials (NIMs) are hybrids prepared from ionically functionalized nanoparticles (NP) neutralized by oligomeric polymer counter-ions. NIMs are designed to behave as liquids under ambient conditions in the absence of solvent and have no volatile organic content, making them useful for a number of applications. We have used NMR relaxation and pulse-field gradient NMR to probe local and collective canopy dynamics in NIMs based on silica nanoparticles (NP), fullerols and proteins in order to understand the relationship between the core and canopy structure and the bulk properties. The NMR studies show that the canopy dynamics depend on the degree of neutralization, the canopy radius of gyration and molecular crowding at the ionically modified NP surface. The viscosity in NIMs can be directly controlled with the addition of ions that enhance the exchange rate for polymers at the NP surface. These results show that NIMs for many applications can be prepared by controlling the dynamics of the NP interface.

  20. SIRAH: a structurally unbiased coarse-grained force field for proteins with aqueous solvation and long-range electrostatics.

    Science.gov (United States)

    Darré, Leonardo; Machado, Matías Rodrigo; Brandner, Astrid Febe; González, Humberto Carlos; Ferreira, Sebastián; Pantano, Sergio

    2015-02-10

    Modeling of macromolecular structures and interactions represents an important challenge for computational biology, involving different time and length scales. However, this task can be facilitated through the use of coarse-grained (CG) models, which reduce the number of degrees of freedom and allow efficient exploration of complex conformational spaces. This article presents a new CG protein model named SIRAH, developed to work with explicit solvent and to capture sequence, temperature, and ionic strength effects in a topologically unbiased manner. SIRAH is implemented in GROMACS, and interactions are calculated using a standard pairwise Hamiltonian for classical molecular dynamics simulations. We present a set of simulations that test the capability of SIRAH to produce a qualitatively correct solvation on different amino acids, hydrophilic/hydrophobic interactions, and long-range electrostatic recognition leading to spontaneous association of unstructured peptides and stable structures of single polypeptides and protein-protein complexes.

  1. Thermodynamics of solvation and solvophobic effect in formamide

    International Nuclear Information System (INIS)

    Sedov, I.A.; Stolov, M.A.; Solomonov, B.N.

    2013-01-01

    Highlights: • Enthalpies of solution of apolar organic compounds in formamide were measured. • Gibbs free energies of solution were experimentally determined. • Influence of the solvophobic effect on solvation thermodynamics was studied. • Thermodynamic features of solutions in formamide resemble those of aqueous solutions. -- Abstract: Using semi-adiabatic calorimetry, we measured the enthalpies of solution for various low-polar compounds including alkanes, aromatic hydrocarbons and their halogenated derivatives in formamide at temperature of 298 K. For the same compounds, the values of limiting activity coefficients in formamide were determined using GC headspace analysis at 298 K, and Gibbs free energies of solution and solvation were calculated. Based on these data and the available literature values of the Gibbs free energy of solvation in formamide for a number of other low-polar solutes, a study of the solvophobic effect in this solvent is performed, and its resemblance to the hydrophobic effect in aqueous solutions is demonstrated. It is shown that the contribution of the solvophobic effect into the solvation Gibbs free energy in formamide is much higher than that in aliphatic alcohols, but lower than that in water. Like in water, the magnitude of this contribution for different solutes linearly increases with the solute molecular volume. Solvophobic effect also significantly affects the enthalpies of dissolution in formamide, causing them to be more negative in the case of alkanes and more positive in the case of arenes

  2. Isotope effect in enthalpy of solvation of the lithium ion

    International Nuclear Information System (INIS)

    Krestov, G.A.; Egorov, G.I.; Korolev, V.P.

    1989-01-01

    At 298.15 K, the authors determined the standard enthalpies of solution for 6 LiCl and 7 LiCl in water, heavy water, dimethylsulfoxide (DMSO) and aqueous solutions of DMSO. The authors have established that solvation of 6 Li + is differentiated in water and DMSO to a greater degree than for 7 Li +

  3. The solvation of carbohydrates in dimethylsulfoxide and water

    International Nuclear Information System (INIS)

    Berger, S.; Diaz, M.D.; Horwat, Ch.

    1999-01-01

    The solvation of sucrose and other carbohydrates in DMSO and water is probed by intermolecular NOE measurements. The NOE effects are interpreted in terms of specific binding of the solvent to certain sites of the molecules. It is shown that DMSO attaches to specific sites of the sucrose molecule, whereas for water such a clear differentiation cannot be proven. (author)

  4. Microscopic picture of the aqueous solvation of glutamic acid

    NARCIS (Netherlands)

    Leenders, E.J.M.; Bolhuis, P.G.; Meijer, E.J.

    2008-01-01

    We present molecular dynamics simulations of glutamic acid and glutamate solvated in water, using both density functional theory (DFT) and the Gromos96 force field. We focus on the microscopic aspects of the solvation−particularly on the hydrogen bond structures and dynamics−and investigate the

  5. On the coupling between molecular diffusion and solvation shell exchange

    DEFF Research Database (Denmark)

    Møller, Klaus Braagaard; Rey, Rossend; Masia, Marco

    2005-01-01

    The connection between diffusion and solvent exchanges between first and second solvation shells is studied by means of molecular dynamics simulations and analytic calculations, with detailed illustrations for water exchange for the Li+ and Na+ ions, and for liquid argon. First, two methods...

  6. Comparison between implicit and hybrid solvation methods for the ...

    Indian Academy of Sciences (India)

    Administrator

    Both implicit solvation method (dielectric polarizable continuum model, DPCM) and hybrid ... the free energy change (ΔGsol) as per the PCM ... Here the gas phase change is written as ΔGg = ΔEelec + ..... bution to the field of electrochemistry.

  7. Polarizability and Aqueous Solvation of the Sulfate Dianion

    Czech Academy of Sciences Publication Activity Database

    Jungwirth, Pavel; Curtis, J. E.; Tobias, D. J.

    2003-01-01

    Roč. 367, - (2003), s. 704-710 ISSN 0009-2614 R&D Projects: GA MŠk LN00A032 Institutional research plan: CEZ:AV0Z4040901 Keywords : polarizability * aqueous solvation * dianion Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.438, year: 2003

  8. Fundamental radiation effect on polymers energy transfer from radiation to polymer

    International Nuclear Information System (INIS)

    Seguchi, T.

    2007-01-01

    Polymer modification as cross-link, chain scission, and graft-polymerization by radiation is initiated by the quantum energy transferred from radiation to polymers. The active species for chemical reactions are produced through ionization or activation of polymer molecules for any radiation source. The energy transfer occurs mainly by ionic interaction between radiation and polymer molecule, and the contribution from the collision interaction is miner. The radiation of electromagnetic wave as X-ray or γ-ray generates the energetic electron which induces ionic interaction with polymer molecule. The energy loss profile along the penetration to polymer material is much different among the radiation sources of EB, γ-ray, and ion beams in the macroscopic mechanism. In this article, the behavior of single event, that is, the event induced by one electron, γ-ray, ion, and neutron is described by the macroscopic mechanism and by the microscopic mechanism. (authors)

  9. Ionic Liquids in Tribology

    Directory of Open Access Journals (Sweden)

    Ichiro Minami

    2009-06-01

    Full Text Available Current research on room-temperature ionic liquids as lubricants is described. Ionic liquids possess excellent properties such as non-volatility, non-flammability, and thermo-oxidative stability. The potential use of ionic liquids as lubricants was first proposed in 2001 and approximately 70 articles pertaining to fundamental research on ionic liquids have been published through May 2009. A large majority of the cations examined in this area are derived from 1,3-dialkylimidazolium, with a higher alkyl group on the imidazolium cation being beneficial for good lubrication, while it reduces the thermo-oxidative stability. Hydrophobic anions provide both good lubricity and significant thermo-oxidative stability. The anions decompose through a tribochemical reaction to generate metal fluoride on the rubbed surface. Additive technology to improve lubricity is also explained. An introduction to tribology as an interdisciplinary field of lubrication is also provided.

  10. Ionic liquids in tribology.

    Science.gov (United States)

    Minami, Ichiro

    2009-06-24

    Current research on room-temperature ionic liquids as lubricants is described. Ionic liquids possess excellent properties such as non-volatility, non-flammability, and thermo-oxidative stability. The potential use of ionic liquids as lubricants was first proposed in 2001 and approximately 70 articles pertaining to fundamental research on ionic liquids have been published through May 2009. A large majority of the cations examined in this area are derived from 1,3-dialkylimidazolium, with a higher alkyl group on the imidazolium cation being beneficial for good lubrication, while it reduces the thermo-oxidative stability. Hydrophobic anions provide both good lubricity and significant thermo-oxidative stability. The anions decompose through a tribochemical reaction to generate metal fluoride on the rubbed surface. Additive technology to improve lubricity is also explained. An introduction to tribology as an interdisciplinary field of lubrication is also provided.

  11. Photophysics of ionic biochromophores

    CERN Document Server

    Brøndsted Nielsen, Steen

    2014-01-01

    This concise guide to studying ionic biochromophores features the first integrated overview of the photophysics of differing classes of biomolecules, from single amino acids to DNA. It includes an appraisal of the latest theories and experimental techniques.

  12. Radiation induced polymerization of MMA in imidazolium ionic liquids and their mixed solutions with organic solvents

    Energy Technology Data Exchange (ETDEWEB)

    Qi Mingying [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, P.O. Box 800-204, Shanghai 201800 (China); Graduate University of the Chinese Academy of Sciences, Beijing 100049 (China); Wu Guozhong [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, P.O. Box 800-204, Shanghai 201800 (China)], E-mail: wuguozhong@sinap.ac.cn; Sha Maolin; Liu Yusheng [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, P.O. Box 800-204, Shanghai 201800 (China); Graduate University of the Chinese Academy of Sciences, Beijing 100049 (China)

    2008-10-15

    Considerably higher molecular weight (M{sub w}) and multi-modal molecular weight distribution (MWD) of poly(methyl methacrylate) (PMMA) were observed in neat ionic liquids ([bmim][PF{sub 6}] and [bmim][BF{sub 4}]), as well as their mixed solutions with organic solvents, probably due to the high viscosity and inhomogeneity of ionic liquids. FTIR spectra for PMMA showed that a slight amount of ionic liquid remained in the resulting polymer, and DSC measurement indicated the increase of glass transition point of PMMA with increasing of ionic liquid fraction in mixed solutions.

