Energy harvesting from the tail beating of a carangiform swimmer using ionic polymer-metal composites.

PubMed

Cha, Youngsu; Verotti, Matteo; Walcott, Horace; Peterson, Sean D; Porfiri, Maurizio

2013-09-01

In this paper, we study energy harvesting from the beating of a biomimetic fish tail using ionic polymer-metal composites. The design of the biomimetic tail is based on carangiform swimmers and is specifically inspired by the morphology of the heterocercal tail of thresher sharks. The tail is constituted of a soft silicone matrix molded in the form of the heterocercal tail and reinforced by a steel beam of rectangular cross section. We propose a modeling framework for the underwater vibration of the biomimetic tail, wherein the tail is assimilated to a cantilever beam with rectangular cross section and heterogeneous physical properties. We focus on base excitation in the form of a superimposed rotation about a fixed axis and we consider the regime of moderately large-amplitude vibrations. In this context, the effect of the encompassing fluid is described through a hydrodynamic function, which accounts for inertial, viscous and convective phenomena. The model is validated through experiments in which the base excitation is systematically varied and the motion of selected points on the biomimetic tail tracked in time. The feasibility of harvesting energy from an ionic polymer-metal composite attached to the vibrating structure is experimentally and theoretically assessed. The response of the transducer is described using a black-box model, where the voltage output is controlled by the rate of change of the mean curvature. Experiments are performed to elucidate the impact of the shunting resistance, the frequency of the base excitation and the placement of the ionic polymer-metal composite on energy harvesting from the considered biomimetic tail.

Development of large-surface Nafion-metal composite actuator and its electrochemical characterization

NASA Astrophysics Data System (ADS)

Noh, Taegeun; Tak, Yong Suk; Nam, Jaedo; Jeon, Jaewook; Kim, Hunmo; Choi, Hyoukryeol; Bae, Sang Sik

2001-07-01

Behaviors of nafion-based actuators are significantly affected by interfacial area between electrode and polymer electrolyte. Replication method was utilized to manufacture a large surface-area composite actuator. Etched aluminum foil was used as a template for replication using liquid nafion solution. Measurement of double layer charging and scanning electron microscopy indicated that interfacial area was greatly increased by replication method. Higher surface area induced a better bending performance of ionic polymer metal composite (IPMC). In parallel, the effect of cations on IPMC was interpreted with constant current experiment, linear sweep voltammetry and electrochemical impedance spectroscopy. For univalent cations, ion size is the most influencing parameter on ionic mobility inside membrane. However, ion-ion interaction affects an ionic mobility for divalent cations.

Comparative study of bending characteristics of ionic polymer actuators containing ionic liquids for modeling actuation

NASA Astrophysics Data System (ADS)

Kikuchi, Kunitomo; Sakamoto, Takumi; Tsuchitani, Shigeki; Asaka, Kinji

2011-04-01

Ionic polymer metal composites (IPMCs) that can operate in air have recently been developed by incorporating an ionic liquid in ionic polymers. To understand transduction in these composites, it is important to determine the role of the ionic liquid in the ionic polymer (Nafion®), to identify the counter cation, and to investigate the interaction of IPMCs with water vapor in the air. We used Fourier-transform infrared spectroscopy to analyze three Nafion® membranes, which were soaked in mixtures of water and an ionic liquid (1-ethyl-3-methyl-imidazolium tetrafluoroborate (EMIBF4), 1-buthyl-3-methyl-imidazolium tetrafluoroborate (BMIBF4), and 1-buthyl-3-methyl-imidazolium hexafluorophosphate (BMIPF6)). The results demonstrate that only cations (EMI+ and BMI+) in the ionic liquids are taken into the Nafion® membranes as counter ions and that the water content of the membranes in air is less than ˜4% that of Nafion® swollen with water. Based on the experimental results, a transduction model is proposed for an IPMC with an ionic liquid. In this model, bending is caused by local swelling due to the volume effect of the bulky counter cations. This model can explain 30-50% of the experimentally observed bending curvature.

"JCE" Classroom Activity Connections: NaCl or CaCl[subscript 2], Smart Polymer Gel Tells More

ERIC Educational Resources Information Center

Chen, Yueh-Huey; Lin, Jia-Ying; Wang, Yu-Chen; Yaung, Jing-Fun

2010-01-01

This classroom activity connection demonstrates the differences between the effects of NaCl (a salt of monovalent metal ions) and CaCl[subscript 2] (a salt of polyvalent metal ions) on swollen superabsorbent polymer gels. Being ionic compounds, NaCl and CaCl[subscript 2] both collapse the swollen polymer gels. The gel contracted by NaCl reswells…

Oxyphosphorus-containing polymers as binders for battery cathodes

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

Pratt, Russell Clayton; Mullin, Scott Allen; Eitouni, Hany Basam

A class of polymeric phosphorous esters can be used as binders for battery cathodes. Metal salts can be added to the polymers to provide ionic conductivity. The polymeric phosphorous esters can be formulated with other polymers either as mixtures or as copolymers to provide additional desirable properties. Examples of such properties include even higher ionic conductivity and improved mechanical properties. Furthermore, cathodes that include the polymeric phosphorous esters can be assembled with a polymeric electrolyte separator and an anode to form a complete battery.

Ionic polymer metal composites with nanoporous carbon electrodes

NASA Astrophysics Data System (ADS)

Palmre, Viljar; Brandell, Daniel; Mäeorg, Uno; Torop, Janno; Volobujeva, Olga; Punning, Andres; Johanson, Urmas; Aabloo, Alvo

2010-04-01

Ionic Polymer Metal Composites (IPMCs) are soft electroactive polymer materials that bend in response to the voltage stimulus (1 - 4 V). They can be used as actuators or sensors. In this paper, we introduce two new highly-porous carbon materials for assembling high specific area electrodes for IPMC actuators and compare their electromechanical performance with recently reported IPMCs based on RuO2 electrodes. We synthesize ionic liquid (Emi-Tf) actuators with either Carbide-Derived Carbon (CDC) (derived from TiC) or coconut shell based activated carbon electrodes. The carbon electrodes are applied onto ionic liquid-swollen Nafion membranes using the direct assembly process. Our results show that actuators assembled with CDC electrodes have the greatest peak-to-peak strain output, reaching up to 20.4 mɛ (equivalent to >2%) at a 2 V actuation signal, exceeding that of the RuO2 electrodes by more than 100%. The electrodes synthesized from TiC-derived carbon also revealed significantly higher maximum strain rate. The differences between the materials are discussed in terms of molecular interactions and mechanisms upon actuation in the different electrodes.

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

NASA Astrophysics Data System (ADS)

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.

Cycling performance of lithium metal polymer cells assembled with ionic liquid and poly(3-methyl thiophene)/carbon nanotube composite cathode

NASA Astrophysics Data System (ADS)

Kim, Dong-Won; Sivakkumar, S. R.; MacFarlane, Douglas R.; Forsyth, Maria; Sun, Yang-Kook

A poly(3-methylthiophene) (PMT)/multi-walled carbon nanotube (CNT) composite is synthesized by in situ chemical polymerization. The PMT/CNT composite is used as an active cathode material in lithium metal polymer cells assembled with ionic liquid (IL) electrolytes. The IL electrolyte consists of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF 4) and LiBF 4. A small amount of vinylene carbonate is added to the IL electrolyte to prevent the reductive decomposition of the imidazolium cation in EMIBF 4. A porous poly(vinylidene fluoride- co-hexafluoropropylene) (P(VdF- co-HFP)) film is used as a polymer membrane for assembling the cells. Electrochemical properties of the PMT/CNT composite electrode in the IL electrolyte are evaluated and the effect of vinylene carbonate on the cycling performance of the lithium metal polymer cells is investigated. The cells assembled with a non-flammable IL electrolyte and a PMT/CNT composite cathode are promising candidates for high-voltage-power sources with enhanced safety.

Soft actuator based on Kraton with GO/Ag/Pani composite electrodes for robotic applications

NASA Astrophysics Data System (ADS)

Khan, Ajahar; Kant Jain, Ravi; Banerjee, Priyabrata; Inamuddin; Asiri, Abdullah M.

2017-11-01

In this work, electrochemically-driven Kraton/graphene oxide/Ag/polyaniline (Kraton/GO/Ag/Pani) polymer composite based ionic polymer metal composite (IPMC) was fabricated as a soft actuator. Silver nanopowder with polyaniline coating used as an electrode material is a novel approach in the fabrication of IPMC, which gives new opportunities for development of the electrode on ionic polymer actuator surfaces directly without electroless plating of Pt or Au metal. The Kraton/GO/Ag/Pani membrane showed much higher water-uptake (WU), ion exchange capacity (IEC), proton conductivity than those of several reported IPMC membranes. The enhanced actuation performance indicates that the Kraton/GO/Ag/Pani is a better alternative to the highly expensive commercialized IPMC actuator.

Triboelectric energy harvesting with surface-charge-fixed polymer based on ionic liquid

PubMed Central

Sano, Chikako; Mitsuya, Hiroyuki; Ono, Shimpei; Miwa, Kazumoto; Toshiyoshi, Hiroshi; Fujita, Hiroyuki

2018-01-01

Abstract A novel triboelectric energy harvester has been developed using an ionic liquid polymer with cations fixed at the surface. In this report, the fabrication of the device and the characterization of its energy harvesting performance are detailed. An electrical double layer was induced in the ionic liquid polymer precursor to attract the cations to the surface where they are immobilized using a UV-based crosslinking reaction. The finalized polymer is capable of generating an electrical current when contacted by a metal electrode. Using this property, energy harvesting experiments were conducted by cyclically contacting a gold-surface electrode with the charge fixed surface of the polymer. Control experiments verified the effect of immobilizing the cations at the surface. By synthesizing a polymer with the optimal composition ratio of ionic liquid to macromonomer, an output of 77 nW/cm2 was obtained with a load resistance of 1 MΩ at 1 Hz. This tuneable power supply with a μA level current output may contribute to Internet of Things networks requiring numerous sensor nodes at remote places in the environment. PMID:29707070

Poly(vinylidene fluoride-hexafluoropropylene) polymer electrolyte for paper-based and flexible battery applications

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

Aliahmad, Nojan; Shrestha, Sudhir; Varahramyan, Kody

2016-06-15

Paper-based batteries represent a new frontier in battery technology. However, low-flexibility and poor ionic conductivity of solid electrolytes have been major impediments in achieving practical mechanically flexible batteries. This work discuss new highly ionic conductive polymer gel electrolytes for paper-based battery applications. In this paper, we present a poly(vinylidene fluoride-hexafluoropropylene) (PVDH-HFP) porous membrane electrolyte enhanced with lithium bis(trifluoromethane sulphone)imide (LiTFSI) and lithium aluminum titanium phosphate (LATP), with an ionic conductivity of 2.1 × 10{sup −3} S cm{sup −1}. Combining ceramic (LATP) with the gel structure of PVDF-HFP and LiTFSI ionic liquid harnesses benefits of ceramic and gel electrolytes in providingmore » flexible electrolytes with a high ionic conductivity. In a flexibility test experiment, bending the polymer electrolyte at 90° for 20 times resulted in 14% decrease in ionic conductivity. Efforts to further improving the flexibility of the presented electrolyte are ongoing. Using this electrolyte, full-cell batteries with lithium titanium oxide (LTO) and lithium cobalt oxide (LCO) electrodes and (i) standard metallic current collectors and (ii) paper-based current collectors were fabricated and tested. The achieved specific capacities were (i) 123 mAh g{sup −1} for standard metallic current collectors and (ii) 99.5 mAh g{sup −1} for paper-based current collectors. Thus, the presented electrolyte has potential to become a viable candidate in paper-based and flexible battery applications. Fabrication methods, experimental procedures, and test results for the polymer gel electrolyte and batteries are presented and discussed.« less

Poly(vinylidene fluoride-hexafluoropropylene) polymer electrolyte for paper-based and flexible battery applications

NASA Astrophysics Data System (ADS)

Aliahmad, Nojan; Shrestha, Sudhir; Varahramyan, Kody; Agarwal, Mangilal

2016-06-01

Paper-based batteries represent a new frontier in battery technology. However, low-flexibility and poor ionic conductivity of solid electrolytes have been major impediments in achieving practical mechanically flexible batteries. This work discuss new highly ionic conductive polymer gel electrolytes for paper-based battery applications. In this paper, we present a poly(vinylidene fluoride-hexafluoropropylene) (PVDH-HFP) porous membrane electrolyte enhanced with lithium bis(trifluoromethane sulphone)imide (LiTFSI) and lithium aluminum titanium phosphate (LATP), with an ionic conductivity of 2.1 × 10-3 S cm-1. Combining ceramic (LATP) with the gel structure of PVDF-HFP and LiTFSI ionic liquid harnesses benefits of ceramic and gel electrolytes in providing flexible electrolytes with a high ionic conductivity. In a flexibility test experiment, bending the polymer electrolyte at 90° for 20 times resulted in 14% decrease in ionic conductivity. Efforts to further improving the flexibility of the presented electrolyte are ongoing. Using this electrolyte, full-cell batteries with lithium titanium oxide (LTO) and lithium cobalt oxide (LCO) electrodes and (i) standard metallic current collectors and (ii) paper-based current collectors were fabricated and tested. The achieved specific capacities were (i) 123 mAh g-1 for standard metallic current collectors and (ii) 99.5 mAh g-1 for paper-based current collectors. Thus, the presented electrolyte has potential to become a viable candidate in paper-based and flexible battery applications. Fabrication methods, experimental procedures, and test results for the polymer gel electrolyte and batteries are presented and discussed.

Analysis and experiment on a self-sensing ionic polymer-metal composite actuator

NASA Astrophysics Data System (ADS)

Nam, Doan Ngoc Chi; Ahn, Kyoung Kwan

2014-07-01

An ionic polymer-metal composite (IPMC) actuator is an electro-active polymer (EAP) that bends in response to a small applied electrical field as a result of the mobility of cations in the polymer network. This paper aims to develop a self-sensing actuator for practical use, since current sensing methods generally face limitations due to the compact size and mobility of the IPMC actuator. Firstly, the variation of surface resistance during bending operations is investigated. Then, the behavior of IPMC corresponding to the variation of surface resistance is mathematically analyzed. Based on the analysis results, a simple configuration to realize the self-sensing behavior is introduced. In this technique, the bending curvature of an IPMC can be obtained accurately by employing several feedback voltage signals along with the IPMC length. Finally, experimental evaluations proved the ability of the proposed scheme to estimate the bending behavior of IPMC actuators.