  13. Dielectric properties of supramolecular ionic structures obtained from multifunctional carboxylic acids and amines

    DEFF Research Database (Denmark)

    Gonzalez, Lidia; Yu, Liyun; Hvilsted, Søren

    2014-01-01

    The dielectric properties of several supramolecular ionic polymers and networks, linked by the ammonium salts of hexamethylene diamine (HMDA), tris(2-aminoethyl)amine (TAEA), poly(propylene imine) (PPI) dendrimers and two short bis carboxymethyl ether-terminated poly(ethylene glycol)s (Di......COOH-PEG), are reported in this paper. All supramolecular ionic polymers and networks exhibit very high relative dielectric permittivities ( 3 0 )( 10 2 – 10 6 ) at low frequencies, and signi fi cantly lower values (from 1 up to 26) at high frequencies. Additionally, the dielectric properties of supramolecular ionic......), are investigated. Here the relative dielectric permittivities of the supramolecular ionic structures formed with the multifunctional carboxylic acids were lower than those from the supramolecular ionic structures formed with the two carboxymethyl ether-terminated poly(ethylene glycol)s....

  14. Fullerol ionic fluids

    KAUST Repository

    Fernandes, Nikhil

    2010-01-01

    We report for the first time an ionic fluid based on hydroxylated fullerenes (fullerols). The ionic fluid was synthesized by neutralizing the fully protonated fullerol with an amine terminated polyethylene/polypropylene oxide oligomer (Jeffamine®). The ionic fluid was compared to a control synthesized by mixing the partially protonated form (sodium form) of the fullerols with the same oligomeric amine in the same ratio as in the ionic fluids (20 wt% fullerol). In the fullerol fluid the ionic bonding significantly perturbs the thermal transitions and melting/crystallization behavior of the amine. In contrast, both the normalized heat of fusion and crystallization of the amine in the control are similar to those of the neat amine consistent with a physical mixture of the fullerols/amine with minimal interactions. In addition to differences in thermal behavior, the fullerol ionic fluid exhibits a complex viscoelastic behavior intermediate between the neat Jeffamine® (liquid-like) and the control (solid-like). © 2010 The Royal Society of Chemistry.

  15. Sensitivities of ionic explosives

    Science.gov (United States)

    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.

  16. Gel electrolytes with ionic liquid plasticiser for electrochromic devices

    International Nuclear Information System (INIS)

    Desai, S.; Shepherd, R.L.; Innis, P.C.; Murphy, P.; Hall, C.; Fabretto, R.; Wallace, G.G.

    2011-01-01

    The comparative performance of conducting polymer electrochromic devices (ECDs) utilising gel polymer electrolytes (GPEs) plasticised with ethylene carbonate/propylene carbonate or (N-butyl-3-methylpyridinium trifluoromethanesulphonylimide (P 14 TFSI) has been made. Lithium perchlorate and lithium trifluoromethanesulphonylimide salts were used in the GPEs to provide enhanced ionic conductivity and inhibit phase separation of the polyethyleneoxide (PEO) and plasticiser. ECDs were assembled from cathodically colouring, polyethylenedioxythiophene (PEDOT), and anodically colouring, polypyrrole (PPy), conducting polymer electrochromes deposited by vapour deposition. The photopic contrast switching over the visible light spectrum, switching speeds and device stability of the ECDs were obtained. These studies demonstrate that the ionic liquid (IL) plasticised GPEs are a suitable replacement for pure IL based devices and volatile organic solvent plasticisers based upon ethylene carbonate/propylene carbonate mixtures.

  17. Gel electrolytes with ionic liquid plasticiser for electrochromic devices

    Energy Technology Data Exchange (ETDEWEB)

    Desai, S.; Shepherd, R.L.; Innis, P.C. [ARC Centre of Excellence for Electromaterials Science, Intelligent Polymer Research Institute, University of Wollongong, Northfields Avenue, Wollongong, NSW 2522 (Australia); Murphy, P. [Ian Wark Research Institute, University of South Australia, Mawson Lakes, SA 5095 (Australia); Mawson Institute, University of South Australia, Mawson Lakes, SA 5095 (Australia); Hall, C.; Fabretto, R. [Ian Wark Research Institute, University of South Australia, Mawson Lakes, SA 5095 (Australia); Wallace, G.G., E-mail: gwallace@uow.edu.a [ARC Centre of Excellence for Electromaterials Science, Intelligent Polymer Research Institute, University of Wollongong, Northfields Avenue, Wollongong, NSW 2522 (Australia)

    2011-04-15

    The comparative performance of conducting polymer electrochromic devices (ECDs) utilising gel polymer electrolytes (GPEs) plasticised with ethylene carbonate/propylene carbonate or (N-butyl-3-methylpyridinium trifluoromethanesulphonylimide (P{sub 14}TFSI) has been made. Lithium perchlorate and lithium trifluoromethanesulphonylimide salts were used in the GPEs to provide enhanced ionic conductivity and inhibit phase separation of the polyethyleneoxide (PEO) and plasticiser. ECDs were assembled from cathodically colouring, polyethylenedioxythiophene (PEDOT), and anodically colouring, polypyrrole (PPy), conducting polymer electrochromes deposited by vapour deposition. The photopic contrast switching over the visible light spectrum, switching speeds and device stability of the ECDs were obtained. These studies demonstrate that the ionic liquid (IL) plasticised GPEs are a suitable replacement for pure IL based devices and volatile organic solvent plasticisers based upon ethylene carbonate/propylene carbonate mixtures.

  18. The role of water in cholinium carboxylate ionic liquid’s aqueous solutions

    International Nuclear Information System (INIS)

    Patinha, David J.S.; Tomé, Liliana C.; Garcia, Helga; Ferreira, Rui; Pereira, Cristina Silva; Rebelo, Luís Paulo N.; Marrucho, Isabel M.

    2015-01-01

    Highlights: • Densities and viscosities of aqueous solutions of cholinium carboxylate ionic liquids. • 1 H NMR experiments were used to probe nanoscale organization of ionic liquids in water. • Different nanoscale organization in water for the 3 ionic liquids. - Abstract: Binary systems composed of water and cholinium carboxylate ionic liquids, namely cholinium lactate ([Ch][Lac]), cholinium propanoate ([Ch][Prop]) and cholinium malonate ([Ch][Mal]) were studied from the neat ionic liquid to very diluted aqueous solutions. Densities and viscosities were measured and atypical behaviors were observed, such as the increasing density of the binary [Ch][Prop] + H 2 O mixtures with increasing water content. In order to get molecular level insights on the IL + H 2 O solvation schemes, 1 H NMR studies were performed. Large deviations were obtained in the aniońs resonances when compared to those of the cation suggesting that water interacts preferentially with the anion counter-part of the ionic liquid. The increasing density of [Ch][Prop] + H 2 O system with increasing water content can be related to the orientation of the alkyl chains, as a result of their nanoscale organization. This behavior was confirmed through the study of the thermophysical properties of [Ch][Hex] + H 2 O mixtures, where this phenomenon is known to occur

  19. Going full circle: phase-transition thermodynamics of ionic liquids.

    Science.gov (United States)

    Preiss, Ulrich; Verevkin, Sergey P; Koslowski, Thorsten; Krossing, Ingo

    2011-05-27

    We present the full enthalpic phase transition cycle for ionic liquids (ILs) as examples of non-classical salts. The cycle was closed for the lattice, solvation, dissociation, and vaporization enthalpies of 30 different ILs, relying on as much experimental data as was available. High-quality dissociation enthalpies were calculated at the G3 MP2 level. From the cycle, we could establish, for the first time, the lattice and solvation enthalpies of ILs with imidazolium ions. For vaporization, lattice, and dissociation enthalpies, we also developed new prediction methods in the course of our investigations. Here, as only single-ion values need to be calculated and the tedious optimization of an ion pair can be circumvented, the computational time is short. For the vaporization enthalpy, a very simple approach was found, using a surface term and the calculated enthalpic correction to the total gas-phase energy. For the lattice enthalpy, the most important constituent proved to be the calculated conductor-like screening model (COSMO) solvation enthalpy in the ideal electric conductor. A similar model was developed for the dissociation enthalpy. According to our assessment, the typical error of the lattice enthalpy would be 9.4 kJ mol(-1), which is less than half the deviation we get when using the (optimized) Kapustinskii equation or the recent volume-based thermodynamics (VBT) theory. In contrast, the non-optimized VBT formula gives lattice enthalpies 20 to 140 kJ mol(-1) lower than the ones we assessed in the cycle, because of the insufficient description of dispersive interactions. Our findings show that quantum-chemical calculations can greatly improve the VBT approaches, which were parameterized for simple, inorganic salts with ideally point-shaped charges. In conclusion, we suggest the term "augmented VBT", or "aVBT", to describe this kind of theoretical approach. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Sodium conducting polymer electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Skaarup, S.; West, K. (eds.)

    1989-04-01

    This section deals with the aspects of ionic conduction in general as well as specific experimental results obtained for sodium systems. The conductivity as a function of temperature and oxygen/metal ratio are given for the systems NaI, NaCF/sub 3/SO/sub 3/ and NaClO/sub 4/ plus polyethylene oxide. Attempts have been made to produce mixed phase solid electrolytes analogous to the lithium systems that have worked well. These consist of mixtures of polymer and a solid electrolyte. The addition of both nasicon and sodium beta alumina unexpectedly decreases the ionic conductivity in contrast to the lithium systems. Addition of the nonconducting silica AEROSIL in order to increase the internal surface area has the effect of retarding the phase transition at 60 deg. C, but does not enhance the conductivity. (author) 23 refs.

  1. Molecular Simulation of Ionic Polyimides and Composites with Ionic Liquids as Gas-Separation Membranes.

    Science.gov (United States)

    Abedini, Asghar; Crabtree, Ellis; Bara, Jason E; Turner, C Heath

    2017-10-24

    Polyimides are at the forefront of advanced membrane materials for CO 2 capture and gas-purification processes. Recently, ionic polyimides (i-PIs) have been reported as a new class of condensation polymers that combine structural components of both ionic liquids (ILs) and polyimides through covalent linkages. In this study, we report CO 2 and CH 4 adsorption and structural analyses of an i-PI and an i-PI + IL composite containing [C 4 mim][Tf 2 N]. The combination of molecular dynamics (MD) and grand canonical Monte Carlo (GCMC) simulations is used to compute the gas solubility and the adsorption performance with respect to the density, fractional free volume (FFV), and surface area of the materials. Our results highlight the polymer relaxation process and its correlation to the gas solubility. In particular, the surface area can provide meaningful guidance with respect to the gas solubility, and it tends to be a more sensitive indicator of the adsorption behavior versus only considering the system density and FFV. For instance, as the polymer continues to relax, the density, FFV, and pore-size distribution remain constant while the surface area can continue to increase, enabling more adsorption. Structural analyses are also conducted to identify the nature of the gas adsorption once the ionic liquid is added to the polymer. The presence of the IL significantly displaces the CO 2 molecules from the ligand nitrogen sites in the neat i-PI to the imidazolium rings in the i-PI + IL composite. However, the CH 4 molecules move from the imidazolium ring sites in the neat i-PI to the ligand nitrogen atoms in the i-PI + IL composite. These molecular details can provide critical information for the experimental design of highly selective i-PI materials as well as provide additional guidance for the interpretation of the simulated adsorption systems.

  2. Ionic Soft Matter Modern Trends in Theory and Applications

    CERN Document Server

    Henderson, Douglas; Trokhymchuk, Andrij

    2006-01-01

    This book is for researchers interested in the statistical mechanical modeling of charged substance as well as for those working in chemical physics, physical chemistry, biophysics and environmental science. The book consists of state of the art reviews of the recent experimental, theoretical and simulation studies on ionic criticality, polyelectrolytes, proton transport in fuel cell membranes, and the design of DNA arrays. A significant portion of the book deals with discussions of the fundamental and applied problems of important phenomena such as ion association, ion adsorption, ion solvation, electrical double layer, thin colloidal film stability, ion collective dynamics, ion screening, etc. using a level of argumentation that is common and understandable for mathematicians, physicists, chemists, biologists and engineers. The book concludes with chapter on physical properties of fuel-containing materials from the inside of the troubled Chornobyl sarcophagus.

  3. Ionic liquid-based materials: a platform to design engineered CO2 separation membranes.

    Science.gov (United States)

    Tomé, Liliana C; Marrucho, Isabel M

    2016-05-21

    During the past decade, significant advances in ionic liquid-based materials for the development of CO2 separation membranes have been accomplished. This review presents a perspective on different strategies that use ionic liquid-based materials as a unique tuneable platform to design task-specific advanced materials for CO2 separation membranes. Based on compilation and analysis of the data hitherto reported, we provide a judicious assessment of the CO2 separation efficiency of different membranes, and highlight breakthroughs and key challenges in this field. In particular, configurations such as supported ionic liquid membranes, polymer/ionic liquid composite membranes, gelled ionic liquid membranes and poly(ionic liquid)-based membranes are detailed, discussed and evaluated in terms of their efficiency, which is attributed to their chemical and structural features. Finally, an integrated perspective on technology, economy and sustainability is provided.

  4. Biodegradable Polymers

    OpenAIRE

    Vroman, Isabelle; Tighzert, Lan

    2009-01-01

    Biodegradable materials are used in packaging, agriculture, medicine and other areas. In recent years there has been an increase in interest in biodegradable polymers. Two classes of biodegradable polymers can be distinguished: synthetic or natural polymers. There are polymers produced from feedstocks derived either from petroleum resources (non renewable resources) or from biological resources (renewable resources). In general natural polymers offer fewer advantages than synthetic polymers. ...

  5. Neutron-scattering studies of a polymer electrolyte, PPO-LiClO4

    DEFF Research Database (Denmark)

    Carlsson, P.; Mattsson, B.; Swenson, J.

    1998-01-01

    changes which are induced by the dopant salt. The phenomena can be explained by local ordering of the chain segments around the solvated cations and by contraction of neighbouring chains via cationic cross links. The QENS results indicate that the segmental motions of the polymer chains, which have been...

  6. 2012 Gordon Research Conference On Molecular And Ionic Clusters

    International Nuclear Information System (INIS)

    McCoy, Anne

    2012-01-01

    The Gordon Research Conference on 'Molecular and Ionic Clusters' focuses on clusters, which are the initial molecular species found in gases when condensation begins to occur. Condensation can take place solely from molecules interacting with each other, mostly at low temperatures, or when molecules condense around charged particles (electrons, protons, metal cations, molecular ions), producing ion molecule clusters. These clusters provide models for solvation, allow a pristine look at geometric as well as electronic structures of molecular complexes or matter in general, their interaction with radiation, their reactivity, their thermodynamic properties and, in particular, the related dynamics. This conference focuses on new ways to make clusters composed of different kinds of molecules, new experimental techniques to investigate the properties of the clusters and new theoretical methods with which to calculate the structures, dynamical motions and energetics of the clusters. Some of the main experimental methods employed include molecular beams, mass spectrometry, laser spectroscopy (from infrared to XUV; in the frequency as well as the time domain) and photoelectron spectroscopy. Techniques include laser absorption spectroscopy, laser induced fluorescence, resonance enhanced photoionization, mass-selected photodissociation, photofragment imaging, ZEKE photoelectron spectroscopy, etc. From the theoretical side, this conference highlights work on potential surfaces and measurable properties of the clusters. The close ties between experiment, theory and computation have been a hallmark of the Gordon Research Conference on Molecular and Ionic Clusters. In the 2012 meeting, we plan to have sessions that will focus on topics including: (1) The use of cluster studies to probe fundamental phenomena; (2) Finite size effects on structure and thermodynamics; (3) Intermolecular forces and cooperative effects; (4) Molecular clusters as models for solvation; and (5) Studies of

  7. Lewis Acidic Ionic Liquids.

    Science.gov (United States)

    Brown, Lucy C; Hogg, James M; Swadźba-Kwaśny, Małgorzata

    2017-08-21

    Until very recently, the term Lewis acidic ionic liquids (ILs) was nearly synonymous with halometallate ILs, with a strong focus on chloroaluminate(III) systems. The first part of this review covers the historical context in which these were developed, speciation of a range of halometallate ionic liquids, attempts to quantify their Lewis acidity, and selected recent applications: in industrial alkylation processes, in supported systems (SILPs/SCILLs) and in inorganic synthesis. In the last decade, interesting alternatives to halometallate ILs have emerged, which can be divided into two sub-sections: (1) liquid coordination complexes (LCCs), still based on halometallate species, but less expensive and more diverse than halometallate ionic liquids, and (2) ILs with main-group Lewis acidic cations. The two following sections cover these new liquid Lewis acids, also highlighting speciation studies, Lewis acidity measurements, and applications.

  8. A solvated electron lithium electrode for secondary batteries

    Science.gov (United States)

    Sammells, A. F.; Semkow, K. W.

    1986-09-01

    Attention is given to a novel method for the achievement of high electro-chemical reversibility in Li-based nonaqueous cells, using a liquid negative electrode that consists of Li dissolved in liquid ammonia as a solvated electron Li electrode. The containment of this liquid negative active material from direct contact to a liquid nonaqueous electrolyte in the positive electrode compartment was realized through the use of a Li-intercalated, electronically conducting ceramic membrane.

  9. Tris[2-(deuteriomethylsulfanylphenyl]phosphine deuteriochloroform 0.125-solvate

    Directory of Open Access Journals (Sweden)

    Seik Weng Ng

    2008-05-01

    Full Text Available The title deuterated tripodal phosphine, C21H12D9PS3·0.125CDCl3, crystallizes as two independent molecules, one of which lies on a general position and the other about a threefold rotation axis, and as a deuteriochloroform solvate. The solvent molecule is disordered about a site of symmetry 3, so that the ratio of phosphine to solvent is 8:1. The P atom adopts a pyramidal coordination geometry.

  10. Solvation dynamics of lithium salts in wet nitrobenzene

    Czech Academy of Sciences Publication Activity Database

    Moakes, G.; Gelbaum, L. T.; Leisen, J.; Janata, J.; Mareček, Vladimír

    2006-01-01

    Roč. 593, 1-2 (2006), s. 111-118 ISSN 0022-0728 R&D Projects: GA ČR GA203/03/0822 Grant - others:Georgia Research Alliance(US) GRA.CG06.D Institutional research plan: CEZ:AV0Z40400503 Keywords : solvation * NMR * FTIR * nitrobenzene/water * solvatomers Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.339, year: 2006

  11. Benzonitrile: Electron affinity, excited states, and anion solvation

    Science.gov (United States)

    Dixon, Andrew R.; Khuseynov, Dmitry; Sanov, Andrei

    2015-10-01

    We report a negative-ion photoelectron imaging study of benzonitrile and several of its hydrated, oxygenated, and homo-molecularly solvated cluster anions. The photodetachment from the unsolvated benzonitrile anion to the X ˜ 1 A 1 state of the neutral peaks at 58 ± 5 meV. This value is assigned as the vertical detachment energy (VDE) of the valence anion and the upper bound of adiabatic electron affinity (EA) of benzonitrile. The EA of the lowest excited electronic state of benzonitrile, a ˜ 3 A 1 , is determined as 3.41 ± 0.01 eV, corresponding to a 3.35 eV lower bound for the singlet-triplet splitting. The next excited state, the open-shell singlet A ˜ 1 A 1 , is found about an electron-volt above the triplet, with a VDE of 4.45 ± 0.01 eV. These results are in good agreement with ab initio calculations for neutral benzonitrile and its valence anion but do not preclude the existence of a dipole-bound state of similar energy and geometry. The step-wise and cumulative solvation energies of benzonitrile anions by several types of species were determined, including homo-molecular solvation by benzonitrile, hydration by 1-3 waters, oxygenation by 1-3 oxygen molecules, and mixed solvation by various combinations of O2, H2O, and benzonitrile. The plausible structures of the dimer anion of benzonitrile were examined using density functional theory and compared to the experimental observations. It is predicted that the dimer anion favors a stacked geometry capitalizing on the π-π interactions between the two partially charged benzonitrile moieties.