Aggregate-mediated charge transport in ionomeric electrolytes

NASA Astrophysics Data System (ADS)

Lu, Keran; Maranas, Janna; Milner, Scott

Polymers such PEO can conduct ions, and have been studied as possible replacements for organic liquid electrolytes in rechargeable metal-ion batteries. More generally, fast room-temperature ionic conduction has been reported for a variety of materials, from liquids to crystalline solids. Unfortunately, polymer electrolytes generally have limited conductivity; these polymers are too viscous to have fast ion diffusion like liquids, and too unstructured to promote cooperative transport like crystalline solids. Ionomers are polymer electrolytes in which ionic groups are covalently bound to the polymer backbone, neutralized by free counterions. These materials also conduct ions, and can exhibit strong ionic aggregation. Using coarse-grained molecular dynamics, we explore the forces driving ionic aggregation, and describe the role ion aggregates have in mediating charge transport. The aggregates are string-like such that ions typically have two neighbors. We find ion aggregates self-assemble like worm-like micelles. Excess charge, or free ions, occasionally coordinate with aggregates and are transported along the chain in a Grotthuss-like mechanism. We propose that controlling ionomer aggregate structure through materials design can enhance cooperative ion transport.

The effect of ionic membrane properties on the performance of ionic polymer-metal composite (IPMC) actuator

NASA Astrophysics Data System (ADS)

Jho, Jae Y.; Han, Man J.; Park, Jong H.; Lee, Jang Y.; Wang, Hyuck S.

2005-05-01

On purpose to overcome the limit of conventional ionic polymer-metal composites (IPMC) using the commercial ionic membranes, novel IPMCs with radiation-grafted ion-exchange membranes were prepared. Poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-co-HFP) and poly(ethylene-co-tetrafluoroethylene) (ETFE) were radiation-grafted with styrene, and then sulfonated. The properties of the membranes were modulated by controlling the amount of polystyrene sulfonic acid (PSSA) groups in the membranes. The amount of PSSA groups were tuned by controlling the total absorbed dose of γ-ray. The membranes were characterized by measuring the water-uptake, the ion-exchange capacity, and the ion conductivity. The performance of the IPMCs using these membranes were analyzed with laser displacement meter. They exhibited much larger bending displacement in comparison with Nafion-based IPMC. With increasing the amount of PSSA groups, the maximum displacement and the bending speed were remarkably increased. The results made sure that the property of ion-exchange membrane was the key element affecting the actuation performance of IPMC.

Dispersions of polymer ionomers: I.

PubMed

Capek, Ignác

2004-12-31

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

Electrically and chemically tunable soft-solid block copolymer structural color (Conference Presentation)

NASA Astrophysics Data System (ADS)

Park, Cheolmin

2016-09-01

1D photonic crystals based on the periodic stacking of two different dielectric layers have been widely studied due to their potential use in low-power reflective mode displays, e-books and sensors, but the fabrication of mechanically flexible polymer structural color (SC) films, with electro-active color switching, remains challenging. Here, we demonstrate free-standing electric field tunable ionic liquid swollen block copolymer films. Placement of a polymer/ionic liquid (IL) film-reservoir adjacent to a self-assembled poly(styrene-block-quaternized 2vinyl pyridine) (PS-b-QP2VP) copolymer SC film allowed the development of R, G and B full-color SC block copolymer films by swelling of the QP2VP domains by the ionic liquid associated with water molecules. The IL-polymer/BCP SC film is mechanically flexible with excellent color stability over several days at ambient conditions. The selective swelling of the QP2VP domains could be controlled by both the ratio of the IL to a polymer in the gel-like IL reservoir layer and by an applied voltage in the range of -3V to +6V using a metal/IL reservoir/SC film/IL reservoir/metal capacitor type device.

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

NASA Astrophysics Data System (ADS)

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.

An ionic polymer-metal composite actuator based on PSMI-incorporated PVDF with chemical stability and performance durability

NASA Astrophysics Data System (ADS)

Lu, Jun; Kim, Sang-Gyun; Lee, Sunwoo; Oh, Il-Kwon

2009-07-01

To develop artificial muscles with improved performance, a novel ionic polymer-metal composite (IPMC) actuator was developed by employing the newly-synthesized ionic networking film of poly (styrene-alt-maleimide) (PSMI)- incorporated poly (vinylidene fluoride) (PVDF). Scanning electron microscope and transmission electron microscopy revealed that much smaller and more uniform nano-sized platinum particles were formed on the surfaces of the film as well as within its polymer matrix after the electroless-plating process. Fourier transform infrared results suggested that no hydrolysis occurred for the as-prepared film actuator before and after the exposure to the elevated PH solutions at 25°C for 48h. The new actuator showed much larger tip displacement than that of a Nafion-based counterpart under the applied electrical stimulus, and overcame the back relaxation of the traditional IPMC actuator under the constant voltage. The current actuator was operated over 6.5h at high-frequency sinusoidal excitation, and its tip displacement was still comparable to that of the referenced Nafion actuator when the test was terminated. The excellent electromechanical performance is due to the inherent large ionic-exchange capacity and the unique hydrophilic nano-channels of the ionic networking film. Furthermore, the working principle of the developed IPMC actuator is thought to be based on a combination of piezoelectricity and ionic transport. The film of PSMI-incorporated PVDF has some advantages over the most widely-used Nafion-based one by diversifying niche applications in biomimetic motion, and the present study is believed to open a new avenue for the design and fabrication of the electro-active polymer film with unique functional properties.

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

NASA Astrophysics Data System (ADS)

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.

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

PubMed

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.

Ionic Liquid Epoxy Resin Monomers

NASA Technical Reports Server (NTRS)

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.

Solid polymer electrolyte compositions

DOEpatents

Garbe, James E.; Atanasoski, Radoslav; Hamrock, Steven J.; Le, Dinh Ba

2001-01-01

An electrolyte composition is featured that includes a solid, ionically conductive polymer, organically modified oxide particles that include organic groups covalently bonded to the oxide particles, and an alkali metal salt. The electrolyte composition is free of lithiated zeolite. The invention also features cells that incorporate the electrolyte composition.

Metal-ion retention properties of water-soluble amphiphilic block copolymer in double emulsion systems (w/o/w) stabilized by non-ionic surfactants.

PubMed

Palencia, Manuel; Rivas, Bernabé L

2011-11-15

Metal-ion retention properties of water-soluble amphiphilic polymers in presence of double emulsion were studied by diafiltration. Double emulsion systems, water-in-oil-in-water, with a pH gradient between external and internal aqueous phases were prepared. A poly(styrene-co-maleic anhydride) (PSAM) solution at pH 6.0 was added to the external aqueous phase of double emulsion and by application of pressure a divalent metal-ion stream was continuously added. Metal-ions used were Cu(2+) and Cd(2+) at the same pH of polymer solution. According to our results, metal-ion retention is mainly the result of polymer-metal interaction. Interaction between PSMA and reverse emulsion globules is strongly controlled by amount of metal-ions added in the external aqueous phase. In addition, as metal-ion concentration was increased, a negative effect on polymer retention capacity and promotion of flocculation phenomena were produced. Copyright © 2011 Elsevier Inc. All rights reserved.

Optimizing Ionic Electrolytes for Dye-Sensitized Solar Cells

NASA Astrophysics Data System (ADS)

Fan, Xiaojuan; Hall, Sarah

2009-03-01

Dye-sensitized solar cells DSSCs provide next generation, low cost, and easy fabrication photovoltaic devices based on organic sensitizing molecules, polymer gel electrolyte, and metal oxide semiconductors. One of the key components is the solvent-free ionic liquid electrolyte that has low volatility and high stability. We report a rapid and low cost method to fabricate ionic polymer electrolyte used in DSSCs. Poly(ethylene oxide) (PEO) is blended with imidazolinium salt without any chemical solvent to form a gel electrolyte. Uniform and crack-free porous TiO2 thin films are sensitized by porphrine dye covered by the synthesized gel electrolyte. The fabricated DSSCs are more stable and potentially increase the photo-electricity conversion efficiency.

Applications of positron annihilation spectroscopy in materials research

NASA Technical Reports Server (NTRS)

Singh, Jag J.

1988-01-01

Positron Annihilation Spectroscopy (PAS) has emerged as a powerful technique for research in condensed matter. It has been used extensively in the study of metals, ionic crystals, glasses and polymers. The present review concentrates on applications of positron lifetime measurements for elucidation of the physicochemical structure of polymers.

Effects of anisotropic surface texture on the performance of ionic polymer-metal composite (IPMC)

NASA Astrophysics Data System (ADS)

He, Qingsong; Yu, Min; Ding, Haitao; Guo, Dongjie; Dai, Zhendong

2010-04-01

Ionic polymer metal composite (IPMC), an electrically activated polymer (EAP), has attracted great attention for the excellent properties such as large deformation, light weight, low noise, flexibility and low driving voltages, which makes the material a possible application as artificial muscle if the output force can be increased. To improve the property, we manufactured the Nafion membrane by casting from liquid solution, modified the surface by sandblasting or polishing, and obtained the isotropic and anisotropic surface texture respectively. The microstructure of the Nafion surface and metal electrode, effects of surface texture on the output force and displacement of IPMC were studied. Results show that the output force of IPMC with the anisotropic surface texture is 2~4 times higher than that with the isotropic surface texture without enormous sacrifice of the displacement. The output force may reach to 6.63gf (Sinusoidal 3.5V and 0.1Hz, length 20mm, width 5mm and thickness 0.66mm), which suggest an effective way to improve the mechanical properties of IPMC.

Poly(1-Vinyl-1,2,4-triazolium) Poly(Ionic Liquid)s: Synthesis and the Unique Behavior in Loading Metal Ions.

PubMed

Zhang, Weiyi; Yuan, Jiayin

2016-07-01

Herein, the synthesis of a series of poly(4-alkyl-1-vinyl-1,2,4-triazolium) poly(ionic liquid)s is reported either via straightforward free radical polymerization of their corresponding ionic liquid monomers or via anion metathesis of the polymer precursors bearing halide as counter anion. The ionic liquid monomers are first prepared via N-alkylation reaction of commercially available 1-vinyl-1,2,4-triazole with alkyl iodides, followed by anion metathesis with targeted fluorinated anions. The thermal properties and solubilities of these poly(ionic liquid)s have been systematically investigated. Interestingly, it is found that the poly(4-ethyl-1-vinyl-1,2,4-triazolium) poly(ionic liquid) exhibited an improved loading capacity of transition metal ions in comparison with its imidazolium counterpart. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2018-03-19

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

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

NASA Astrophysics Data System (ADS)

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.

Microscopic signature of insulator-to-metal transition in highly doped semicrystalline conducting polymers in ionic-liquid-gated transistors

NASA Astrophysics Data System (ADS)

Tanaka, Hisaaki; Nishio, Satoshi; Ito, Hiroshi; Kuroda, Shin-ichi

2015-12-01

Electronic state of charge carriers, in particular, in highly doped regions, in thin-film transistors of a semicrystalline conducting polymer poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene), has been studied by using field-induced electron spin resonance (ESR) spectroscopy. By adopting an ionic-liquid gate insulator, a gate-controlled reversible electrochemical hole-doping of the polymer backbone is achieved, as confirmed from the change of the optical absorption spectra. The edge-on molecular orientation in the pristine film is maintained even after the electrochemical doping, which is clarified from the angular dependence of the g value. As the doping level increases, spin 1/2 polarons transform into spinless bipolarons, which is demonstrated from the spin-charge relation showing a spin concentration peak around 1%, contrasting to the monotonic increase in the charge concentration. At high doping levels, a drastic change in the linewidth anisotropy due to the generation of conduction electrons is observed, indicating the onset of metallic state, which is also supported by the temperature dependence of the spin susceptibility and the ESR linewidth. Our results suggest that semicrystalline conducting polymers become metallic with retaining their molecular orientational order, when appropriate doping methods are chosen.

Electroactive polymers for sensing

PubMed Central

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

Ionic electroactive hybrid transducers

NASA Astrophysics Data System (ADS)

Akle, Barbar J.; Bennett, Matthew D.; Leo, Donald J.

2005-05-01

Ionic electroactive actuators have received considerable attention in the past ten years. Ionic electroactive polymers, sometimes referred to as artificial muscles, have the ability to generate large bending strain and moderate stress at low applied voltages. Typical types of ionic electroactive polymer transducers include ionic polymers, conducting polymers, and carbon nanotubes. Preliminary research combining multiple types of materials proved to enhance certain transduction properties such as speed of response, maximum strain, or quasi-static actuation. Recently it was demonstrated that ionomer-ionic liquid transducers can operate in air for long periods of time (>250,000 cycles) and showed potential to reduce or eliminate the back-relaxation issue associated with ionomeric polymers. In addition, ionic liquids have higher electrical stability window than those operated with water as the solvent thereby increasing the maximum strain that the actuator can produce. In this work, a new technique developed for plating metal particulates on the surface of ionomeric materials is applied to the development of hybrid transducers that incorporate carbon nanotubes and conducting polymers as electrode materials. The new plating technique, named the direct assembly process, consists of mixing a conducting powder with an ionomer solution. This technique has demonstrated improved response time and strain output as compared to previous methods. Furthermore, the direct assembly process is less costly to implement than traditional impregnation-reduction methods due to less dependence on reducing agents, it requires less time, and is easier to implement than other processes. Electrodes applied using this new technique of mixing RuO2 (surface area 45~65m2/g) particles and Nafion dispersion provided 5x the displacement and 10x the force compared to a transducer made with conventional methods. Furthermore, the study illustrated that the response speed of the transducer is optimized by varying the vol% of metal in the electrode. For RuO2, the optimal loading was approximately 45%. This study shows that carbon nanotubes electrodes have an optimal performance at loadings around 30 vol%, while PANI electrodes are optimized at 95 vol%. Due to low percolation threshold, carbon nanotubes actuators perform better at lower loading than other conducting powders. The addition of nanotubes to the electrode tends to increase both the strain rate and the maximum strain of the hybrid actuator. SWNT/RuO2 hybrid transducer has a strain rate of 2.5%/sec, and a maximum attainable peak-to-peak strain of 9.38% (+/- 2V). SWNT/PANI hybrid also increased both strain and strain rate but not as significant as with RuO2. PANI/RuO2 actuator had an overwhelming back relaxation.

Multivalent Ion Transport in Polymers via Metal-Ligand Coordination

NASA Astrophysics Data System (ADS)

Sanoja, Gabriel; Schauser, Nicole; Evans, Christopher; Majumdar, Shubhaditya; Segalman, Rachel

Elucidating design rules for multivalent ion conducting polymers is critical for developing novel high-performance materials for electrochemical devices. Herein, we molecularly engineer multivalent ion conducting polymers based on metal-ligand interactions and illustrate that both segmental dynamics and ion coordination kinetics are essential for ion transport through polymers. We present a novel statistical copolymer, poly(ethylene oxide-stat-imidazole glycidyl ether) (i.e., PEO-stat-PIGE), that synergistically combines the structural hierarchy of PEO with the Lewis basicity of tethered imidazole ligands (xIGE = 0.17) required to coordinate a series of transition metal salts containing bis(trifluoromethylsulfonyl)imide anions. Complexes of PEO-stat-PIGE with salts exhibit a nanostructure in which ion-enriched regions alternate with ion-deficient regions, and an ionic conductivity above 10-5 S/cm. Novel normalization schemes that account for ion solvation kinetics are presented to attain a universal scaling relationship for multivalent ion transport in polymers via metal-ligand coordination. AFOSR MURI program under FA9550-12-1.

Intelligent control of an IPMC actuated manipulator using emotional learning-based controller

NASA Astrophysics Data System (ADS)

Shariati, Azadeh; Meghdari, Ali; Shariati, Parham

2008-08-01

In this research an intelligent emotional learning controller, Takagi- Sugeno- Kang (TSK) is applied to govern the dynamics of a novel Ionic-Polymer Metal Composite (IPMC) actuated manipulator. Ionic-Polymer Metal Composites are active actuators that show very large deformation in existence of low applied voltage. In this research, a new IPMC actuator is considered and applied to a 2-dof miniature manipulator. This manipulator is designed for miniature tasks. The control system consists of a set of neurofuzzy controller whose parameters are adapted according to the emotional learning rules, and a critic with task to assess the present situation resulted from the applied control action in terms of satisfactory achievement of the control goals and provides the emotional signal (the stress). The controller modifies its characteristics so that the critic's stress decreased.

A model for ionic polymer metal composites as sensors

NASA Astrophysics Data System (ADS)

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.

NMR study on mechanisms of ionic polymer-metal composites deformation with water content

NASA Astrophysics Data System (ADS)

Zhu, Zicai; Chen, Hualing; Wang, Yongquan; Luo, Bin; Chang, Longfei; Li, Bo; Chen, Luping

2011-10-01

Ionic polymer-metal composites (IPMCs) exhibit a large dynamic bending deformation under exterior electric field. The states and proportions of water within the IPMCs have great effect on the IPMCs deformation properties. This letter investigates the influence of the proportion changes of different types of water on the deformation, which may disclose the working mechanisms of the IPMCs. We give a deformation trend of IPMCs with the reduction of water content firstly. Then by the method of nuclear magnetic resonance, various water types (water bonded to sulfonates, loosely bound water and free water) of IPMCs and their proportions are investigated in the drying process which corresponds to their different deformation states. It is obtained that the deformation properties of IPMCs depend strongly on their water content and the excess free water is responsible for the relaxation deformation.

Extensional ionomeric polymer conductor composite actuators with ionic liquids

NASA Astrophysics Data System (ADS)

Liu, Sheng; Lin, Minren; Zhang, Qiming

2008-03-01

Although the Ionic Polymer-Metal Composite (IPMC) actuators developed up to date are in the form of bending actuators, development of extensional actuators based on IMPC is highly desirable from practical applications and fundamental understanding points of view. This talk presents the design, fabrication and characterization of a recent work on an extensional Ionic Polymer-Metal Composite actuator. The extensional actuator consists of the Nafion ionomer as the matrix and the sub-micron size RuO II particles as the conductive filler for the conductor/ionomr composites. In this investigation, several ionic liquids (IL) were investigated. For a Nafion/RuO II composite with 1-Ethyl-3-methylimidazolium trifluoromethanesulfonate (EMI-Tf) IL, it was found that as the ions are driven into the ionomer/RuO II composite (the composite under negative voltage), an extensional strain of 0.9% was observed; while as the ions were expelled from the ionomer/RuO II composite (under positive voltage), a contraction of -1.2% was observed. The results indicate that multiple ions are participating in charge transport and actuation process. In this paper, we also discuss several design considerations for future extensional actuators with fast response, much improved strain and stress level. Especially an actuator based on multilayer configuration can significantly increase the electric field level in the actuator and consequently significantly improve the actuator speed. The extensional actuator investigated here provides a unique platform to investigate various phenomena related to ion transport and their interaction with the ionomer/conductor matrix to realize high electromechanical performance.

Ionic liquids as lubricants of metal-polymer contacts. Preparation and properties of the first dispersions of ionic liquids and nanoparticles in polymers

NASA Astrophysics Data System (ADS)

Sanes Molina, Jose

Room-temperature ionic liquids (ILs) are high performance fluids that stand out because of a wide range of functional properties and exhibit a great potential for engineering applications. Although they have been employed as lubricants in metal-metal, metal-ceramic and ceramic-ceramic contacts, in this thesis we present the first study about the use of ILs as pure lubricants in polymer/steel contacts. The tests have established the efficacy of the ILs to reduce friction coefficient and wear rates in a variety of kinds of contacts, and criogenic to high temperature performance. Novel dispersions of ILs in polymers have been obtained with epoxy resin and thermoplastics as matrix. Therefore, the thermal, mechanical and tribological properties of the materials have studied and are discussed in the present thesis. Furthermore, the contents of ILs in the polymer matrix have been studied in relation to the tribological properties using Scanning Electron Microscopy (SEM) and Energy Dispersive X-Ray Spectrometry (EDS), the wear mechanisms that operated in the contacts were established. The novel dispersions showed a reduction in the friction coefficient and wear in comparison with neat polymers, reaching in some cases a decrease of 79%. In the case of thermoplastics such as polystyrene and polyamide 6, the new dispersions showed a reduction in friction coefficient and wear in the same range as that of the ILs when used as external lubricants in the steel/polymer contact. In addition nanoparticles of zinc oxide were used to obtain polycarbonate based nanohybrids with the purpose of improving the tribological properties. Novel nanohybrids of zinc oxide and modified zinc oxide were obtained. The mechanical, thermal and tribological properties were studied. The results of experiments clearly demonstrated that the use of ILs modifies the shape and size of the ZnO nanoparticles, increasing the tribological properties of the novel nanohybrids. Different techniques such as EDS, Transmission Electron Microscopy (TEM), X-Ray Diffraction (XRD) and X-Ray Photoelectron Spectrometry (XPS) were used to examine and establish the surface interactions and mechanism that operated between ILs and ZnO. In summary, the results reveal the importance of the processing parameters on the stability of the nature of the anion in the ILs.

A theoretical framework for the study of compression sensing in ionic polymer metal composites

NASA Astrophysics Data System (ADS)

Volpini, Valentina; Bardella, Lorenzo; Rodella, Andrea; Cha, Youngsu; Porfiri, Maurizio

2017-04-01

Ionic Polymer Metal Composites (IPMCs) are electro-responsive materials for sensing and actuation, consisting of an ion-exchange polymeric membrane with ionized units, plated within noble metal electrodes. In this work, we investigate the sensing response of IPMCs that are subject to a through-the-thickness compression, by specializing the continuum model introduced by Cha and Porfiri,1 to this one-dimensional problem. This model modifies the classical Poisson-Nernst-Plank system governing the electrochemistry in the absence of mechanical effects, by accounting for finite deformations underlying the actuation and sensing processes. With the aim of accurately describing the IPMC dynamic compressive behavior, we introduce a spatial asymmetry in the properties of the membrane, which must be accounted for to trigger a sensing response. Then, we determine an analytical solution by applying the singular perturbation theory, and in particular the method of matched asymptotic expansions. This solution shows a good agreement with experimental findings reported in literature.

NafionxAE-based polymer actuators with ionic liquids as solvent incorporated at room temperature

NASA Astrophysics Data System (ADS)

Kikuchi, Kunitomo; Tsuchitani, Shigeki

2009-09-01

Nafion®-based ionic polymer-metal composites (IPMCs), with ionic liquids as solvent, were fabricated by exchanging counterions to ionic liquids at room temperature. Ion exchange is performed by only immersing IPMC in a mixture of de-ionized water and ionic liquids at room temperature for 48 h. The fabricated IPMCs exhibited a bending curvature the same as or larger than that of conventional IPMCs with ionic liquids, formed by ion exchange to ionic liquids at an elevated temperature up to about 100 °C, and also had long-term stability in operation in air, with a fluctuation smaller than 21% in bending curvature during a 180 min operation. The effective ion exchange to ionic liquids in the present method is probably due to an increase in diffusion speed of ionic liquids into IPMC by adsorption of water in a Nafion® membrane. It is a surprise that among IPMCs with ionic liquids 1-ethyl-3-methyl-imidazolium tetrafluoroborate, 1-buthyl-3-methyl-imidazolium tetrafluoroborate (BMIBF4), and 1-buthyl-3-methyl-imidazolium hexafluorophosphate (BMIPF6), IPMC with water-insoluble BMIPF6 exhibited a larger bending curvature than that IPMC with water-miscible BMIBF4. This might be due to effective incorporation of BMIPF6 into IPMC, since BMIPF6 has a higher affinity with IPMC than with water in the mixture of water and BMIPF6. From measurements of complex impedance and step voltage response of the driving current of IPMCs with ionic liquid, they are expressed by an equivalent circuit of a parallel combination of a serial circuit of membrane resistance of Nafion® and electric double layer capacitance at metal electrodes, with membrane capacitance of Nafion®, in a frequency range higher than about 0.1 Hz. The difference in magnitude of bending curvature in three kinds of IPMCs with ionic liquids is mainly due to the difference in bending response speed coming from the difference in the membrane resistance.

Electrochemical testing of industrially produced PEO-based polymer electrolytes

NASA Astrophysics Data System (ADS)

Appetecchi, G. B.; Alessandrini, F.; Duan, R. G.; Arzu, A.; Passerini, S.

The present report describes the results of the electrochemical tests performed on polyethyleneoxide-based polymer electrolyte thin films industrially manufactured by blown-extrusion. The polymer electrolyte composition was PEO 20 LiCF 3SO 3: 16.7% γLiAlO 2. The polymer electrolyte film was tested to evaluate the ionic conductivity as well as the interfacial properties with lithium metal anodes. The work was developed within the advanced lithium polymer electrolyte (ALPE) project, an Italian project devoted to the realization of lithium polymer batteries for electric vehicle applications, in collaboration with Union Carbide.

Mechanistic Studies in Friction and Wear of Bulk Materials

NASA Astrophysics Data System (ADS)

Sawyer, W. Gregory; Argibay, Nicolas; Burris, David L.; Krick, Brandon A.

2014-07-01

From the context of a contemporary understanding of the phenomenological origins of friction and wear of materials, we review insightful contributions from recent experimental investigations of three classes of materials that exhibit uniquely contrasting tribological behaviors: metals, polymers, and ionic solids. We focus on the past decade of research by the community to better understand the correlations between environment parameters, materials properties, and tribological behavior in systems of increasingly greater complexity utilizing novel synthesis and in situ experimental techniques. In addition to such review, and a half-century after seminal publications on the subject, we present recently acquired evidence linking anisotropy in friction response with anisotropy in wear behavior of crystalline ionic solids as a function of crystallographic orientation. Although the tribological behaviors of metals, polymers, and ionic solids differ widely, it is increasingly more evident that the mechanistic origins (such as fatigue, corrosion, abrasion, and adhesion) are essentially the same. However, we hope to present a clear and compelling argument favoring the prominent and irreplaceable role of in situ experimental techniques as a bridge between fundamental atomistic and molecular processes and emergent behaviors governing tribological contacts.

Preparation of metallic cation conducting polymers based on sterically hindered phenols containing polymeric systems

DOEpatents

Skotheim, Terje A.; Okamoto, Yoshiyuki; Lee, Hung S.

1989-01-01

The present invention relates to ion-conducting solvent-free polymeric systems characterized as being cationic single ion conductors. The solvent-free polymer electrolytes comprise a flexible polymer backbone to which is attached a metal salt, such as a lithium, sodium or potassium salt, of a sterically hindered phenol. The solid polymer electrolyte may be prepared either by (1) attaching the hindered phenol directly to a flexible polymeric backbone, followed by neutralization of the phenolic OH's or (2) reacting the hindered phenol with a polymer precursor which is then polymerized to form a flexible polymer having phenolic OH's which are subsequently neutralized. Preferably the hindered phenol-modified polymeric backbone contains a polyether segment. The ionic conductivity of these solvent-free polymer electrolytes has been measured to be in the range of 10.sup.-4 to 10.sup.-7 S cm.sup.-1 at room temperature.

Preparation of metallic cation conducting polymers based on sterically hindered phenols containing polymeric systems

DOEpatents

Skotheim, T.A.; Okamoto, Yoshiyuki; Lee, H.S.

1989-11-21

The present invention relates to ion-conducting solvent-free polymeric systems characterized as being cationic single ion conductors. The solvent-free polymer electrolytes comprise a flexible polymer backbone to which is attached a metal salt, such as a lithium, sodium or potassium salt, of a sterically hindered phenol. The solid polymer electrolyte may be prepared either by (1) attaching the hindered phenol directly to a flexible polymeric backbone, followed by neutralization of the phenolic OH's or (2) reacting the hindered phenol with a polymer precursor which is then polymerized to form a flexible polymer having phenolic OH's which are subsequently neutralized. Preferably the hindered phenol-modified polymeric backbone contains a polyether segment. The ionic conductivity of these solvent-free polymer electrolytes has been measured to be in the range of 10[sup [minus]4] to 10[sup [minus]7] S cm[sup [minus]1] at room temperature.

Toward ambient temperature operation with all-solid-state lithium metal batteries with a sp3 boron-based solid single ion conducting polymer electrolyte

NASA Astrophysics Data System (ADS)

Zhang, Yunfeng; Cai, Weiwei; Rohan, Rupesh; Pan, Meize; Liu, Yuan; Liu, Xupo; Li, Cuicui; Sun, Yubao; Cheng, Hansong

2016-02-01

The ionic conductivity decay problem of poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) when increase the lithium salt of the SPEs up to high concentration is here functionally overcome by the incorporation of a charge delocalized sp3 boron based single ion conducting polymer electrolyte (SIPE) with poly(ethylene oxide) to fabricate solid-state sp3 boron based SIPE membranes (S-BSMs). By characterizations, particularly differential scanning calorimeter (DSC) and ionic conductivity studies, the fabricated S-BSMs showed decreased melting points and increased ionic conductivity as steadily increase the content of sp3 boron based SIPE, which significantly improved the low temperature performance of the all-solid-state lithium batteries. The fabricated Li | S-BSMs | LiFePO4 cells exhibit highly electrochemical stability and excellent cycling at temperature below melting point of PEO, which has never been reported so far for SIPEs based all-solid-state lithium batteries.