  12. Functional ionic liquids

    International Nuclear Information System (INIS)

    Baecker, Tobias

    2012-01-01

    In the thesis at hand, new functional ionic liquids were investigated. Main focus was attended to their structure property relations and the structural features leading to a decrease of the melting point. New compounds of the type 1-butyl-3-methylimidazolium tris(N,Ndialkyldithiocarbamato) uranylate with variously substituated dithiocarbamato ligands were synthesized and characterized. Ligands with asymmetrical substitution pattern proved to be most suitable for ionic liquid formation. The single-crystal X-ray structures revealed the interactions in the solid state. Here, the first spectroscopic investigation of the U-S bond in sulfur donated uranyl complexes, up to now only observed in single-crystal X-ray structures, is presented, and the participation of the uranium f-orbitals is shown by theoretical calculations. Electrochemical investigations showed the accessibility of the respective U V O 2 + compounds. As well, ionic liquids with [FeCl 4 ] - and [Cl 3 FeOFeCl 3 ] 2- as anion were synthesized. Both of these anions contain high-spin Fe(III) centres in distorted tetrahedral environment, but exhibit different magnetic behaviour. The tetrachloroferrates show the usual paramagnetism, the m-oxobis(trichloroferrate) exhibits unexpectedly strong antiferromagnetic coupling, as was observed by NMR experiments and susceptibility measurements. To investigate structure-property relations in functionalized ionic liquids, a set of protic, primary alkylammonium and aprotic, quarternary trimethylalkylammonium based ionic liquids was synthesized, and characterized. The length of the alkyl chain was systematically varied, and all compounds were synthesized with and without hydroxyl group, as well as formate and bis(triflyl)amide salts, aiming at getting insight into the influence of the different structure parts on the respective ionic liquid's properties.

  13. Comparison of solvation dynamics of electrons in four polyols

    Energy Technology Data Exchange (ETDEWEB)

    Lampre, I.; Pernot, P.; Bonin, J. [Laboratoire de Chimie Physique/ELYSE, Universite Paris-Sud 11, UMR 8000, Bat. 349, Orsay F-91405 (France); CNRS, Orsay F-91405 (France); Mostafavi, M. [Laboratoire de Chimie Physique/ELYSE, Universite Paris-Sud 11, UMR 8000, Bat. 349, Orsay F-91405 (France); CNRS, Orsay F-91405 (France)], E-mail: mehran.mostafavi@lcp.u-psud.fr

    2008-10-15

    Using pump-probe transient absorption spectroscopy, we studied the solvation dynamics of the electron in liquid polyalcohols: ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol and propane-1,2,3-triol. Time-resolved absorption spectra ranging from 440 to 720 nm were measured. Our study shows that the excess electron in the diols presents an intense and wide absorption band in the visible and near-IR spectral domain at early time after two-photon ionization of the neat solvent. Then, for the first tens of picoseconds, the electron spectrum shifts toward the blue domain and its bandwidth decreases as the red part of the initial spectrum rapidly drops, while the blue part hardly evolves. In contrast, in the triol, the absorption spectrum of the electron is early situated in the visible range after the pump pulse and then solely evolves in the red part. The Bayesian data analysis of the observed picosecond solvation dynamics with different models is in favor of a heterogeneous continuous relaxation. That is corroborated by the analogy between the change in the absorption band with increasing time or decreasing temperature. That tends to indicate a similar organization disorder of the solvent. Moreover, the electron solvation dynamics is very fast in propane-1,2,3-triol despite its high viscosity and highlight the role of the OH-group in that process.

  14. Improvements to the APBS biomolecular solvation software suite.

    Science.gov (United States)

    Jurrus, Elizabeth; Engel, Dave; Star, Keith; Monson, Kyle; Brandi, Juan; Felberg, Lisa E; Brookes, David H; Wilson, Leighton; Chen, Jiahui; Liles, Karina; Chun, Minju; Li, Peter; Gohara, David W; Dolinsky, Todd; Konecny, Robert; Koes, David R; Nielsen, Jens Erik; Head-Gordon, Teresa; Geng, Weihua; Krasny, Robert; Wei, Guo-Wei; Holst, Michael J; McCammon, J Andrew; Baker, Nathan A

    2018-01-01

    The Adaptive Poisson-Boltzmann Solver (APBS) software was developed to solve the equations of continuum electrostatics for large biomolecular assemblages that have provided impact in the study of a broad range of chemical, biological, and biomedical applications. APBS addresses the three key technology challenges for understanding solvation and electrostatics in biomedical applications: accurate and efficient models for biomolecular solvation and electrostatics, robust and scalable software for applying those theories to biomolecular systems, and mechanisms for sharing and analyzing biomolecular electrostatics data in the scientific community. To address new research applications and advancing computational capabilities, we have continually updated APBS and its suite of accompanying software since its release in 2001. In this article, we discuss the models and capabilities that have recently been implemented within the APBS software package including a Poisson-Boltzmann analytical and a semi-analytical solver, an optimized boundary element solver, a geometry-based geometric flow solvation model, a graph theory-based algorithm for determining pK a values, and an improved web-based visualization tool for viewing electrostatics. © 2017 The Protein Society.

  15. Toward protic ionic liquid and organic ionic plastic crystal electrolytes for fuel cells

    International Nuclear Information System (INIS)

    Rana, Usman Ali; Forsyth, Maria; MacFarlane, Douglas R.; Pringle, Jennifer M.

    2012-01-01

    Highlights: ► Polymer electrolyte membrane fuel cells that can operate above 120 °C, without humidification, would be much more commercially viable. ► Protic ionic liquids and organic ionic plastic crystals are showing increasing promise as anhydrous proton conductors in fuel cells. ► Here we review the recent progress in these two areas. - Abstract: There is increasing demand for the development of anhydrous proton conducting electrolytes, most notably to allow the development of fuel cells that can operate at temperatures above 120 °C, without the need for constant and controlled humidification. The emerging field of protic ionic liquids (PILs) represents a promising new direction for this research and the development of these materials has made significant progress in recent years. In a related but as yet little-explored avenue, proton conducting organic ionic plastic crystals offer the potential advantage of providing a solid state matrix for anhydrous proton conductivity. Here we discuss the recent progress in these areas and identify the key challenges for future research.

  16. Ionic molar volumes in methanol mixtures with acetonitrile, N,N-dimethylformamide and propylene carbonate at T = 298.15 K

    International Nuclear Information System (INIS)

    Pietrzak, A.; Piekarski, H.

    2014-01-01

    Highlights: • Densities of electrolyte solutions in methanol mixtures were measured at T = 298.15 K. • Apparent molar volumes of sodium cation and iodide anion were determined. • TPTB as a calculation method was used. • Preferential solvation of ions by organic solvents was examined. - Abstract: The densities of dilute solutions of three electrolytes (NaI, NaBPh 4 and Ph 4 PI) in methanol mixtures with propylene carbonate (PC), N,N-dimethylformamide (DMF) and acetonitrile (AN) have been measured by Anton Paar 5000 densimeter at T = 298.15 K. Apparent molar volumes, V Φ have been determined at an electrolyte concentration of 0.06 mol · kg −1 over the entire mixed solvent composition range. Single ionic apparent molar volumes of transfer, Δ t V Φ (ion) were calculated using the tetraphenylphosphonium tetraphenylborate (TPTB) assumption. The results are discussed in terms of ionic preferential solvation

  17. Trivalent europium speciation in a room-temperature ionic liquid

    International Nuclear Information System (INIS)

    Mekki, S.

    2006-10-01

    microscopic scale. The manuscript is structured with four parts. In a first chapter, we present the main physico-chemical properties of an imidazolium-based ionic liquid family, and then we choose the ionic liquid bumimTf 2 N for the whole thesis and start with the electrochemical study. In the second chapter, we present the study of europium solvation in the ionic liquid media. In the third part, we expose the results concerning TTA solvation and its complexation with europium in bumimTf 2 N under different conditions. Finally in the last chapter, we present the results obtained for the europium extraction in a three-stage extraction system: water/bumimTf 2 N/supercritical CO 2 . This work highlights the potential use of ionic liquids and particularly bumimTf 2 N in the spent nuclear fuel reprocessing. The ability to extract quantitatively a trivalent lanthanide has been demonstrated. This fundamental study can be regarded as a feasibility demonstration to build an ionic liquid-containing extraction system, in the aim of possible large-scale application. (author)

  18. Ionic Resistance and Permselectivity Tradeoffs in Anion Exchange Membranes

    KAUST Repository

    Geise, Geoffrey M.

    2013-10-23

    Salinity gradient energy technologies, such as reverse electrodialysis (RED) and capacitive mixing based on Donnan potential (Capmix CDP), could help address the global need for noncarbon-based energy. Anion exchange membranes (AEMs) are a key component in these systems, and improved AEMs are needed in order to optimize and extend salinity gradient energy technologies. We measured ionic resistance and permselectivity properties of quaternary ammonium-functionalized AEMs based on poly(sulfone) and poly(phenylene oxide) polymer backbones and developed structure-property relationships between the transport properties and the water content and fixed charge concentration of the membranes. Ion transport and ion exclusion properties depend on the volume fraction of water in the polymer membrane, and the chemical nature of the polymer itself can influence fine-tuning of the transport properties to obtain membranes with other useful properties, such as chemical and dimensional stability. The ionic resistance of the AEMs considered in this study decreased by more than 3 orders of magnitude (i.e., from 3900 to 1.6 Ω m) and the permselectivity decreased by 6% (i.e., from 0.91 to 0.85) as the volume fraction of water in the polymer was varied by a factor of 3.8 (i.e., from 0.1 to 0.38). Water content was used to rationalize a tradeoff relationship between the permselectivity and ionic resistance of these AEMs whereby polymers with higher water content tend to have lower ionic resistance and lower permselectivity. The correlation of ion transport properties with water volume fraction and fixed charge concentration is discussed with emphasis on the importance of considering water volume fraction when interpreting ion transport data. © 2013 American Chemical Society.