Conductivity through Polymer Electrolytes and Its Implications in Lithium-Ion Batteries: Real-World Application of Periodic Trends

ERIC Educational Resources Information Center

Compton, Owen C.; Egan, Martin; Kanakaraj, Rupa; Higgins, Thomas B.; Nguyen, SonBinh T.

2012-01-01

Periodic conductivity trends are placed in the scope of lithium-ion batteries, where increases in the ionic radii of salt components affect the conductivity of a poly(ethyleneoxide)-based polymer electrolyte. Numerous electrolytes containing varying concentrations and types of metal salts are prepared and evaluated in either one or two laboratory…

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

NASA Astrophysics Data System (ADS)

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.

Underwater energy harvesting from a turbine hosting ionic polymer metal composites

NASA Astrophysics Data System (ADS)

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

2014-08-01

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

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

NASA Astrophysics Data System (ADS)

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.

A resonant force sensor based on ionic polymer metal composites

NASA Astrophysics Data System (ADS)

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.

Alkaline polymer electrolyte fuel cells stably working at 80 °C

NASA Astrophysics Data System (ADS)

Peng, Hanqing; Li, Qihao; Hu, Meixue; Xiao, Li; Lu, Juntao; Zhuang, Lin

2018-06-01

Alkaline polymer electrolyte fuel cells are a new class of polymer electrolyte fuel cells that fundamentally enables the use of nonprecious metal catalysts. The cell performance mostly relies on the quality of alkaline polymer electrolytes, including the ionic conductivity and the chemical/mechanical stability. For a long time, alkaline polymer electrolytes are thought to be too weak in stability to allow the fuel cell to be operated at elevated temperatures, e.g., above 60 °C. In the present work, we report a progress in the state-of-the-art alkaline polymer electrolyte fuel cell technology. By using a newly developed alkaline polymer electrolyte, quaternary ammonia poly (N-methyl-piperidine-co-p-terphenyl), which simultaneously possesses high ionic conductivity and excellent chemical/mechanical stability, the fuel cell can now be stably operated at 80 °C with high power density. The peak power density reaches ca. 1.5 W/cm2 at 80 °C with Pt/C catalysts used in both the anode and the cathode. The cell works stably in a period of study over 100 h.

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

PubMed

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.

A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles

NASA Astrophysics Data System (ADS)

Choudhury, Snehashis; Mangal, Rahul; Agrawal, Akanksha; Archer, Lynden A.

2015-12-01

Rough electrodeposition, uncontrolled parasitic side-reactions with electrolytes and dendrite-induced short-circuits have hindered development of advanced energy storage technologies based on metallic lithium, sodium and aluminium electrodes. Solid polymer electrolytes and nanoparticle-polymer composites have shown promise as candidates to suppress lithium dendrite growth, but the challenge of simultaneously maintaining high mechanical strength and high ionic conductivity at room temperature has so far been unmet in these materials. Here we report a facile and scalable method of fabricating tough, freestanding membranes that combine the best attributes of solid polymers, nanocomposites and gel-polymer electrolytes. Hairy nanoparticles are employed as multifunctional nodes for polymer crosslinking, which produces mechanically robust membranes that are exceptionally effective in inhibiting dendrite growth in a lithium metal battery. The membranes are also reported to enable stable cycling of lithium batteries paired with conventional intercalating cathodes. Our findings appear to provide an important step towards room-temperature dendrite-free batteries.

A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles.

PubMed

Choudhury, Snehashis; Mangal, Rahul; Agrawal, Akanksha; Archer, Lynden A

2015-12-04

Rough electrodeposition, uncontrolled parasitic side-reactions with electrolytes and dendrite-induced short-circuits have hindered development of advanced energy storage technologies based on metallic lithium, sodium and aluminium electrodes. Solid polymer electrolytes and nanoparticle-polymer composites have shown promise as candidates to suppress lithium dendrite growth, but the challenge of simultaneously maintaining high mechanical strength and high ionic conductivity at room temperature has so far been unmet in these materials. Here we report a facile and scalable method of fabricating tough, freestanding membranes that combine the best attributes of solid polymers, nanocomposites and gel-polymer electrolytes. Hairy nanoparticles are employed as multifunctional nodes for polymer crosslinking, which produces mechanically robust membranes that are exceptionally effective in inhibiting dendrite growth in a lithium metal battery. The membranes are also reported to enable stable cycling of lithium batteries paired with conventional intercalating cathodes. Our findings appear to provide an important step towards room-temperature dendrite-free batteries.

A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles

PubMed Central

Choudhury, Snehashis; Mangal, Rahul; Agrawal, Akanksha; Archer, Lynden A.

2015-01-01

Rough electrodeposition, uncontrolled parasitic side-reactions with electrolytes and dendrite-induced short-circuits have hindered development of advanced energy storage technologies based on metallic lithium, sodium and aluminium electrodes. Solid polymer electrolytes and nanoparticle-polymer composites have shown promise as candidates to suppress lithium dendrite growth, but the challenge of simultaneously maintaining high mechanical strength and high ionic conductivity at room temperature has so far been unmet in these materials. Here we report a facile and scalable method of fabricating tough, freestanding membranes that combine the best attributes of solid polymers, nanocomposites and gel-polymer electrolytes. Hairy nanoparticles are employed as multifunctional nodes for polymer crosslinking, which produces mechanically robust membranes that are exceptionally effective in inhibiting dendrite growth in a lithium metal battery. The membranes are also reported to enable stable cycling of lithium batteries paired with conventional intercalating cathodes. Our findings appear to provide an important step towards room-temperature dendrite-free batteries. PMID:26634644

Method for conversion of carbohydrate polymers to value-added chemical products

DOEpatents

Zhang, Zongchao C [Norwood, NJ; Brown, Heather M [Kennewick, WA; Su, Yu [Richland, WA

2012-02-07

Methods are described for conversion of carbohydrate polymers in ionic liquids, including cellulose, that yield value-added chemicals including, e.g., glucose and 5-hydroxylmethylfurfural (HMF) at temperatures below 120.degree. C. Catalyst compositions that include various mixed metal halides are described that are selective for specified products with yields, e.g., of up to about 56% in a single step process.

Polymer Micelles with Cross-Linked Polyanion Core for Delivery of a Cationic Drug Doxorubicin

PubMed Central

Kim, Jong Oh; Kabanov, Alexander V.; Bronich, Tatiana K.

2009-01-01

Polymer micelles with cross-linked ionic cores were prepared by using block ionomer complexes of poly(ethylene oxide)-b-poly(methacrylic acid) (PEO-b-PMA) copolymer and divalent metal cations as templates. Doxorubicin (DOX), an anthracycline anticancer drug, was successfully incorporated into the ionic cores of such micelles via electrostatic interactions. A substantial drug loading level (up to 50 w/w %) was achieved and it was strongly dependent on the structure of the cross-linked micelles and pH. The drug-loaded micelles were stable in aqueous dispersions exhibiting no aggregation or precipitation for a prolonged period of time. The DOX-loaded polymer micelles exhibited noticeable pH-sensitive behavior with accelerated release of DOX in acidic environment due to the protonation of carboxylic groups in the cores of the micelles. The attempt to protect the DOX-loaded core with the polycationic substances resulted in the decrease of loading efficacy and had a slight effect on the release characteristics of the micelles. The DOX-loaded polymer micelles exhibited a potent cytotoxicity against human A2780 ovarian carcinoma cells. These results point to a potential of novel polymer micelles with cross-linked ionic cores to be attractive carriers for the delivery of DOX. PMID:19386272

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

PubMed

Voortman, Thomas P; Chiechi, Ryan C

2015-12-30

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 hydrophobic-hydrophobic, form smooth, structured, homogeneous films from water (ionic) or tetrahydrofuran (hydrophobic). Mismatched conjugated polymers, by contrast, form inhomogeneous films with rough topologies. The polymers with ionic backbone chains are conjugated polyions (conjugated polymers with closed-shell charges in the backbone), which are semiconducting materials with tunable bad-gaps, not unlike uncharged conjugated polymers.

A model framework for actuation and sensing of ionic polymer-metal composites: prospective on frequency and shear response through simulation tools

NASA Astrophysics Data System (ADS)

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

2017-04-01

Ionic polymer-metal composite (IPMC) is a promising material for soft-robotic actuator and sensor applications. This material system offers large deformation response for low input voltage and has an aptitude for operation in hydrated environments. Researchers have been developing IPMC actuators and sensors for applications with examples of self-sensing actuators, artificial fish fins and biomimicry of other aquatic lifeforms, and in medical operations such as in guided catheter devices. IPMCs have been developed in a range of geometric configurations, with tube or cylindrical and flat-plate rectangular as the most common shapes. Several mathematical and physics-based models have been developed for describing the transduction effects of IPMCs. In this work, the underlying theories of electromechanical and mechanoelectrical transduction in IPMCs are discussed, and simulated results of frequency response and shear response are presented. A model backbone is utilized which is primarily based on ion-transport and charge dynamics within the polymer membrane. The electromechanical model, that is with an IPMC as an actuator, is caused when an electric field is applied across the membrane causing ionic migration and swelling in the polymer membrane, which is based on the Poisson-Nernst-Planck equations and solid mechanics models. The mechanoelectric model is similar in underlying physics; however, the primary mechanisms of transduction are of different significance, where anion concentrations are as important as cations. COMSOL Multiphysics is utilized for simulations. Example applications of the modeling framework are presented. The simulated results provide additional support for the underlying physics theories discussed.

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

NASA Astrophysics Data System (ADS)

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

2014-08-01

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

A novel hybrid metal-organic framework-polymeric monolith for solid-phase microextraction.

PubMed

Lin, Chen-Lan; Lirio, Stephen; Chen, Ya-Ting; Lin, Chia-Her; Huang, Hsi-Ya

2014-03-17

This study describes the fabrication of a novel hybrid metal-organic framework- organic polymer (MOF-polymer) for use as a stationary phase in fritless solid-phase microextraction (SPME) for validating analytical methods. The MOF-polymer was prepared by using ethylene dimethacrylate (EDMA), butyl methacrylate (BMA), and an imidazolium-based ionic liquid as porogenic solvent followed by microwave-assisted polymerization with the addition of 25 % MOF. This novel hybrid MOF-polymer was used to extract penicillin (penicillin G, penicillin V, oxacillin, cloxacillin, nafcillin, dicloxacillin) under different conditions. Quantitative analysis of the extracted penicillin samples using the MOF-organic polymer for SPME was conducted by using capillary electrochromatography (CEC) coupled with UV analysis. The penicillin recovery was 63-96.2 % with high reproducibility, sensitivity, and reusability. The extraction time with the proposed fabricated SPME was only 34 min. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

NASA Astrophysics Data System (ADS)

Pandian, Amaresh Samuthira; Chen, X. Chelsea; Chen, Jihua; Lokitz, Bradley S.; Ruther, Rose E.; Yang, Guang; Lou, Kun; Nanda, Jagjit; Delnick, Frank M.; Dudney, Nancy J.

2018-06-01

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtain composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. A remarkable Li+ transference number of 0.79 is discovered for the composite electrolyte.

Electrical research on solar cells and photovoltaic materials

NASA Technical Reports Server (NTRS)

Orehotsky, J.

1984-01-01

The flat-plate solar cell array program which increases the service lifetime of the photovoltaic modules used for terrestrial energy applications is discussed. The current-voltage response characteristics of the solar cells encapsulated in the modules degrade with service time and this degradation places a limitation on the useful lifetime of the modules. The most desirable flat-plate array system involves solar cells consisting of highly polarizable materials with similar electrochemical potentials where the cells are encapsulated in polymers in which ionic concentrations and mobilities are negligibly small. Another possible mechanism limiting the service lifetime of the photovoltaic modules is the gradual loss of the electrical insulation characteristics of the polymer pottant due to water absorption or due to polymer degradation from light or heat effects. The mechanical properties of various polymer pottant materials and of electrochemical corrosion mechanisms in solar cell material are as follows: (1) electrical and ionic resistivity; (2) water absorption kinetics and water solubility limits; and (3) corrosion characterization of various metallization systems used in solar cell construction.

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

PubMed

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.

Nanothorn electrodes for ionic polymer-metal composite artificial muscles

PubMed Central

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

2014-01-01

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. PMID:25146561

Charge modeling of ionic polymer-metal composites for dynamic curvature sensing

NASA Astrophysics Data System (ADS)

Bahramzadeh, Yousef; Shahinpoor, Mohsen

2011-04-01

A curvature sensor based on Ionic Polymer-Metal Composite (IPMC) is proposed and characterized for sensing of curvature variation in structures such as inflatable space structures in which using low power and flexible curvature sensor is of high importance for dynamic monitoring of shape at desired points. The linearity of output signal of sensor for calibration, effect of deflection rate at low frequencies and the phase delay between the output signal and the input deformation of IPMC curvature sensor is investigated. An analytical chemo-electro-mechanical model for charge dynamic of IPMC sensor is presented based on Nernst-Planck partial differential equation which can be used to explain the phenomena observed in experiments. The rate dependency of output signal and phase delay between the applied deformation and sensor signal is studied using the proposed model. The model provides a background for predicting the general characteristics of IPMC sensor. It is shown that IPMC sensor exhibits good linearity, sensitivity, and repeatability for dynamic curvature sensing of inflatable structures.

Porous Ionic Polymers as a Robust and Efficient Platform for Capture and Chemical Fixation of Atmospheric CO2.

PubMed

Sun, Qi; Jin, Yingyin; Aguila, Briana; Meng, Xiangju; Ma, Shengqian; Xiao, Feng-Shou

2017-03-22

Direct use of atmospheric CO 2 as a C 1 source to synthesize high-value chemicals through environmentally benign processes is of great interest, yet challenging. Porous heterogeneous catalysts that are capable of simultaneously capturing and converting CO 2 are promising candidates for such applications. Herein, a family of organic ionic polymers with nanoporous structure, large surface area, strong affinity for CO 2 , and very high density of catalytic active sites (halide ions) was synthesized through the free-radical polymerization of vinylfunctionalized quaternary phosphonium salts. The resultant porous ionic polymers (PIPs) exhibit excellent activities in the cycloaddition of epoxides with atmospheric CO 2 , outperforming the corresponding soluble phosphonium salt analogues and ranking among the highest of known metal-free catalytic systems. The high CO 2 uptake capacity of the PIPs facilitates the enrichment of CO 2 molecules around the catalytic centers, thereby benefiting its conversion. We have demonstrated for the first time that atmospheric CO 2 can be directly converted to cyclic carbonates at room temperature using a heterogeneous catalytic system under metal-solvent free conditions. Moreover, the catalysts proved to be robust and fully recyclable, demonstrating promising potential for practical utilization for the chemical fixation of CO 2 . Our work thereby paves a way to the advance of PIPs as a new type of platform for capture and conversion of CO 2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Boundary layer charge dynamics in ionic liquid-ionic polymer transducers

NASA Astrophysics Data System (ADS)

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

2011-01-01

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

Selective and Responsive Nanopore-Filled Membranes

DTIC Science & Technology

2011-03-14

Materials Science and Engineering Poster Competition 15. Chen, H.; Elabd, Y.A. Ionic Liquid Polymers: Electrospinning and Solution Properties. Fall...hydrophilic ionic polymer gels within a hydrophobic polymer host matrix. The specific tasks of this project include (1) synthesizing stimuli...on polymer-polymer nanocomposites of hydrophilic ionic polymer gels within a hydrophobic polymer host matrix. The specific tasks of this project

Prominent roles of impurities in ionic liquid for catalytic conversion of carbohydrates

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

Zhao, Haibo; Brown, Heather M.; Holladay, Johnathan E.