  19. Ionic liquids in chemical engineering.

    Science.gov (United States)

    Werner, Sebastian; Haumann, Marco; Wasserscheid, Peter

    2010-01-01

    The development of engineering applications with ionic liquids stretches back to the mid-1990s when the first examples of continuous catalytic processes using ionic liquids and the first studies of ionic liquid-based extractions were published. Ever since, the use of ionic liquids has seen tremendous progress in many fields of chemistry and engineering, and the first commercial applications have been reported. The main driver for ionic liquid engineering applications is to make practical use of their unique property profiles, which are the result of a complex interplay of coulombic, hydrogen bonding and van der Waals interactions. Remarkably, many ionic liquid properties can be tuned in a wide range by structural modifications at their cation and anion. This review highlights specific examples of ionic liquid applications in catalysis and in separation technologies. Additionally, the application of ionic liquids as working fluids in process machines is introduced.

  20. Thermodynamics of hydrogen bonding and van der Waals interactions of organic solutes in solutions of imidazolium based ionic liquids: “Structure-property” relationships

    Energy Technology Data Exchange (ETDEWEB)

    Varfolomeev, Mikhail A., E-mail: vma.ksu@gmail.com; Khachatrian, Artashes A.; Akhmadeev, Bulat S.; Solomonov, Boris N.

    2016-06-10

    Highlights: • Solution enthalpies of organic solutes in imidazolium based ionic liquids were measured. • van der Waals interactions scale of imidazolium based ionic liquids was proposed. • Enthalpies of solvation of organic solutes in ionic liquids were determined. • Hydrogen bond enthalpies of organic solutes with ionic liquids were calculated. • Relationships between structure of ionic liquids and thermochemical data were obtained. - Abstract: In the present work thermochemistry of intermolecular interactions of organic compounds in solutions of imidazolium based ionic liquids (ILs) has been studied using solution calorimetry method. Enthalpies of solution at infinite dilution of non-polar (alkanes, aromatic hydrocarbons) and polar (alcohols, amides, and etc.) organic solutes in two ionic liquids 1-butyl-3-methylimidazolium tetrafluoroborate and 1-butyl-3-methylimidazolium trifluoromethanesulfonate were measured at 298.15 K. The scale of van der Waals interactions of imidazolium based ILs has been proposed on the basis of solution enthalpies of n-alkanes in their media. The effect of the cation and anion structure of ILs on the enthalpies of solvation was analyzed. Enthalpies of hydrogen bonding of organic solutes with imidazolium based ILs were determined. It has been shown that these values are close to zero for proton acceptor solutes. At the same time, enthalpies of hydrogen bonding of proton donor solutes with ionic liquids are increased depending the anion: tetrafluoroborate ≈ bis(trifluoromethylsulfonyl)imide < 2-(2-methoxyethoxy)ethyl sulfate < trifluoromethanesulfonate. Enthalpies of van der Waals interactions and hydrogen bonding in the solutions of imidazolium based ionic liquids were compared with the same data for molecular solvents.

  1. Thermodynamics of hydrogen bonding and van der Waals interactions of organic solutes in solutions of imidazolium based ionic liquids: “Structure-property” relationships

    International Nuclear Information System (INIS)

    Varfolomeev, Mikhail A.; Khachatrian, Artashes A.; Akhmadeev, Bulat S.; Solomonov, Boris N.

    2016-01-01

    Highlights: • Solution enthalpies of organic solutes in imidazolium based ionic liquids were measured. • van der Waals interactions scale of imidazolium based ionic liquids was proposed. • Enthalpies of solvation of organic solutes in ionic liquids were determined. • Hydrogen bond enthalpies of organic solutes with ionic liquids were calculated. • Relationships between structure of ionic liquids and thermochemical data were obtained. - Abstract: In the present work thermochemistry of intermolecular interactions of organic compounds in solutions of imidazolium based ionic liquids (ILs) has been studied using solution calorimetry method. Enthalpies of solution at infinite dilution of non-polar (alkanes, aromatic hydrocarbons) and polar (alcohols, amides, and etc.) organic solutes in two ionic liquids 1-butyl-3-methylimidazolium tetrafluoroborate and 1-butyl-3-methylimidazolium trifluoromethanesulfonate were measured at 298.15 K. The scale of van der Waals interactions of imidazolium based ILs has been proposed on the basis of solution enthalpies of n-alkanes in their media. The effect of the cation and anion structure of ILs on the enthalpies of solvation was analyzed. Enthalpies of hydrogen bonding of organic solutes with imidazolium based ILs were determined. It has been shown that these values are close to zero for proton acceptor solutes. At the same time, enthalpies of hydrogen bonding of proton donor solutes with ionic liquids are increased depending the anion: tetrafluoroborate ≈ bis(trifluoromethylsulfonyl)imide < 2-(2-methoxyethoxy)ethyl sulfate < trifluoromethanesulfonate. Enthalpies of van der Waals interactions and hydrogen bonding in the solutions of imidazolium based ionic liquids were compared with the same data for molecular solvents.

  2. Thermodynamic functions of ion solvation in normal alcohols of aliphatic series

    International Nuclear Information System (INIS)

    Sergeeva, I.A.

    1978-01-01

    Thermodynamic functions of ion solvation of alkali, alkaline earth metals and halogenides in 9 alcohols are calculated using the earlier suggested method. It is shown that summary values are in good accord with experimental ones, the deviations do not surpass 0-5%, solvation energies of one and the same electrolyte in the series of n-alcohols do not change, enthalpy and entropy of solvation increase from lower alcohols to higher ones

  3. Multiple time step molecular dynamics in the optimized isokinetic ensemble steered with the molecular theory of solvation: Accelerating with advanced extrapolation of effective solvation forces

    International Nuclear Information System (INIS)

    Omelyan, Igor; Kovalenko, Andriy

    2013-01-01

    We develop efficient handling of solvation forces in the multiscale method of multiple time step molecular dynamics (MTS-MD) of a biomolecule steered by the solvation free energy (effective solvation forces) obtained from the 3D-RISM-KH molecular theory of solvation (three-dimensional reference interaction site model complemented with the Kovalenko-Hirata closure approximation). To reduce the computational expenses, we calculate the effective solvation forces acting on the biomolecule by using advanced solvation force extrapolation (ASFE) at inner time steps while converging the 3D-RISM-KH integral equations only at large outer time steps. The idea of ASFE consists in developing a discrete non-Eckart rotational transformation of atomic coordinates that minimizes the distances between the atomic positions of the biomolecule at different time moments. The effective solvation forces for the biomolecule in a current conformation at an inner time step are then extrapolated in the transformed subspace of those at outer time steps by using a modified least square fit approach applied to a relatively small number of the best force-coordinate pairs. The latter are selected from an extended set collecting the effective solvation forces obtained from 3D-RISM-KH at outer time steps over a broad time interval. The MTS-MD integration with effective solvation forces obtained by converging 3D-RISM-KH at outer time steps and applying ASFE at inner time steps is stabilized by employing the optimized isokinetic Nosé-Hoover chain (OIN) ensemble. Compared to the previous extrapolation schemes used in combination with the Langevin thermostat, the ASFE approach substantially improves the accuracy of evaluation of effective solvation forces and in combination with the OIN thermostat enables a dramatic increase of outer time steps. We demonstrate on a fully flexible model of alanine dipeptide in aqueous solution that the MTS-MD/OIN/ASFE/3D-RISM-KH multiscale method of molecular dynamics

  4. New Polymer Electrolyte Cell Systems

    Science.gov (United States)

    Smyrl, William H.; Owens, Boone B.; Mann, Kent; Pappenfus, T.; Henderson, W.

    2004-01-01

    PAPERS PUBLISHED: 1. Pappenfus, Ted M.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; Smyrl, William H. Complexes of Lithium Imide Salts with Tetraglyme and Their Polyelectrolyte Composite Materials. Journal of the Electrochemical Society (2004), 15 1 (2), A209-A2 15. 2. Pappenfus, Ted M.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; Smyrl, William H. Ionic-liquidlpolymer electrolyte composite materials for electrochemical device applications. Polymeric Materials Science and Engineering (2003), 88 302. 3. Pappenfus, Ted R.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; and Smyrl, William H. Ionic Conductivity of a poly(vinylpyridinium)/Silver Iodide Solid Polymer Electrolyte System. Solid State Ionics (in press 2004). 4. Pappenfus Ted M.; Mann, Kent R; Smyrl, William H. Polyelectrolyte Composite Materials with LiPFs and Tetraglyme. Electrochemical and Solid State Letters, (2004), 7(8), A254.

  5. Polymer compound

    NARCIS (Netherlands)

    1995-01-01

    A Polymer compound comprising a polymer (a) that contains cyclic imidesgroups and a polymer (b) that contains monomer groups with a 2,4-diamino-1,3,5-triazine side group. According to the formula (see formula) whereby themole percentage ratio of the cyclic imides groups in the polymer compoundwith

  6. Positrons in ionic crystals

    International Nuclear Information System (INIS)

    Pareja, R.

    1988-01-01

    Positron annihilation experiments in ionic crystals are reviewed and their results are arranged. A discussion about the positron states in these materials is made in the light of these results and the different proposed models. The positronium in alkali halides is specially considered. (Author)

  7. Ionic smoke detectors

    CERN Document Server

    2002-01-01

    Ionic smoke detectors are products incorporating radioactive material. This article summarises the process for their commercialization and marketing, and how the activity is controlled, according to regulations establishing strict design and production requisites to guarantee the absence of radiological risk associated both with their use and their final handling as conventional waste. (Author)

  8. Polymer electronics

    CERN Document Server

    Hsin-Fei, Meng

    2013-01-01

    Polymer semiconductor is the only semiconductor that can be processed in solution. Electronics made by these flexible materials have many advantages such as large-area solution process, low cost, and high performance. Researchers and companies are increasingly dedicating time and money in polymer electronics. This book focuses on the fundamental materials and device physics of polymer electronics. It describes polymer light-emitting diodes, polymer field-effect transistors, organic vertical transistors, polymer solar cells, and many applications based on polymer electronics. The book also disc

  9. PEO nanocomposite polymer electrolyte for solid state symmetric

    Indian Academy of Sciences (India)

    Physical and electrochemical properties of polyethylene oxide (PEO)-based nanocomposite solid polymer electrolytes (NPEs) were investigated for symmetric capacitor applications. Nanosize fillers, i.e., Al2O3 and SiO2 incorporated polymer electrolyte exhibited higher ionic conductivity than those with filler-free composites ...

  10. Structural and Morphological Features of Acid-Bearing Polymers for PEM Fuel Cells

    DEFF Research Database (Denmark)

    Yang, Yunsong; Siu, Ana; Peckham, Timothy J.

    2008-01-01

    Chemical structure, polymer microstructure, sequence distribution, and morphology of acid-bearing polymers are important factors in the design of polymer electrolyte membranes (PEMs) for fuel cells. The roles of ion aggregation and phase separation in vinylic- and aromatic-based polymers in proton...... conductivity and water transport are described. The formation, dimensions, and connectivity of ionic pathways are consistently found to play an important role in determining the physicochemical properties of PEMs. For polymers that possess low water content, phase separation and ionic channel formation...

  11. Polymer Coatings Reduce Electro-osmosis

    Science.gov (United States)

    Herren, Blair J.; Snyder, Robert; Shafer, Steven G.; Harris, J. Milton; Van Alstine, James M.

    1989-01-01

    Poly(ethylene glycol) film controls electrostatic potential. Electro-osmosis in quartz or glass chambers reduced or reversed by coating inside surface of chambers with monomacromolecular layers of poly(ethylene glycol). Stable over long times. Electrostatic potential across surface of untreated glass or plastic chamber used in electro-phoresis is negative and attracts cations in aqueous electrolyte. Cations solvated, entrains flow of electrolyte migrating toward cathode. Electro-osmotic flow interferes with desired electrophoresis of particles suspended in electrolyte. Polymer coats nontoxic, transparent, and neutral, advantageous for use in electrophoresis.

  12. Ab initio joint density-functional theory of solvated electrodes, with model and explicit solvation

    Science.gov (United States)

    Arias, Tomas

    2015-03-01

    the electrochemical context and how it is needed for realistic description of solvated electrode systems [], and how simple ``implicit'' polarized continuum methods fail radically in this context. Finally, we shall present a series of results relevant to battery, supercapacitor, and solar-fuel systems, one of which has led to a recent invention disclosure for improving battery cycle lifetimes. Supported as a part of the Energy Materials Center at Cornell, an Energy Frontier Research Center funded by DOE/BES (award de-sc0001086) and by the New York State Division of Science, Technology and Innovation (NYSTAR, award 60923).

  13. Using ethane and butane as probes to the molecular structure of 1-alkyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl] imide ionic liquids.

    Science.gov (United States)

    Costa Gomes, Margarida F; Pison, Laure; Pensado, Alfonso S; Pádua, Agilio A H

    2012-01-01

    In this work, we have studied the solubility and the thermodynamic properties of solvation, between 298 and 343 K and at pressures close to atmospheric, of ethane and n-butane in several ionic liquids based on the bis[(trifluoromethyl) sulfonyl]imide anion and on 1-alkyl-3-methylimidazolium cations, [CnC1Im] [NTf2], with alkyl side-chains varying from two to ten carbon atoms. The solubility of butane is circa one order of magnitude larger than that of ethane with mole fractions as high as 0.15 in [C10C1Im][NTf2] at 300 K. The solubilities of both n-butane and ethane gases are higher for ionic liquids with longer alkyl chains. The behaviour encountered is explained by the preferential solvation of the gases in the non-polar domains of the solvents, the larger solubility of n-butane being attributed to the dispersive contributions to the interaction energy. The rise in solubility with increasing size of the alkyl-side chain is explained by a more favourable entropy of solvation in the ionic liquids with larger cations. These conclusions are corroborated by molecular dynamics simulation studies.

  14. Ionic transport in polypyrrole doped with dianionic counterion hexafluorosilicate

    International Nuclear Information System (INIS)

    Kepas, Anna; Grzeszczuk, Maria

    2006-01-01

    Electrodeposition, redox switching, ion transport/exchange, surface topography for a thin polypyrrole film on gold in aqueous sodium hexafluorosilicate solution is reported. The properties have been compared with that corresponding to polypyrrole doped with hexafluoroaluminate and related systems. The dianionic counterion enhances electroactivity of the polymer, slows down ionic transport in the polymer phase, makes a strong impact on a surface structure of the polymer film. An improvement in stability of the anion-exchanger properties is observed. Several electroanalytical methods: chronoamperometry (Canada), cyclic voltammetry (CV), electrochemical quartz crystal microbalance (EQCM), electrochemical impedance spectroscopy (EIS), and a microscopic examination of the polymer film surface by scanning electron microscopy (SEM) have been used in the experimental work

  15. Recent advances in the use of ionic liquids for electrochemical sensing.

    Science.gov (United States)

    Silvester, Debbie S

    2011-12-07

    Ionic Liquids are salts that are liquid at (or just above) room temperature. They possess several advantageous properties (e.g. high intrinsic conductivity, wide electrochemical windows, low volatility, high thermal stability and good solvating ability), which make them ideal as non-volatile electrolytes in electrochemical sensors. This mini-review article describes the recent uses of ionic liquids in electrochemical sensing applications (covering the last 3 years) in the context of voltammetric sensing at solid/liquid, liquid/liquid interfaces and carbon paste electrodes, as well as their use in gas sensing, ion-selective electrodes, and for detecting biological molecules, explosives and chemical warfare agents. A comment on the future direction and challenges in this field is also presented.

  16. Lithium-conducting ionic melt electrolytes from polyether-functionalized fluorosulfonimide anions

    International Nuclear Information System (INIS)

    Hallac, B.B.; Geiculescu, O.E.; Rajagopal, R.V.; Creager, S.E.; DesMarteau, D.D.

    2008-01-01

    Solvent-free lithium-conducting ionic melt (IM) electrolytes were synthesized and characterized with respect to chemical structure, purity, and ion transport properties. The melts consist of lithium (perfluorovinylether)sulfonimide salts attached covalently to a lithium-solvating polyether chain. Ionic conductivities are relatively high which is a consequence of the favorable combination of the low lattice energy of the lithium fluorosulfonimide salt (low basicity of the fluorosulfonimide anion), the relatively low viscosity of the polyether matrix, and the relatively high salt content of the melts. Galvanostatic dc polarization experiments, using cells with non-blocking Li electrodes, indicate that salt concentration polarization does not occur in these electrolytes as dc current is passed through them

  17. Solid electrolyte material manufacturable by polymer processing methods

    Science.gov (United States)

    Singh, Mohit; Gur, Ilan; Eitouni, Hany Basam; Balsara, Nitash Pervez

    2012-09-18

    The present invention relates generally to electrolyte materials. According to an embodiment, the present invention provides for a solid polymer electrolyte material that is ionically conductive, mechanically robust, and can be formed into desirable shapes using conventional polymer processing methods. An exemplary polymer electrolyte material has an elastic modulus in excess of 1.times.10.sup.6 Pa at 90 degrees C. and is characterized by an ionic conductivity of at least 1.times.10.sup.-5 Scm-1 at 90 degrees C. An exemplary material can be characterized by a two domain or three domain material system. An exemplary material can include material components made of diblock polymers or triblock polymers. Many uses are contemplated for the solid polymer electrolyte materials. For example, the present invention can be applied to improve Li-based batteries by means of enabling higher energy density, better thermal and environmental stability, lower rates of self-discharge, enhanced safety, lower manufacturing costs, and novel form factors.

  18. Full characterization of polypyrrole thin films electrosynthesized in room temperature ionic liquids, water or acetonitrile

    International Nuclear Information System (INIS)

    Viau, L.; Hihn, J.Y.; Lakard, S.; Moutarlier, V.; Flaud, V.; Lakard, B.

    2014-01-01

    Highlights: • Polypyrrole films were electrodeposited from three room temperature ionic liquids. • Polymer films were characterized using many surface analysis techniques. • The incorporation of anions and/or cations inside the polymer films was evidenced. • The influence of the ionic liquid on the polymer properties was deeply studied. - Abstract: Pyrrole was electrochemically oxidized in two conventional media (water and acetonitrile) and in three room temperature ionic liquids: 1-butyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, and 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide. Infrared and Raman Spectroscopies confirmed the formation of polypyrrole by electropolymerization but were unable to demonstrate the presence of anions in the polymer films. The use of ionic liquids as growth media resulted in polymer films having a good electrochemical activity. The difference of activity from one polymer film to the other was mainly attributed to the difference of viscosity between the solvents used. The morphological features of the polypyrrole films were also fully studied. Profilometric measurements demonstrated that polymer films grown, at the same potential, in ionic liquids were thinner and had a smaller roughness than those grown in other solvents. Atomic Force Microscopy showed that polypyrrole films had nearly similar micrometric nodular structure whatever the growth medium even if some differences of porosity and homogeneity were observed using Scanning Electron Microscopy. The incorporation of counter-anions at the top surface of the films was finally evidenced by X-ray Photoelectron Spectroscopy. These anions were also incorporated inside the polymer film with a uniform distribution as shown by Glow Discharge Optical Emission Spectroscopy

  19. Lithium conducting ionic liquids based on lithium borate salts

    Energy Technology Data Exchange (ETDEWEB)

    Zygadlo-Monikowska, E.; Florjanczyk, Z.; Sluzewska, K.; Ostrowska, J.; Langwald, N.; Tomaszewska, A. [Warsaw University of Technology, Faculty of Chemistry, ul. Noakowskiego 3, 00-664 Warsaw (Poland)