2012-02-07

In the last two decades, ionic liquids have emerged as new and versatile solvents, and many of them are also catalysts for a broad range of catalytic reactions. Certain ionic liquids have been found to possess the unique capability of dissolving cellulosic biomass. The potential of such ionic liquids as solvent to enable catalytic conversion of cellulosic polymers was first explored and demonstrated by Zhao et al. This field of research has since experienced a rapid growth. Most ionic liquids have negligible vapor pressure and excellent thermal stability over a wide temperature range. For example, ionic liquids composed of 1-ethyl-3-methylimidazoliummore » (EMIM+) cation and Cl- anion was reported to be stable up to 285 C, while salts of the same cation with other anions such as BF4- and PF6- are thermally stable above 380 C under inert atmosphere. It is well known that presence of impurities in ionic liquids typically causes changes in physical properties, e.g. decreasing in melting point and viscosity. Addition of Lewis acidic metal chlorides, e.g. AlCl3 to 1-alkyl-3-methylimidazolium chloride, [AMIM]Cl, is an exothermic reaction and considerably reduces the melting point by forming [AMIM]AlCl4 or [AMIM]Al2Cl7 that are also ionic liquids but have much lower melting point than the parent [AMIM]Cl. While most early research on catalysis of ionic liquids involving metallohalide anions were typically conducted from stoichiometric ratio of such anions to organic cations, e.g. [AMIM]+, the use of pure ionic liquids only as a solvent to carry out catalysis by a catalytic amount of a metal halide as catalyst truly displayed the solvent property of such ionic liquids.4 In such reaction systems, catalytic amounts of metal halides were used to catalyze the conversion of glucose and cellulose.4,11,12 The metal chloride catalyst concentration was in the order of 10-3 M. The presence of another metal chloride in the ionic liquids, even in the order of 10-5 M concentration was found to bring a dramatic synergistic effect. Therefore, the catalytic performance of the metal halide catalyst for the conversion of carbohydrates in the ionic liquid systems is highly sensitive to the presence of impurities. This work presents findings on the role of impurities that were present in some commercially available ionic liquids used for the conversion of the cellulose.« less

Ionic-liquid materials for the electrochemical challenges of the future.

PubMed

Armand, Michel; Endres, Frank; MacFarlane, Douglas R; Ohno, Hiroyuki; Scrosati, Bruno

2009-08-01

Ionic liquids are room-temperature molten salts, composed mostly of organic ions that may undergo almost unlimited structural variations. This review covers the newest aspects of ionic liquids in applications where their ion conductivity is exploited; as electrochemical solvents for metal/semiconductor electrodeposition, and as batteries and fuel cells where conventional media, organic solvents (in batteries) or water (in polymer-electrolyte-membrane fuel cells), fail. Biology and biomimetic processes in ionic liquids are also discussed. In these decidedly different materials, some enzymes show activity that is not exhibited in more traditional systems, creating huge potential for bioinspired catalysis and biofuel cells. Our goal in this review is to survey the recent key developments and issues within ionic-liquid research in these areas. As well as informing materials scientists, we hope to generate interest in the wider community and encourage others to make use of ionic liquids in tackling scientific challenges.

Ionic-liquid materials for the electrochemical challenges of the future

NASA Astrophysics Data System (ADS)

Armand, Michel; Endres, Frank; Macfarlane, Douglas R.; Ohno, Hiroyuki; Scrosati, Bruno

2009-08-01

Ionic liquids are room-temperature molten salts, composed mostly of organic ions that may undergo almost unlimited structural variations. This review covers the newest aspects of ionic liquids in applications where their ion conductivity is exploited; as electrochemical solvents for metal/semiconductor electrodeposition, and as batteries and fuel cells where conventional media, organic solvents (in batteries) or water (in polymer-electrolyte-membrane fuel cells), fail. Biology and biomimetic processes in ionic liquids are also discussed. In these decidedly different materials, some enzymes show activity that is not exhibited in more traditional systems, creating huge potential for bioinspired catalysis and biofuel cells. Our goal in this review is to survey the recent key developments and issues within ionic-liquid research in these areas. As well as informing materials scientists, we hope to generate interest in the wider community and encourage others to make use of ionic liquids in tackling scientific challenges.

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

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

Pandian, Amaresh Samuthira; Chen, Xi Chelsea; Chen, Jihua

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtainmore » composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. As a result, a remarkable Li + transference number of 0.79 is discovered for the composite electrolyte.« less

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

DOE PAGES

Pandian, Amaresh Samuthira; Chen, Xi Chelsea; Chen, Jihua; ...

2018-04-24

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtainmore » composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. As a result, a remarkable Li + transference number of 0.79 is discovered for the composite electrolyte.« less

Ionic Liquids in Polymer Design: From Energy to Health

DTIC Science & Technology

2016-10-19

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...2016 Final Report: Ionic Liquids in Polymer Design: From Energy to Health The views, opinions and/or findings contained in this report are those of

Ultrahigh Ionic Conduction in Water-Stable Close-Packed Metal-Carbonate Frameworks.

PubMed

Manna, Biplab; Desai, Aamod V; Illathvalappil, Rajith; Gupta, Kriti; Sen, Arunabha; Kurungot, Sreekumar; Ghosh, Sujit K

2017-08-21

Utilization of the robust metal-carbonate backbone in a series of water-stable, anionic frameworks has been harnessed for the function of highly efficient solid-state ion-conduction. The compact organization of hydrophilic guest ions facilitates water-assisted ion-conduction in all the compounds. The dense packing of the compounds imparts high ion-conducting ability and minimizes the possibility of fuel crossover, making this approach promising for design and development of compounds as potential components of energy devices. This work presents the first report of evaluating ion-conduction in a purely metal-carbonate framework, which exhibits high ion-conductivity on the order of 10 -2 S cm -1 along with very low activation energy, which is comparable to highly conducting well-known crystalline coordination polymers or commercialized organic polymers like Nafion.

Dynamic NMR studies of polymer electrolyte materials for application to lithium-ion batteries and fuel cells

NASA Astrophysics Data System (ADS)

Khalfan, Amish N.

This dissertation investigates the structural and dynamical properties of polymer electrolyte materials for applications to lithium-ion batteries and fuel cells. The nuclear magnetic resonance (NMR) technique was used to characterize these materials. NMR aids in understanding the local environments of nuclei and the mobility of a molecular/ionic species. Five research projects were carried out, and they have been outlined in this work. NASA has developed rod-coil block copolymers for use as electrolytes in lithium-ion batteries. The copolymers exhibit a microphase separation within their structure leading to the formation of ionically conducting channels. We studied ion transport properties of the copolymers, and determined the predominant mechanism for transport to occur in the amorphous phase. Seven gel polymer electrolytes, each containing a mixture of LiBETI salt and organic solvents, were studied. Two of them incorporated BMI (1-n-butyl-3-methylimidazolium) ionic liquid. Ionic liquids are room temperature molten salts. BMI had been thought to enhance ion mobility. However, the BMI component was observed to restrict ion mobility. Gel polymer electrolytes containing LiTFSI salt and P13TFSI ionic liquid with or without the inclusion of ethylene carbonate (EC) were studied for application to lithium metal/air batteries, which have high theoretical energy densities. The addition of EC was found to improve lithium ion transport. The gels with EC therefore prove to be favorable for use as electrolytes in lithium metal/air batteries. Highly sulfonated poly(arylenethioethersulfone) (SPTES) membranes were examined for use in direct methanol fuel cells (DMFCs) as an alternative to the Nafion membrane. DMFCs use methanol as a fuel instead of reformed hydrogen as in conventional proton exchange membrane fuel cells. Compared to Nafion, the SPTES membranes were shown to retain water better at high temperatures and yield lower methanol diffusion. SPTES membranes with the addition of fluorine groups (6F-SPTES) were also studied, and these membranes had been thought to show an improvement in water transport properties over SPTES. However, water diffusion studies of the 6F-SPTES membranes revealed the fluorinated membranes to be unfavorable. The morphology of the FSPTES is suspected to be more susceptible to the loss of bound water at higher temperatures than SPTES.

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

PubMed Central

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.

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

PubMed

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.

Fabrication and Characterization of a Micromachined Swirl-Shaped Ionic Polymer Metal Composite Actuator with Electrodes Exhibiting Asymmetric Resistance

PubMed Central

Feng, Guo-Hua; Liu, Kim-Min

2014-01-01

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. PMID:24824370

Ionic Liquid Activation of Amorphous Metal-Oxide Semiconductors for Flexible Transparent Electronic Devices

DOE PAGES

Pudasaini, Pushpa Raj; Noh, Joo Hyon; Wong, Anthony T.; ...

2016-02-09

To begin this abstract, amorphous metal-oxide semiconductors offer the high carrier mobilities and excellent large-area uniformity required for high performance, transparent, flexible electronic devices; however, a critical bottleneck to their widespread implementation is the need to activate these materials at high temperatures which are not compatible with flexible polymer substrates. The highly controllable activation of amorphous indium gallium zinc oxide semiconductor channels using ionic liquid gating at room temperature is reported. Activation is controlled by electric field-induced oxygen migration across the ionic liquid-semiconductor interface. In addition to activation of unannealed devices, it is shown that threshold voltages of a transistormore » can be linearly tuned between the enhancement and depletion modes. Finally, the first ever example of transparent flexible thin film metal oxide transistor on a polyamide substrate created using this simple technique is demonstrated. Finally, this study demonstrates the potential of field-induced activation as a promising alternative to traditional postdeposition thermal annealing which opens the door to wide scale implementation into flexible electronic applications.« less

A physics-based model of the electrical impedance of ionic polymer metal composites

NASA Astrophysics Data System (ADS)

Cha, Youngsu; Aureli, Matteo; Porfiri, Maurizio

2012-06-01

In this paper, we analyze the chemoelectrical behavior of ionic polymer metal composites (IPMCs) in the small voltage range with a novel hypothesis on the charge dynamics in proximity of the electrodes. In particular, we homogenize the microscopic properties of the interfacial region through a so-called composite layer which extends between the polymer membrane and the metal electrode. This layer accounts for the dissimilar properties of its constituents by describing the charge distribution via two species of charge carriers, that is, electrons and mobile counterions. We model the charge dynamics in the IPMC by adapting the multiphysics formulation based on the Poisson-Nernst-Planck (PNP) framework, which is enriched through an additional term to capture the electron transport in the composite layer. Under the hypothesis of small voltage input, we use the linearized PNP model to derive an equivalent IPMC circuit model with lumped elements. The equivalent model comprises a resistor connected in series with the parallel of a capacitor and a Warburg impedance element. These elements idealize the phenomena of charge build up in the double layer region and the faradaic impedance related to mass transfer, respectively. We validate the equivalent model through measurements on in-house fabricated samples addressing both IPMC step response and impedance, while assessing the influence of repeated plating cycles on the electrical properties of IPMCs. Experimental results are compared with theoretical findings to identify the equivalent circuit parameters. Findings from this study are compared with alternative impedance models proposed in the literature.

One molecule of ionic liquid and tert-alcohol on a polystyrene-support as catalysts for efficient nucleophilic substitution including fluorination.

PubMed

Shinde, Sandip S; Patil, Sunil N

2014-12-07

The tert-alcohol and ionic liquid solvents in one molecule [mim-(t)OH][OMs] was immobilized on polystyrene and reported to be a highly efficient catalyst in aliphatic nucleophilic substitution using alkali metal salts. Herein, we investigated the catalytic activity of a new structurally modified polymer-supported tert-alcohol functionalized imidazolium salt catalyst in nucleophilic substitution of 2-(3-methanesulfonyloxypropyoxy)naphthalene as a model substrate with various metal nucleophiles. The tert-alcohol moiety of the ionic liquid with a hexyl chain distance from polystyrene had a better catalytic activity compared to the other resin which lacked an alkyl linker and tert-alcohol moiety. We found that the maximum [mim-(t)OH][OMs] loading had the best catalytic efficacy among the tested polystyrene-based ionic liquids (PSILs) in nucleophilic fluorination. The catalytic efficiency of the PS[him-(t)OH][OMs] as a phase transfer catalyst (PTC) was determined by carrying out various nucleophilic substitutions using the corresponding alkali metal salts from the third to sixth periodic in CH3CN or tert-BuOH media. The scope of this protocol with primary and secondary polar substrates containing many heteroatoms is also reported. This PS[him-(t)OH][OMs] catalyst not only enhances the reactivity of alkali metal salts and reduces the formation of by-products but also affords high yield with easy isolation.

Charge transport in metal oxide nanocrystal-based materials

NASA Astrophysics Data System (ADS)

Runnerstrom, Evan Lars

There is probably no class of materials more varied, more widely used, or more ubiquitous than metal oxides. Depending on their composition, metal oxides can exhibit almost any number of properties. Of particular interest are the ways in which charge is transported in metal oxides: devices such as displays, touch screens, and smart windows rely on the ability of certain metal oxides to conduct electricity while maintaining visible transparency. Smart windows, fuel cells, and other electrochemical devices additionally rely on efficient transport of ionic charge in and around metal oxides. Colloidal synthesis has enabled metal oxide nanocrystals to emerge as a relatively new but highly tunable class of materials. Certain metal oxide nanocrystals, particularly highly doped metal oxides, have been enjoying rapid development in the last decade. As in myriad other materials systems, structure dictates the properties of metal oxide nanocrystals, but a full understanding of how nanocrystal synthesis, the processing of nanocrystal-based materials, and the structure of nanocrystals relate to the resulting properties of nanocrystal-based materials is still nascent. Gaining a fundamental understanding of and control over these structure-property relationships is crucial to developing a holistic understanding of metal oxide nanocrystals. The unique ability to tune metal oxide nanocrystals by changing composition through the introduction of dopants or by changing size and shape affords a way to study the interplay between structure, processing, and properties. This overall goal of this work is to chemically synthesize colloidal metal oxide nanocrystals, process them into useful materials, characterize charge transport in materials based on colloidal metal oxide nanocrystals, and develop ways to manipulate charge transport. In particular, this dissertation characterizes how the charge transport properties of metal oxide nanocrystal-based materials depend on their processing and structure. Charge transport can obviously be taken to mean the conduction of electrons, but it also refers to the motion of ions, such as lithium ions and protons. In many cases, the transport of ions is married to the motion of electrons as well, either through an external electrical circuit, or within the same material in the case of mixed ionic electronic conductors. The collective motion of electrons over short length scales, that is, within single nanocrystals, is also a subject of study as it pertains to plasmonic nanocrystals. Finally, charge transport can also be coupled to or result from the formation of defects in metal oxides. All of these modes of charge transport in metal oxides gain further complexity when considered in nanocrystalline systems, where the introduction of numerous surfaces can change the character of charge transport relative to bulk systems, providing opportunities to exploit new physical phenomena. Part I of this dissertation explores the combination of electronic and ionic transport in electrochromic devices based on nanocrystals. Colloidal chemistry and solution processing are used to fabricate nanocomposites based on electrochromic tin-doped indium oxide (ITO) nanocrystals. The nanocomposites, which are completely synthesized using solution processing, consist of ITO nanocrystals and lithium bis(trifluoromethylsulfonyl)amide (LiTFSI) salt dispersed in a lithium ion-conducting polymer matrix of either poly(ethylene oxide) (PEO) or poly(methyl methacrylate) (PMMA). ITO nanocrystals are prepared by colloidal synthetic methods and the nanocrystal surface chemistry is modified to achieve favorable nanocrystal-polymer interactions. Homogeneous solutions containing polymer, ITO nanocrystals, and lithium salt are thus prepared and deposited by spin casting. Characterization by DC electronic measurements, microscopy, and x-ray scattering techniques show that the ITO nanocrystals form a complete, connected electrode within a polymer electrolyte matrix, and that the morphology and properties of the nanocomposites can be manipulated by changing the chemical composition of the deposition solution. Careful application of AC impedance spectroscopy techniques and DC measurements are used to show that the nanocomposites exhibit mixed ionic and electronic conductivity, where electronic charge is transported through the ITO nanocrystal phase, and ionic charge is transported through the polymer matrix phase. The synthetic methods developed here and understanding of charge transport ultimately lead to the fabrication of a solid state nanocomposite electrochromic device based on nanocrystals of ITO and cerium oxide. Part II of this dissertation considers electron transport within individual metal oxide nanocrystals themselves. It primarily examines relationships between synthetic chemistry, doping mechanisms in metal oxides, and the accompanying physics of free carrier scattering within the interior of highly doped metal oxide nanocrystals, with particular mind paid to ITO nanocrystals. Additionally, synthetic methods as well as metal oxide defect chemistry influences the balance between activation and compensation of dopants, which limits the nanocrystals' free carrier concentration. Furthermore, because of ionized impurity scattering of the oscillating electrons by dopant ions, scattering must be treated in a fundamentally different way in semiconductor metal oxide materials when compared with conventional metals. (Abstract shortened by ProQuest.).

Ionic polymer-metal composite enabled robotic manta ray

NASA Astrophysics Data System (ADS)

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).

Bio-applications of ionic polymer metal composite transducers

NASA Astrophysics Data System (ADS)

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.

A nonlinear model for ionic polymer metal composites as actuators

NASA Astrophysics Data System (ADS)

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.

Design and control of 2-axis tilting actuator for endoscope using ionic polymer metal composites

NASA Astrophysics Data System (ADS)

Kim, Sung-Joo; Kim, Chul-Jin; Park, No-Cheol; Yang, Hyun-Seok; Park, Young-Pil

2009-03-01

In field of endoscopy, in order to overcome limitation in conventional endoscopy, capsule endoscope has been developed and has been recently applied in medical field in hospital. However, since capsule endoscope moves passively through GI tract by peristalsis, it is not able to control direction of head including camera. It is possible to miss symptoms of disease. Therefore, in this thesis, 2-Axis Tilting Actuator for Endoscope, based on Ionic Polymer Metal Composites (IPMC), is presented. In order to apply to capsule endoscope, the actuator material should satisfy a size, low energy consumption and low working voltage. Since IPMC is emerging material that exhibits a large bending deflection at low voltage, consume low energy and it can be fabricated in any size or any shape, IPMC are selected as an actuator. The system tilts camera module of endoscope to reduce invisible area of the intestines and a goal of tilting angle is selected to be an angle of 5 degrees for each axis. In order to control tiling angle, LQR controller and the full order observer is designed.

Composite Electrolytes for Lithium Batteries: Ionic Liquids in APTES Crosslinked Polymers

NASA Technical Reports Server (NTRS)

Tigelaar, Dean M.; Meador, Mary Ann B.; Bennett, William R.

2007-01-01

Solvent free polymer electrolytes were made consisting of Li(+) and pyrrolidinium salts of trifluoromethanesulfonimide added to a series of hyperbranched poly(ethylene oxide)s (PEO). The polymers were connected by triazine linkages and crosslinked by a sol-gel process to provide mechanical strength. The connecting PEO groups were varied to help understand the effects of polymer structure on electrolyte conductivity in the presence of ionic liquids. Polymers were also made that contain poly(dimethylsiloxane) groups, which provide increased flexibility without interacting with lithium ions. When large amounts of ionic liquid are added, there is little dependence of conductivity on the polymer structure. However, when smaller amounts of ionic liquid are added, the inherent conductivity of the polymer becomes a factor. These electrolytes are more conductive than those made with high molecular weight PEO imbibed with ionic liquids at ambient temperatures, due to the amorphous nature of the polymer.

Development of safe, green and high performance ionic liquids-based batteries (ILLIBATT project)

NASA Astrophysics Data System (ADS)

Balducci, A.; Jeong, S. S.; Kim, G. T.; Passerini, S.; Winter, M.; Schmuck, M.; Appetecchi, G. B.; Marcilla, R.; Mecerreyes, D.; Barsukov, V.; Khomenko, V.; Cantero, I.; De Meatza, I.; Holzapfel, M.; Tran, N.

This manuscript presents the work carried out within the European project ILLIBATT, which was dedicated to the development of green, safe and high performance ionic liquids-based lithium batteries. Different types of ionic liquids-based electrolytes were developed in the project, based on different ionic liquids and polymers. Using these electrolytes, the performance of several anodic and cathodic materials has been tested and promising results have been obtained. Also, electrodes were formulated using water soluble binders. Using these innovative components, lithium-ion and lithium-metal battery prototypes (0.7-0.8 Ah) have been assembled and cycled between 100% and 0% SOC. The results of these tests showed that such ionic liquids-based prototypes are able to display high capacity, high coulombic efficiency and high cycle life. Moreover, safety tests showed that the introduction of these alternative electrolytes positively contribute to the safety of the batteries.

A Highly Aromatic and Sulfonated Ionomer for High Elastic Modulus Ionic Polymer Membrane Micro-Actuators

DTIC Science & Technology

2012-05-01

fluorophenyl)sulfone (DPA-PS:BP) is investigated for ionic polymer actuators. The uniqueness of DPA-PS:BP is that it can have a high ionic liquid (IL... ionic liquid Q M Zhang, Gokhan Hatipoglu, Yang Liu, Ran Zhao, Mitra Yoonessi, Dean M Tigelaar, Srinivas Tadigadapa Virginia Polytechnic Institute...DPA-PS:BP) is investigated for ionic polymer actuators. The uniqueness of DPA-PS:BP is that it can have a high ionic liquid (IL) uptake and

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

NASA Astrophysics Data System (ADS)

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.

Ionic-Liquid-Based Polymer Electrolytes for Battery Applications.

PubMed

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.

Transformation of metal-organic framework to polymer gel by cross-linking the organic ligands preorganized in metal-organic framework.

PubMed

Ishiwata, Takumi; Furukawa, Yuki; Sugikawa, Kouta; Kokado, Kenta; Sada, Kazuki

2013-04-10

Until now, seamless fusion of metal-organic frameworks (MOFs) and covalently cross-linked polymer gels (PG) at molecular level has been extremely rare, since these two matters have been regarded as opposite, that is, hard versus soft. In this report, we demonstrate transformation of cubic MOF crystals to PG via inner cross-linking of the organic linkers in the void space of MOF, followed by decomposition of the metal coordination. The obtained PG behaved as a polyelectrolyte gel, indicating the high content of ionic groups inside. Metal ions were well adsorbed in the PG due to its densely packed carboxylate groups. A chimera-type hybrid material consisting of MOF and PG was obtained by partial hydrolysis of resulting cross-linked MOF. The shape of resulting PG network well reflected the crystal structure of MOF employed as a template. Our results will connect the two different network materials that have been ever studied in the two different fields to provide new soft and hard hybrid materials, and the unique copolymerization in the large void space of the MOF will open a new horizon toward "ideal network polymers" never prepared before now.

Optimization of neural network for ionic conductivity of nanocomposite solid polymer electrolyte system (PEO-LiPF 6-EC-CNT)

NASA Astrophysics Data System (ADS)

Johan, Mohd Rafie; Ibrahim, Suriani

2012-01-01

In this study, the ionic conductivity of a nanocomposite polymer electrolyte system (PEO-LiPF 6-EC-CNT), which has been produced using solution cast technique, is obtained using artificial neural networks approach. Several results have been recorded from experiments in preparation for the training and testing of the network. In the experiments, polyethylene oxide (PEO), lithium hexafluorophosphate (LiPF 6), ethylene carbonate (EC) and carbon nanotubes (CNT) are mixed at various ratios to obtain the highest ionic conductivity. The effects of chemical composition and temperature on the ionic conductivity of the polymer electrolyte system are investigated. Electrical tests reveal that the ionic conductivity of the polymer electrolyte system varies with different chemical compositions and temperatures. In neural networks training, different chemical compositions and temperatures are used as inputs and the ionic conductivities of the resultant polymer electrolytes are used as outputs. The experimental data is used to check the system's accuracy following the training process. The neural network is found to be successful for the prediction of ionic conductivity of nanocomposite polymer electrolyte system.

Computer-aided design of polymers and composites

NASA Technical Reports Server (NTRS)

Kaelble, D. H.

1985-01-01

This book on computer-aided design of polymers and composites introduces and discusses the subject from the viewpoint of atomic and molecular models. Thus, the origins of stiffness, strength, extensibility, and fracture toughness in composite materials can be analyzed directly in terms of chemical composition and molecular structure. Aspects of polymer composite reliability are considered along with characterization techniques for composite reliability, relations between atomic and molecular properties, computer aided design and manufacture, polymer CAD/CAM models, and composite CAD/CAM models. Attention is given to multiphase structural adhesives, fibrous composite reliability, metal joint reliability, polymer physical states and transitions, chemical quality assurance, processability testing, cure monitoring and management, nondestructive evaluation (NDE), surface NDE, elementary properties, ionic-covalent bonding, molecular analysis, acid-base interactions, the manufacturing science, and peel mechanics.

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

PubMed

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

2018-06-13

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

Electromechanical fatigue in IPMC under dynamic energy harvesting conditions

NASA Astrophysics Data System (ADS)

Krishnaswamy, Arvind; Roy Mahapatra, D.

2011-04-01

Ionic polymer-metal composites (IPMCs) are an interesting subset of smart, multi-functional materials that have shown promises in energy conversion technologies. Being electromechanically coupled, IPMCs can function as dynamic actuators and sensors, transducers for energy conversion and harvesting, as well as artificial muscles for medical and industrial applications. Like all natural materials, even IPMCs undergo fatigue under dynamic load conditions. Here, we investigate the electromechanical fatigue induced in the IPMCs due to the application of cyclic mechanical bending deformation under hydrodynamic energy harvesting condition. Considering the viscoelastic nature of the IPMC, we employ an analytical approach to modeling electromechanical fatigue primarily under the cyclic stresses induced in the membrane. The polymer-metal composite undergoes cyclic softening throughout the fatigue life without attaining a saturated state of charge migration. However, it results in (1) degradation of electromechanical performance; (2) nucleation and growth of microscopic cracks in the metal electrodes; (3) delamination of metal electrodes at the polymer-electrode interface. To understand these processes, we employ a phenomenological approach based on experimentally measured relaxation properties of the IPMC membrane. Electromechanical performance improves significantly with self-healing like properties for a certain range of relaxation time. This is due to reorientation of the backbone polymer chains which eventually leads to a regenerative process with increased charge transport.

Reliability of high-strain ionomeric polymer transducers fabricated using the novel direct assembly process

NASA Astrophysics Data System (ADS)

Akle, Barbar; Nawshin, Saila; Leo, Donald

2006-03-01

Ionomeric polymer transducers have received considerable attention in the past several years. These actuators, sometimes referred to as artificial muscles, have the ability to generate large bending strain and moderate stress at low applied voltages. Typically, ionic polymer actuators are composed of Nafion-117 membranes with platinum electrodes and are saturated with water diluents. Recently the authors have developed a novel fabrication technique named the Direct Assembly Process (DAP), which allowed good control on electrode morphology and composition. The DAP consists of spraying two high surface area metal-ionomer electrodes on a Nafion membrane. A single- walled carbon nanotubes (SWNT) and ruthenium dioxide (RuO II) hybrid electrode was sprayed on a Formamide hydrated Nafion-117 membrane using the DAP method. This transducer was shown to generate 9.4% peak-peak strain under the application of +/-2V at a strain rate of 1%/sec. Furthermore using the DAP one is capable of incorporating several types of diluents in ionomeric polymer transducers. Transducers with ionic liquid diluents are demonstrated to operate in air for long periods of time. In this work we will present a reliability study of transducers fabricated using the DAP. Each transducer is tested under a frequency range of 0.2Hz to 1Hz, and a potential of +/-1V to +/-3V. Water hydrated transducers dehydrates and stop moving within 5 minutes while operating in air under +/-2V. Transducers with Formamide diluents operate for 20,000 cycles under +/-1.5V and 0.5Hz (around 11hrs), while they degrade in less than 3000 cycles under +/-2V and 0.5Hz. Ionic liquid based transducers are demonstrated to operate in air for over 400,000 with little loss in performance, and over 1 million cycle with a loss of only 43%. Actuators with several electrode compositions are fabricated and a correlation between the reliability of ionic liquid-ionic polymer transducers and maximum strain will be presented. This correlation will be used to assess the adhesion between the high surface area electrodes and the Nafion membrane. SEM images of tested transducers will be presented.