    2010-09-15

    The simple reaction of trialkoxyborates with butyllithium resulted in the obtaining of new lithium borate salts: Li{l_brace}[CH{sub 3}(OCH{sub 2}CH{sub 2}){sub n}O]{sub 3}BC{sub 4}H{sub 9}{r_brace}, containing oxyethylene substituents (EO) of n=1, 2, 3 and 7. Salts of n {>=} 2 show properties of room temperature ionic liquid (RTIL) of low glass transition temperature, T{sub g} of the order from -70 to -80 C. The ionic conductivity of the salts depends on the number of EO units, the highest conductivity is shown by the salt with n = 3; in bulk its ambient temperature conductivity is 2 x 10{sup -5} S cm{sup -1} and in solution in cyclic propylene sulfite or EC/PC mixture, conductivity increases by an order of magnitude. Solid polymer electrolytes with borate salts over a wide concentration range, from 10 to 90 mol.% were obtained and characterized. Three types of polymeric matrices: poly(ethylene oxide) (PEO), poly(trimethylene carbonate) (PTMC) and two copolymers of acrylonitrile and butyl acrylate p(AN-BuA) were used in them as polymer matrices. It has been found that for systems of low salt concentration (10 mol.%) the best conducting properties were shown by solid polymer electrolytes with PEO, whereas for systems of high salt concentration, of the polymer-in-salt type, good results were achieved for PTMC as polymer matrix. (author)

  20. Hydrogen production from glucose in ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Assenbaum, D.W.; Taccardi, N.; Berger, M.E.M.; Boesmann, A.; Enzenberger, F.; Woelfel, R.; Wasserscheid, P. [Erlangen-Nuernberg Univ. (Germany). Lehrstuhl fuer chemische Reaktionstechnik

    2010-07-01

    technologies suffer from the fact that the overall reaction rates are often restricted by mass and heat transport problems. Lastly, there are severe limitations concerning the feedstock selection as for some important substrates, such as e.g. glucose, the process can only be operated in very diluted systems to avoid rapid tar formation [22,23,24]. In this contribution we describe for the first time a catalytic reaction system producing hydrogen from glucose in astonishingly high selectivities using a single reaction step under very mild conditions. The catalytic reaction system is characterized by its homogeneous nature and comprises a Ru-complex catalyst dissolved and stabilized in an ionic liquid medium. Ionic liquids are salts of melting points below 100 C [25]. These liquid materials have attracted much interest in the last decade as solvents for catalytic reactions [26] and separation technologies (extraction, distillation) [27,28,29,30,31,32]. Besides, these liquids have found industrial applications as process fluids for mechanic [33] and electrochemical applications [34]. Finally, from the pioneering work of Rogers and co-workers, it is known that ionic liquids are able to dissolve significant amounts of water-insoluble biopolymers (such as e.g. cellulose and chitin)[35] and even complex biopolymer mixtures, such as e.g. wood, have been completely dissolved in some ionic liquids [36]. In our specific application, the role of the ionic liquid is threefold: a) the ionic liquid dissolves the carbohydrate starting material thus expanding the range of applicable carbohydrate to water insoluble polymers; b) the ionic liquid provides a medium to dissolve and stabilize the catalyst; c) the ionic liquid dissolves hydrogen at a very low level, so inhibiting any possible collateral hydrogen-consuming process (detailed investigation of the hydrogen solubility in ionic liquids have been reported by e.g. Brennecke and coworkers [37]). (orig.)

  1. Ductile thermoset polymers via controlling network flexibility.

    Science.gov (United States)

    Hameed, N; Salim, N V; Walsh, T R; Wiggins, J S; Ajayan, P M; Fox, B L

    2015-06-18

    We report the design and synthesis of a polymer structure from a cross-linkable epoxy-ionic liquid system which behaves like a hard and brittle epoxy thermoset, perfectly ductile thermoplastic and an elastomer, all depending on controllable network compositions.

  2. Recent advances on ionic liquid uses in separation techniques.

    Science.gov (United States)

    Berthod, A; Ruiz-Ángel, M J; Carda-Broch, S

    2018-07-20

    The molten organic salts with melting point below 100°C, commonly called ionic liquids (ILs) have found numerous uses in separation sciences due to their exceptional properties as non molecular solvents, namely, a negligible vapor pressure, a high thermal stability, and unique solvating properties due to polarity and their ionic character of molten salts. Other properties, such as viscosity, boiling point, water solubility, and electrochemical window, are adjustable playing with which anion is associated with which cation. This review focuses on recent development of the uses of ILs in separation techniques actualizing our 2008 article (same authors, J. Chromatogr. A, 1184 (2008) 6-18) focusing on alkyl methylimidazolium salts. These developments include the use of ILs in nuclear waste reprocessing, highly thermally stable ILs that allowed for the introduction of polar gas chromatography capillary columns able to work at temperature never seen before (passing 300°C), the use of ILs in liquid chromatography and capillary electrophoresis, and the introduction of tailor-made ILs for mass spectrometry detection of trace anions at the few femtogram level. The recently introduced deep eutectic solvents are not exactly ILs, they are related enough so that their properties and uses in countercurrent chromatography are presented. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Polarizability effects on the structure and dynamics of ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Cavalcante, Ary de Oliveira, E-mail: arycavalcante@ufam.edu.br [Institute of Chemistry, University of Campinas – UNICAMP, Cx. P. 6154, Campinas, SP 13084-862 (Brazil); Departamento de Química, Universidade Federal do Amazonas, Av. Rodrigo Octávio, 6200, Coroado, Manaus, AM (Brazil); Ribeiro, Mauro C. C. [Laboratório de Espectroscopia Molecular, Instituto de Química, Universidade de São Paulo, São Paulo, SP C.P. 26077, 05513 970 São Paulo, SP (Brazil); Skaf, Munir S. [Institute of Chemistry, University of Campinas – UNICAMP, Cx. P. 6154, Campinas, SP 13084-862 (Brazil)

    2014-04-14

    Polarization effects on the structure and dynamics of ionic liquids are investigated using molecular dynamics simulations. Four different ionic liquids were simulated, formed by the anions Cl{sup −} and PF{sub 6}{sup −}, treated as single fixed charge sites, and the 1-n-alkyl-3-methylimidazolium cations (1-ethyl and 1-butyl-), which are polarizable. The partial charge fluctuation of the cations is provided by the electronegativity equalization model (EEM) and a complete parameter set for the cations electronegativity (χ) and hardness (J) is presented. Results obtained from a non-polarizable model for the cations are also reported for comparison. Relative to the fixed charged model, the equilibrium structure of the first solvation shell around the imidazolium cations shows that inclusion of EEM polarization forces brings cations closer to each other and that anions are preferentially distributed above and below the plane of the imidazolium ring. The polarizable model yields faster translational and reorientational dynamics than the fixed charges model in the rotational-diffusion regime. In this sense, the polarizable model dynamics is in better agreement with the experimental data.

  4. Super ionic conductive glass

    Science.gov (United States)

    Susman, S.; Volin, K.J.

    Described is an ionically conducting glass for use as a solid electrolyte in a power or secondary cell containing an alkali metal-containing anode and a cathode separated by an alkali metal ion conducting glass having an ionic transference number of unity and the general formula: A/sub 1 + x/D/sub 2-x/3/Si/sub x/P/sub 3 - x/O/sub 12 - 2x/3/, wherein A is a network modifier for the glass and is an alkali metal of the anode, D is an intermediate for the glass and is selected from the class consisting of Zr, Ti, Ge, Al, Sb, Be, and Zn and X is in the range of from 2.25 to 3.0. Of the alkali metals, Na and Li are preferred and of the intermediate, Zr, Ti and Ge are preferred.

  5. Ionic liquid marbles.

    Science.gov (United States)

    Gao, Lichao; McCarthy, Thomas J

    2007-10-09

    Liquid marbles have been reported during this decade and have been argued to be potentially useful for microfluidic and lab-on-a-chip applications. The liquid marbles described to date have been composed of either water or glycerol as the liquid and hydrophobized lycopodium or silica as the stabilizing particles. Both of these components are potentially reactive and do not permit the use of organic chemistry; the liquids are volatile. We report the use of perfluoroalkyl particles (oligomeric (OTFE) and polymeric (PTFE) tetrafluoroethylene, which are unreactive) to support/stabilize a range of ionic liquid marbles. Ionic liquids are not volatile and have been demonstrated to be versatile solvents for chemical transformations. Water marbles prepared with OTFE are much more robust than those prepared with hydrophobized lycopodium or silica.

  6. Solvation quantities from a COSMO-RS equation of state

    International Nuclear Information System (INIS)

    Panayiotou, C.; Tsivintzelis, I.; Aslanidou, D.; Hatzimanikatis, V.

    2015-01-01

    Highlights: • Extension of the successful COSMO-RS model to an equation-of-state model. • Two scaling constants, obtained from atom-specific contributions. • Overall estimation of the solvation quantities and contributions. - Abstract: This work focuses on the extension of the successful COSMO-RS model of mixtures into an equation-of-state model of fluids and its application for the estimation of solvation/hydration quantities of a variety of chemical substances. These quantities include free-energies, enthalpies and entropies of hydration as well as the separate contributions to each of them. Emphasis is given on the estimation of contributions from the conformational changes of solutes upon solvation and the associated restructuring of solvent in its immediate neighborhood. COSMO-RS is a quantum-mechanics based group/segment contribution model in which the Quasi-Chemical (QC) approach is used for the description of the non-random distribution of interacting segments in the system. Thus, the equation-of-state development is done through such a QC framework. The new model will not need any adjustable parameters for the strong specific interactions, such as hydrogen bonds, since they will be provided by the quantum-mechanics based cosmo-files – a key feature of COSMO-RS model. It will need, however, one volumetric and one energy parameter per fluid, which are scaling constants or molecular descriptors of the fluid and are obtained from rather easily available data such as densities, boiling points, vapor pressures, heats of vaporization or second virial coefficients. The performance and the potential of the new equation-of-state model to become a fully predictive model are critically discussed

  7. POSS Ionic Liquid.

    Science.gov (United States)

    Tanaka, Kazuo; Ishiguro, Fumiyasu; Chujo, Yoshiki

    2010-12-22

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

  8. Thermodynamic estimation: Ionic materials

    International Nuclear Information System (INIS)