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

NASA Astrophysics Data System (ADS)

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

2006-03-01

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

Jeffamine® based polymers as highly conductive polymer electrolytes and cathode binder materials for battery application

NASA Astrophysics Data System (ADS)

Aldalur, Itziar; Zhang, Heng; Piszcz, Michał; Oteo, Uxue; Rodriguez-Martinez, Lide M.; Shanmukaraj, Devaraj; Rojo, Teofilo; Armand, Michel

2017-04-01

We report a simple synthesis route towards a new type of comb polymer material based on polyether amines oligomer side chains (i.e., Jeffamine® compounds) and a poly(ethylene-alt-maleic anhydride) backbone. Reaction proceeds by imide ring formation through the NH2 group allowing for attachment of side chains. By taking advantage of the high configurational freedoms and flexibility of propylene oxide/ethylene oxide units (PO/EO) in Jeffamine® compounds, novel polymer matrices were obtained with good elastomeric properties. Fully amorphous solid polymer electrolytes (SPEs) based on lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and Jeffamine®-based polymer matrices show low glass transition temperatures around -40 °C, high ionic conductivities and good electrochemical stabilities. The ionic conductivities of Jeffamine-based SPEs (5.3 × 10-4 S cm-1 at 70 °C and 4.5 × 10-5 S cm-1 at room temperature) are higher than those of the conventional SPEs comprising of LiTFSI and linear poly(ethylene oxide) (PEO), due to the amorphous nature and the high concentration of mobile end-groups of the Jeffamine-based polymer matrices rather than the semi-crystalline PEO The feasibility of Jeffamine-based compounds in lithium metal batteries is further demonstrated by the implementation of Jeffamine®-based polymer as a binder for cathode materials, and the stable cycling of Li|SPE|LiFePO4 and Li|SPE|S cells using Jeffamine-based SPEs.

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

NASA Astrophysics Data System (ADS)

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

2007-04-01

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

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

PubMed

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

2009-04-23

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

Molecular dynamics simulation of polymer electrolytes based on poly(ethylene oxide) and ionic liquids. I. Structural properties.

PubMed

Costa, Luciano T; Ribeiro, Mauro C C

2006-05-14

Molecular dynamics (MD) simulations have been performed for prototype models of polymer electrolytes in which the salt is an ionic liquid based on 1-alkyl-3-methylimidazolium cations and the polymer is poly(ethylene oxide), PEO. The MD simulations were performed by combining the previously proposed models for pure ionic liquids and polymer electrolytes containing simple inorganic ions. A systematic investigation of ionic liquid concentration, temperature, and the 1-alkyl- chain length, [1,3-dimethylimidazolium]PF6, and [1-butyl-3-methylimidazolium]PF6, effects on resulting equilibrium structure is provided. It is shown that the ionic liquid is dispersed in the polymeric matrix, but ionic pairs remain in the polymer electrolyte. Imidazolium cations are coordinated by both the anions and the oxygen atoms of PEO chains. Probability density maps of occurrences of nearest neighbors around imidazolium cations give a detailed physical picture of the environment experienced by cations. Conformational changes on PEO chains upon addition of the ionic liquid are identified. The equilibrium structure of simulated systems is also analyzed in reciprocal space by using the static structure factor, S(k). Calculated S(k) display a low wave-vector peak, indicating that spatial correlation in an extended-range order prevail in the ionic liquid polymer electrolytes. Long-range correlations are assigned to nonuniform distribution of ionic species within the simulation box.

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

PubMed

Shojaatalhosseini, Mansoureh; Elamin, Khalid; Swenson, Jan

2017-10-19

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

Physics of transduction in ionic liquid-swollen Nafion membranes

NASA Astrophysics Data System (ADS)

Bennett, Matthew; Leo, Donald

2006-03-01

Ionic polymer transducers are a class of electroactive polymers that are able to generate large strains (1-5%) in response to low voltage inputs (1-5 V). Additionally, these materials generate electrical charge in response to mechanical strain and are therefore able to operate as soft, distributed sensors. Traditionally, ionic polymer transducers have been limited in their application by their hydration dependence. This work seeks to overcome this limitation by replacing the water with an ionic liquid. Ionic liquids are molten salts that exhibit very high thermal and electrochemical stability while also possessing high ionic conductivity. Results have shown that an ionic liquid-swollen ionic polymer transducer can operate for more than 250,000 cycles in air as compared to about 2,000 cycles for a water-swollen transducer. The current work examines the mechanisms of transduction in ionic liquid-swollen transducers based on Nafion polymer membranes. Specifically, the morphology and relevant ion associations within these membranes are investigated by the use of small-angle X-ray scattering (SAXS), Fourier transform infrared spectroscopy (FTIR), and nuclear magnetic resonance spectroscopy (NMR). These results reveal that the ionic liquid interacts with the membrane in much the same way that water does, and that the counterions of the Nafion polymer are the primary charge carriers. The results of these analyses are compared to the macroscopic transduction behavior in order to develop a model of the charge transport mechanism responsible for electromechanical coupling in these membranes.

An experimental and numerical approach to understand the effect of the IPMC composition on its sensing and energy harvesting behavior

NASA Astrophysics Data System (ADS)

Akle, Barbar; Khairallah, Reef; Challita, Elio

2014-03-01

Ionic Polymer Metal Composite (IPMC) is an Electo-Active Polymer (EAP) that is well-known for its actuation and sensing behavior. It has been shown that in charge sensing mode an IPMC generates one order of magnitude larger current as compared to piezoelectric materials. However the voltage generated is on the order of couple millivolts, making it less attractive as a sensor and energy harvester. Previous numerical work by the author, demonstrated that increasing the ionic concentration of the ionomer will increase the current and voltage generated by an IPMC. Conversely, the previous study showed that the electrode composition and architecture had minimal effects. This paper will present an experimental investigation of the effect of changing the composition of the ionomer, the membrane thickness, and electrode architecture on the sensing and energy harvesting behavior. The response of all IPMC transducers is analyzed and compared to numerical simulations.

Block copolymers for alkaline fuel cell membrane materials

NASA Astrophysics Data System (ADS)

Li, Yifan

Alkaline fuel cells (AFCs) using anion exchange membranes (AEMs) as electrolyte have recently received considerable attention. AFCs offer some advantages over proton exchange membrane fuel cells, including the potential of non-noble metal (e.g. nickel, silver) catalyst on the cathode, which can dramatically lower the fuel cell cost. The main drawback of traditional AFCs is the use of liquid electrolyte (e.g. aqueous potassium hydroxide), which can result in the formation of carbonate precipitates by reaction with carbon dioxide. AEMs with tethered cations can overcome the precipitates formed in traditional AFCs. Our current research focuses on developing different polymer systems (blend, block, grafted, and crosslinked polymers) in order to understand alkaline fuel cell membrane in many aspects and design optimized anion exchange membranes with better alkaline stability, mechanical integrity and ionic conductivity. A number of distinct materials have been produced and characterized. A polymer blend system comprised of poly(vinylbenzyl chloride)-b-polystyrene (PVBC-b-PS) diblock copolymer, prepared by nitroxide mediated polymerization (NMP), with poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) or brominated PPO was studied for conversion into a blend membrane for AEM. The formation of a miscible blend matrix improved mechanical properties while maintaining high ionic conductivity through formation of phase separated ionic domains. Using anionic polymerization, a polyethylene based block copolymer was designed where the polyethylene-based block copolymer formed bicontinuous morphological structures to enhance the hydroxide conductivity (up to 94 mS/cm at 80 °C) while excellent mechanical properties (strain up to 205%) of the polyethylene block copolymer membrane was observed. A polymer system was designed and characterized with monomethoxy polyethylene glycol (mPEG) as a hydrophilic polymer grafted through substitution of pendent benzyl chloride groups of a PVBC-b-PS. The incorporation of the hydrophilic polymer allows for an investigation of the effect of hydration on ionic conductivity, resulting in the increase in membrane water affinity, enhancement of conductivity and reduced dependence of conductivity on relative humidity. A study of crosslinking of block copolymers was done wherein the crosslinking occurs in the non-matrix phase in order to maintain mechanical properties. The formation of a cationic crosslinked structure improves the mechanical integrity of the membrane in water while showing little deleterious effect on ionic conductivity and mechanical properties.

Ion Transport via Structural Relaxations in Polymerized Ionic Liquids

NASA Astrophysics Data System (ADS)

Ganesan, Venkat; Mogurampelly, Santosh

We study the mechanisms underlying ion transport in poly(1-butyl-3-vinylimidazolium-hexafluorophosphate) polymer electrolytes. We consider polymer electrolytes of varying polymerized ionic liquid to ionic liquid (polyIL:IL) ratios and use atomistic molecular dynamics (MD) simulations to probe the dynamical and structural characteristics of the electrolyte. Our results reveal that anion diffusion along polymer backbone occurs primarily viathe formation and breaking of ion-pairs involving threepolymerized cationic monomers of twodifferent polymer chains. Moreover, we observe that the ionic diffusivities exhibit a direct correlation with the structural relaxation times of the ion-pairs and hydrogen bonds (H-bonds). These results provide new insights into the mechanisms underlying ion transport in polymerized ionic liquid electrolytes.

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

PubMed Central

Wei, Hsiang-Chun; Su, Guo-Dung John

2012-01-01

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. PMID:23112648

A moisture and electric coupling stimulated ionic polymer-metal composite actuator with controllable deformation behavior

NASA Astrophysics Data System (ADS)

Ru, Jie; Zhu, Zicai; Wang, Yanjie; Chen, Hualing; Bian, Changsheng; Luo, Bin; Li, Dichen

2018-02-01

Ionic polymer-metal composite (IPMC) actuator can generate large and rapid deformation based on ion migration under a relatively low driving voltage. Under full hydrated conditions, the deformation is always prone to relaxation. At room humidity conditions, the deformation increases substantially at the early stage of actuation, and then decreases gradually. Generally, most researchers considered that the change of water content or relative humidity mainly leads to the deformation instabilities, which severely limits the practical applications of IPMC. In this Letter, a novel actuation mode is proposed to control the deformation behavior of IPMC by employing moisture as an independent or collaborative incentive source together with the electric field. The deformation response is continuously measured under electric field, electric field-moisture coupling stimulus and moisture stimulus. The result shows that moisture can be a favorable driving factor for IPMC actuation. Such an electric field-moisture coupling stimulus can avoid the occurrence of deformation instabilities and guarantee a superior controllable deformation in IPMC actuation. This research provides a new method to obtain stable and large deformation of IPMC, which is of great significance for the guidance of material design and application for IPMC and IPMC-type iEAP materials.

Kinematically stable bipedal locomotion using ionic polymer-metal composite actuators

NASA Astrophysics Data System (ADS)

Hosseinipour, Milad; Elahinia, Mohammad

2013-08-01

Ionic conducting polymer-metal composites (abbreviated as IPMCs) are interesting actuators that can act as artificial muscles in robotic and microelectromechanical systems. Various black or gray box models have modeled the electrochemical-mechanical behavior of these materials. In this study, the governing partial differential equation of the behavior of IPMCs is solved using finite element methods to find the critical actuation parameters, such as strain distribution, maximum strain, and response time. One-dimensional results of the FEM solution are then extended to 2D to find the tip displacement of a flap actuator and experimentally verified. A model of a seven-degree-of-freedom biped robot, actuated by IPMC flaps, is then introduced. The possibility of fast and stable bipedal locomotion using IPMC artificial muscles is the main motivation of this study. Considering the actuator limits, joint path trajectories are generated to achieve a fast and smooth motion. The stability of the proposed gait is then evaluated using the ZMP criterion and motion simulation. The fabrication parameters of each actuator, such as length, platinum plating thickness and installation angle, are then determined using the generated trajectories. A discussion on future studies on force-torque generation of IPMCs for biped locomotion concludes this paper.

Fluid flow sensing with ionic polymer-metal composites

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

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

PubMed Central

Feng, Guo-Hua; Huang, Wei-Lun

2016-01-01

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. PMID:27023549

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

PubMed Central

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

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

PubMed

Wang, Yanjie; 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.

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

PubMed

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.

A multiple-shape memory polymer-metal composite actuator capable of programmable control, creating complex 3D motion of bending, twisting, and oscillation

NASA Astrophysics Data System (ADS)

Shen, Qi; Trabia, Sarah; Stalbaum, Tyler; Palmre, Viljar; Kim, Kwang; Oh, Il-Kwon

2016-04-01

Development of biomimetic actuators has been an essential motivation in the study of smart materials. However, few materials are capable of controlling complex twisting and bending deformations simultaneously or separately using a dynamic control system. Here, we report an ionic polymer-metal composite actuator having multiple-shape memory effect, and is able to perform complex motion by two external inputs, electrical and thermal. Prior to the development of this type of actuator, this capability only could be realized with existing actuator technologies by using multiple actuators or another robotic system. This paper introduces a soft multiple-shape-memory polymer-metal composite (MSMPMC) actuator having multiple degrees-of-freedom that demonstrates high maneuverability when controlled by two external inputs, electrical and thermal. These multiple inputs allow for complex motions that are routine in nature, but that would be otherwise difficult to obtain with a single actuator. To the best of the authors’ knowledge, this MSMPMC actuator is the first solitary actuator capable of multiple-input control and the resulting deformability and maneuverability.

A multiple-shape memory polymer-metal composite actuator capable of programmable control, creating complex 3D motion of bending, twisting, and oscillation

PubMed Central

Shen, Qi; Trabia, Sarah; Stalbaum, Tyler; Palmre, Viljar; Kim, Kwang; Oh, Il-Kwon

2016-01-01

Development of biomimetic actuators has been an essential motivation in the study of smart materials. However, few materials are capable of controlling complex twisting and bending deformations simultaneously or separately using a dynamic control system. Here, we report an ionic polymer-metal composite actuator having multiple-shape memory effect, and is able to perform complex motion by two external inputs, electrical and thermal. Prior to the development of this type of actuator, this capability only could be realized with existing actuator technologies by using multiple actuators or another robotic system. This paper introduces a soft multiple-shape-memory polymer-metal composite (MSMPMC) actuator having multiple degrees-of-freedom that demonstrates high maneuverability when controlled by two external inputs, electrical and thermal. These multiple inputs allow for complex motions that are routine in nature, but that would be otherwise difficult to obtain with a single actuator. To the best of the authors’ knowledge, this MSMPMC actuator is the first solitary actuator capable of multiple-input control and the resulting deformability and maneuverability. PMID:27080134

A multiple-shape memory polymer-metal composite actuator capable of programmable control, creating complex 3D motion of bending, twisting, and oscillation.