    Glasser, Leslie

    2013-01-01

    Thermodynamics establishes equilibrium relations among thermodynamic parameters (“properties”) and delineates the effects of variation of the thermodynamic functions (typically temperature and pressure) on those parameters. However, classical thermodynamics does not provide values for the necessary thermodynamic properties, which must be established by extra-thermodynamic means such as experiment, theoretical calculation, or empirical estimation. While many values may be found in the numerous collected tables in the literature, these are necessarily incomplete because either the experimental measurements have not been made or the materials may be hypothetical. The current paper presents a number of simple and relible estimation methods for thermodynamic properties, principally for ionic materials. The results may also be used as a check for obvious errors in published values. The estimation methods described are typically based on addition of properties of individual ions, or sums of properties of neutral ion groups (such as “double” salts, in the Simple Salt Approximation), or based upon correlations such as with formula unit volumes (Volume-Based Thermodynamics). - Graphical abstract: Thermodynamic properties of ionic materials may be readily estimated by summation of the properties of individual ions, by summation of the properties of ‘double salts’, and by correlation with formula volume. Such estimates may fill gaps in the literature, and may also be used as checks of published values. This simplicity arises from exploitation of the fact that repulsive energy terms are of short range and very similar across materials, while coulombic interactions provide a very large component of the attractive energy in ionic systems. Display Omitted - Highlights: • Estimation methods for thermodynamic properties of ionic materials are introduced. • Methods are based on summation of single ions, multiple salts, and correlations. • Heat capacity, entropy

  9. Solvation of the electron in alcohols studied using the Argonne picosecond pulse radiolysis system

    International Nuclear Information System (INIS)

    Jonah, C.D.; Kenney-Wallace, G.A.

    1979-01-01

    With a stroboscopic pulse radiolysis system, it is possible to measure the reactions of solvated electrons and dry electrons and the solvation time of electrons in alcohols from 20 psec to 350 psec. The solvation in alcohol and alcohol-alkane solutions is a complex process which depends on the microscopic structure of the fluid, so that the studies of solvation in alcohols as a function of temperature or as a function of the concentration of the alcohols must take into account the structure of the fluid being studied. The relaxation processes may not be dominant at low temperature. However, in room temperature alcohols, pre-existing traps are the dominant means of electron trapping. The extrapolation to water may be reasonable since water and alcohols both give similar final species. To obtain such idea of the solvation process in alcohols, the change of the absorption of electrons at 500 nm was measured. At very low concentration of alcohols in alkanes, electrons form a complex with a cluster of alcohol molecules, and the most probable size of this cluster is two alcohols (C 4 , C 10 ). The species formed is not solvated electrons, since the characteristic spectrum of solvated electrons is absent, and the conductivity of the species is far above that of solvated electrons. (Yamashita, S.)

  10. Molecular dynamics study of the solvation of an alpha-helical transmembrane peptide by DMSO

    NARCIS (Netherlands)

    Duarte, A.M.; Mierlo, van C.P.M.; Hemminga, M.A.

    2008-01-01

    10-ns molecular dynamics study of the solvation of a hydrophobic transmembrane helical peptide in dimethyl sulfoxide (DMSO) is presented. The objective is to analyze how this aprotic polar solvent is able to solvate three groups of amino acid residues (i.e., polar, apolar, and charged) that are

  11. Studies of base pair sequence effects on DNA solvation based on all

    Indian Academy of Sciences (India)

    Detailed analyses of the sequence-dependent solvation and ion atmosphere of DNA are presented based on molecular dynamics (MD) simulations on all the 136 unique tetranucleotide steps obtained by the ABC consortium using the AMBER suite of programs. Significant sequence effects on solvation and ion localization ...

  12. Femtosecond spectroscopic study of the solvation of amphiphilic molecules by water

    NARCIS (Netherlands)

    Rezus, Y.L.A.; Bakker, H.J.

    2008-01-01

    We use polarization-resolved mid-infrared pump-probe spectroscopy to study the aqueous solvation of proline and N-methylacetamide. These molecules serve as models to study the solvation of proteins. We monitor the orientational dynamics of partly deuterated water molecules (HDO) that are present at

  13. Competitive solvation of (bis)(trifluoromethanesulfonyl)imide anion by acetonitrile and water

    DEFF Research Database (Denmark)

    Chaban, Vitaly

    2014-01-01

    Competitive solvation of an ion by two or more solvents is one of the key phenomena determining the identity of our world. Solvation in polar solvents frequently originates from non-additive non-covalent interactions. Pre-parametrized potentials poorly capture these interactions, unless the force...

  14. Time-dependent friction and solvation time correlation function

    International Nuclear Information System (INIS)

    Samanta, Alok; Ali, Sk Musharaf; Ghosh, Swapan K

    2005-01-01

    We have derived a new relation between the time-dependent friction and solvation time correlation function (STCF) for non-polar fluids. The friction values calculated using this relation and simulation results on STCF for a Lennard-Jones fluid are shown to have excellent agreement with the same obtained through mode-coupling theory. Also derived is a relation between the time-dependent dielectric friction and STCF for polar fluids. Routes are thus provided to obtain the time-dependent friction (non-polar as well as dielectric) from an experimentally measured quantity like STCF, even if the interparticle interaction potential is not known

  15. Equilibrium and nonequilibrium solvation and solute electronic structure

    International Nuclear Information System (INIS)

    Kim, H.J.; Hynes, J.T.

    1990-01-01

    When a molecular solute is immersed in a polar and polarizable solvent, the electronic wave function of the solute system is altered compared to its vacuum value; the solute electronic structure is thus solvent-dependent. Further, the wave function will be altered depending upon whether the polarization of the solvent is or is not in equilibrium with the solute charge distribution. More precisely, while the solvent electronic polarization should be in equilibrium with the solute electronic wave function, the much more sluggish solvent orientational polarization need not be. We call this last situation non-equilibrium solvation. We outline a nonlinear Schroedinger equation approach to these issues

  16. Role of trapped and solvated electrons in Ps formation

    International Nuclear Information System (INIS)

    Stepanov, S.V.; Byakov, V.M.; Mikhin, K.V.; He, C.; Hirade, T.

    2005-01-01

    Role of trapped and solvated electrons in Ps formation is discussed. Combination of thermalized positron with such electrons is possible from the view point of the energy balance and may results in Ps formation. This process proceeds during all e = lifetime matter. Fitting of raw experimental e + -e - annihilation spectra has to be based on an adequate physical input, which often leads to necessity of nonexponential deconvolution of the spectra. We have interpreted the Ps formation data in polyethylene, ethylene-methylmethacrylate and polymethylmethacrylate in dark and in light vs. tome of the measurement and temperature. parameters characterized accumulation of trapped electrons and their recombination with counter ions and positrons are obtained. (author)

  17. Electrochemical redox reactions in solvated silica sol-gel glass

    International Nuclear Information System (INIS)

    Opallo, M.

    2002-01-01

    The studies of electrochemical redox reactions in solvated silica sol-gel glass were reviewed. The methodology of the experiments with emphasis on the direct preparation of the solid electrolyte and the application ultra microelectrodes was described. Generally, the level of the electrochemical signal is not much below that observed in liquid electrolyte. The current depends on time elapsed after gelation, namely the longer time, the smaller current. The differences between electrochemical behaviour of the redox couples in monoliths and thin layers were described. (author)

  18. Ionic .pi.-conjugated polyelectrolytes by catalyst free polymerization of bis(pyridyl)acetylenes and bis[(pyridyl)ethynyl]benzenes

    Czech Academy of Sciences Publication Activity Database

    Faukner, T.; Trhlíková, Olga; Zedník, J.; Sedláček, J.

    2015-01-01

    Roč. 216, č. 14 (2015), s. 1540-1554 ISSN 1022-1352 R&D Projects: GA ČR GAP108/12/1143 Institutional support: RVO:61389013 Keywords : conjugated polymers * ionic polymers * polyacetylenes Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.495, year: 2015

  19. Course on Ionic Channels

    CERN Document Server

    1986-01-01

    This book is based on a series of lectures for a course on ionic channels held in Santiago, Chile, on November 17-20, 1984. It is intended as a tutorial guide on the properties, function, modulation, and reconstitution of ionic channels, and it should be accessible to graduate students taking their first steps in this field. In the presentation there has been a deliberate emphasis on the spe­ cific methodologies used toward the understanding of the workings and function of channels. Thus, in the first section, we learn to "read" single­ channel records: how to interpret them in the theoretical frame of kinetic models, which information can be extracted from gating currents in re­ lation to the closing and opening processes, and how ion transport through an open channel can be explained in terms of fluctuating energy barriers. The importance of assessing unequivocally the origin and purity of mem­ brane preparations and the use of membrane vesicles and optical tech­ niques in the stUGY of ionic channels a...

  20. Fabrication of Greener Membranes from Ionic Liquid Solutions

    KAUST Repository

    Kim, DooLi

    2017-06-01

    Membrane technology plays a crucial role in different separation processes such as biotechnology, pharmaceutical, and food industries, drinking water supply, and wastewater treatment. However, there is a growing concern that solvents commonly used for membrane fabrication, such as dimethylformamide (DMF), dimethylacetamide (DMAc), and 1-methyl-2-pyrrolidone (NMP), are toxic to the environment and human health. To explore the possibility of substituting these toxic solvents by less toxic or safer solvents, polymers commonly used for membrane fabrication, such as polyacrylonitrile (PAN), cellulose acetate (CA), polyethersulfone (PES), and poly(ether imide sulfone) (EXTEMTM), were dissolved in ionic liquids. Flat sheet and hollow fiber membranes were then fabricated. The thermodynamics of the polymer solutions, the kinetics of phase inversion and other factors, which resulted in significant differences in the membrane structure, compared to those of membranes fabricated from more toxic solvents, were investigated. Higher water permeance with smaller pores, unique and uniform morphologies, and narrower pore size distribution, were observed in the ionic liquid-based membranes. Furthermore, comparable performance on separation of peptides and proteins with various molecular weights was achieved with the membranes fabricated from ionic liquid solutions. In summary, we propose less hazardous polymer solutions to the environment, which can be used for the membrane fabrication with better performance and more regular morphology.