PubMed

Shen, Qi; Trabia, Sarah; Stalbaum, Tyler; Palmre, Viljar; Kim, Kwang; Oh, Il-Kwon

2016-04-15

Development of biomimetic actuators has been an essential motivation in the study of smart materials. However, few materials are capable of controlling complex twisting and bending deformations simultaneously or separately using a dynamic control system. Here, we report an ionic polymer-metal composite actuator having multiple-shape memory effect, and is able to perform complex motion by two external inputs, electrical and thermal. Prior to the development of this type of actuator, this capability only could be realized with existing actuator technologies by using multiple actuators or another robotic system. This paper introduces a soft multiple-shape-memory polymer-metal composite (MSMPMC) actuator having multiple degrees-of-freedom that demonstrates high maneuverability when controlled by two external inputs, electrical and thermal. These multiple inputs allow for complex motions that are routine in nature, but that would be otherwise difficult to obtain with a single actuator. To the best of the authors' knowledge, this MSMPMC actuator is the first solitary actuator capable of multiple-input control and the resulting deformability and maneuverability.

Ionogels Based on Poly(methyl methacrylate) and Metal-Containing Ionic Liquids: Correlation between Structure and Mechanical and Electrical Properties.

PubMed

Zehbe, Kerstin; Kollosche, Matthias; Lardong, Sebastian; Kelling, Alexandra; Schilde, Uwe; Taubert, Andreas

2016-03-16

Ionogels (IGs) based on poly(methyl methacrylate) (PMMA) and the metal-containing ionic liquids (ILs) bis-1-butyl-3-methlimidazolium tetrachloridocuprate(II), tetrachloride cobaltate(II), and tetrachlorido manganate(II) have been synthesized and their mechanical and electrical properties have been correlated with their microstructure. Unlike many previous examples, the current IGs show a decreasing stability in stress-strain experiments on increasing IL fractions. The conductivities of the current IGs are lower than those observed in similar examples in the literature. Both effects are caused by a two-phase structure with micrometer-sized IL-rich domains homogeneously dispersed an IL-deficient continuous PMMA phase. This study demonstrates that the IL-polymer miscibility and the morphology of the IGs are key parameters to control the (macroscopic) properties of IGs.

Ionogels Based on Poly(methyl methacrylate) and Metal-Containing Ionic Liquids: Correlation between Structure and Mechanical and Electrical Properties

PubMed Central

Zehbe, Kerstin; Kollosche, Matthias; Lardong, Sebastian; Kelling, Alexandra; Schilde, Uwe; Taubert, Andreas

2016-01-01

Ionogels (IGs) based on poly(methyl methacrylate) (PMMA) and the metal-containing ionic liquids (ILs) bis-1-butyl-3-methlimidazolium tetrachloridocuprate(II), tetrachloride cobaltate(II), and tetrachlorido manganate(II) have been synthesized and their mechanical and electrical properties have been correlated with their microstructure. Unlike many previous examples, the current IGs show a decreasing stability in stress-strain experiments on increasing IL fractions. The conductivities of the current IGs are lower than those observed in similar examples in the literature. Both effects are caused by a two-phase structure with micrometer-sized IL-rich domains homogeneously dispersed an IL-deficient continuous PMMA phase. This study demonstrates that the IL-polymer miscibility and the morphology of the IGs are key parameters to control the (macroscopic) properties of IGs. PMID:26999112

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

PubMed Central

Choi, Kisuk; Olsen, Zakai; Hwang, Taeseon; Nam, Jae-Do

2018-01-01

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. PMID:29693584

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

PubMed

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.

Coarse-Grained Molecular Dynamics Simulation of Ionic Polymer Networks

DTIC Science & Technology

2008-07-01

AFRL-RX-WP-TP-2009-4198 COARSE-GRAINED MOLECULAR DYNAMICS SIMULATION OF IONIC POLYMER NETWORKS (Postprint) T.E. Dirama, V. Varshney, K.L...GRAINED MOLECULAR DYNAMICS SIMULATION OF IONIC POLYMER NETWORKS (Postprint) 5a. CONTRACT NUMBER FA8650-05-D-5807-0052 5b. GRANT NUMBER 5c...We studied two types of networks which differ only by one containing ionic pairs that amount to 7% of the total number of bonds present. The stress

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

NASA Astrophysics Data System (ADS)

Mogurampelly, Santosh; Ganesan, Venkat

2017-02-01

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

Ionic liquids as novel solvents for ionic polymer transducers

NASA Astrophysics Data System (ADS)

Bennett, Matthew D.; Leo, Donald J.

2004-07-01

The use of ionic liquids as solvents for ionic polymer (specifically, Nafion) transducers is demonstrated. Ionic liquids are attractive for this application because of their high inherent stability. Ionic liquids are salts that exist as liquids at room temperature and have no measureable vapor pressure. Therefore, the use of ionic liquids as solvents for ionic polymer transducers can eliminate the traditional problem of water evaporation in these devices. Another benefit of the use of ionic liquids in this way is the reduction or elimination of the characteristic back-relaxation common in water-solvated ionic polymer actuators. The results demonstrate that the viscosity of the ionic liquid and the degree to which the ionic liquid swells the membrane are the important physical parameters to consider. Five ionic liquids were studied, based on substituted pyrrolidinium, phosphonium, or imidazolium cations and fluoroanions. Of these five ionic liquids, transduction is demonstrated in three of them and the best results are obtained with 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid. This substance has an electrochemical stability window of 4.1 V, a melting point of -10 °C, and a viscosity of 35-45 cP [19]. Results demonstrate that platinum-plated Nafion transducers solvated with this ionic liquid exhibit sensing and actuation responses and that these transducers are stable in air. Endurance testing of this sample reveals a decrease in the free strain of only 25 % after 250,000 actuation cycles in air.

Development and Characterization of Poly(1-vinylpyrrolidone-co-vinyl acetate) Copolymer Based Polymer Electrolytes

PubMed Central

Sa'adun, Nurul Nadiah; Subramaniam, Ramesh; Kasi, Ramesh

2014-01-01

Gel polymer electrolytes (GPEs) are developed using poly(1-vinylpyrrolidone-co-vinyl acetate) [P(VP-co-VAc)] as the host polymer, lithium bis(trifluoromethane) sulfonimide [LiTFSI] as the lithium salt and ionic liquid, and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide [EMImTFSI] by using solution casting technique. The effect of ionic liquid on ionic conductivity is studied and the optimum ionic conductivity at room temperature is found to be 2.14 × 10−6 S cm−1 for sample containing 25 wt% of EMImTFSI. The temperature dependence of ionic conductivity from 303 K to 353 K exhibits Arrhenius plot behaviour. The thermal stability of the polymer electrolyte system is studied by using thermogravimetric analysis (TGA) while the structural and morphological properties of the polymer electrolyte is studied by using Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction analysis (XRD), respectively. PMID:25431781

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

PubMed

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

2016-01-13

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

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

PubMed

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.

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

NASA Astrophysics Data System (ADS)

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

2015-07-01

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

EDITORIAL: Artificial Muscles: Selected papers from the 5th World Congress on Biomimetics, Artificial Muscles and Nano-Bio (Osaka, Japan, 25-27 November 2009) Artificial Muscles: Selected papers from the 5th World Congress on Biomimetics, Artificial Muscles and Nano-Bio (Osaka, Japan, 25-27 November 2009)

NASA Astrophysics Data System (ADS)

Shahinpoor, Mohsen

2011-12-01

The 5th World Congress on Biomimetics, Artificial Muscles and Nano-Bio and the 4th International Conference on Artificial Muscles were held in Osaka, Japan, 23-27 November 2009. This special section of Smart Materials and Structures is devoted to a selected number of research papers presented at this international conference and congress. Of the 76 or so papers presented at the conference, only 10 papers were finally selected, reviewed and accepted for this special section, following the regular reviewing procedures of the journal. This special section is focused on polymeric artificial muscles, electroactive polymers, multifunctional nanocomposites and their applications. In particular, an electromechanical model for self-sensing ionic polymer-metal composite actuating devices with patterned surface electrodes is presented which discusses the concept of creating self-sensing ionic polymer-metal composite (IPMC) actuating devices with patterned surface electrodes where actuator and sensor elements are separated by a grounded shielding electrode. Eventually, an electromechanical model of the device is also proposed and validated. Following that, there is broad coverage of polytetrahydrofurane-polyethylene oxide-PEDOT conducting interpenetrating polymer networks (IPNs) for high speed actuators. The conducting polymer (poly(3,4-ethylenedioxythiophene)) is incorporated within the IPNs, which are synthesized from polyethylene oxide (PEO)/polytetrahydrofurane (PTHF) networks. PEO/PTHF IPNs are prepared using poly(ethylene glycol) methacrylate and dimethacrylate and hydroxythelechelic PTHF as starting materials. The conducting IPN actuators are prepared by oxidative polymerization of 3,4-ethylenedioxithiophene (EDOT) using FeCl3 as an oxidizing agent within the PEO/PTHF IPN host matrix. Subsequently, giant and reversible magnetorheology of carrageenan/iron oxide magnetic gels are discussed and the effect of magnetic fields on the viscoelastic properties, magnetorheological effect of carrageenan gel containing iron oxide particles are investigated using dynamic viscoelastic measurements under magnetic fields. Furthermore, the relationship between the magnetorheology and the elasticity of magnetic gel is discussed. This special section then covers the characteristics of ionic polymer-metal composite with chemically-doped TiO2 particles to improve the bending performance of ionic polymer-metal composite (IPMC) actuators. This study is mainly focused on the characterization of the physical, electrochemical, and electromechanical properties of TiO2-doped ionic polymer membranes, and IPMCs prepared by the sol-gel method, which results in a uniform distribution of the particles inside the polymer membrane. It was determined that the lifetime of IPMC is strongly dependent on the level of water uptake. This paper is then followed by a presentation on training and shape retention in conducting polymer artificial muscles. Electrochemomechanical deformation (ECMD) of the conducting polymer, polyaniline film, is studied to investigate the behavior of actuation under tensile loads. The ECMD is induced by strains due to insertion of ionic species (cyclic strain) and a creep due to applied loads during the redox cycle. The cyclic strain is enhanced by the experience of high tensile loads, indicating a training effect. The training effect is explained by the enhanced electrochemical activity of the film. The special section then presents a paper on the current status and future prospects of power generators using dielectric elastomers. Electroactive polymer artificial muscle (EPAM), known as 'dielectric elastomer', appears to offer unique capabilities as an actuator and electrical power generator. However, the power output levels of such generators are small and the efficiencies are rather high. For example, electrical energy conversion efficiency of over 70% has been achieved. The ability of EPAM to produce hydrogen fuel for energy storage was also demonstrated. Because the energy conversion principle of EPAM is capacitive in nature, the performance is largely size-independent. Formation of motile assembly of microtubules driven by kinesins is presented next. Microtubule (MT) and kinesin are rail and motor proteins that are involved in various moving events of eukaryotic cells in natural systems. In vitro, the sliding motion of microtubules (rail) can be reproduced on a kinesin (motor protein)-coated surface coupled with adenosine triphosphate (ATP) hydrolysis, which is called a 'motility assay'. Based on this technique, a method is reported for forming MT assemblies by an active self-assembly (AcSA) process, in which MTs are crosslinked during a sliding motion on a kinesin-coated surface. Streptavidin (ST) is employed as glue to crosslink biotin-labeled MTs. This discussion is then followed by a paper on the performances of fast-moving low-voltage electromechanical actuators based on single-walled carbon nanotubes and ionic liquids. Here the mechanical and electrical properties of the polymer-free single-walled carbon nanotube (SWNT) sheets containing different contents of ionic liquids (ILs) are reported. The polymer-free SWNT sheets are prepared with the knowledge that millimeter-long 'super growth' carbon nanotubes (SG-SWNTs), produced by a water-assisted modified CVD method, associate together tightly with ILs. The molecular mechanism of electroactive polymer actuators is then discussed in the next paper. Movement of ionic electroactive polymer actuators utilizes their anisotropic volume change, which is induced by the applied voltage. The mechanism of the volume change is, however, not well understood, especially at the molecular level. The current understanding of the mechanism of the volume change at the molecular level is reviewed, focusing on the actuators made with carbon materials. Then, the pressure generated in the actuators in response to the applied voltage based on the results of the Monte Carlo simulation is discussed. It is shown that the mechanism of the actuators can be analyzed at the molecular level in terms of the balance between the electrostatic and volume exclusion interactions that act among the electrode materials and the electrolyte ions. The special section then presents a master curve for analyzing the electrochemical aging and memory effects of poly(3,4-ethylenedioxythiophene). The memory effect of conducting polymers in an electrochemical environment is investigated. This memory effect is related to the electromechanical responses of the conducting polymer. Poly(3,4-ethylenedioxythiophene) is chosen because of its interesting properties—mainly its chemical and electrochemical stabilities. By means of cyclic voltammetry, the influence of the waiting time tw at a holding potential Ew in relation to the conformational relaxation process occurring in the conducting polymer is analyzed. The effect of electrochemical aging on the electrical properties is also explained from the viewpoint of the rearrangement of polymer chains. This completes a brief report on the content of the special section on artificial muscles. I would like to thank the contributing authors of this collection of papers on artificial muscles for their outstanding and unique contributions. I am also indebted to all of the reviewers, editors and editorial staff who handled the reviews of all the papers for their time and effort. I would like to express my sincere thanks and appreciation to Professor E Garcia, Editor-in-Chief, for his encouragement and support, and for providing the opportunity to publish this special section of Smart Materials and Structures. I am also grateful to the IOP Publishing team for their support. In particular, I am greatly indebted to publisher Natasha Leeper, for her help and excellent management in the preparation of this special section on artificial muscles.

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

PubMed

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.

Gel polymer electrolytes for batteries

DOEpatents

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.

Active disturbance rejection control for output force creep characteristics of ionic polymer metal composites

NASA Astrophysics Data System (ADS)

Xiong, Yan; Chen, Yang; Sun, Zhiyong; Hao, Lina; Dong, Jie

2014-07-01

Ionic polymer metal composites (IPMCs) are a type of electroactive polymer (EAP) that can be used as both sensors and actuators. An IPMC has enormous potential application in the field of biomimetic robotics, medical devices, and so on. However, an IPMC actuator has a great number of disadvantages, such as creep and time-variation, making it vulnerable to external disturbances. In addition, the complex actuation mechanism makes it difficult to model and the demand of the control algorithm is laborious to implement. In this paper, we obtain a creep model of the IPMC by means of model identification based on the method of creep operator linear superposition. Although the mathematical model is not approximate to the IPMC accurate model, it is accurate enough to be used in MATLAB to prove the control algorithm. A controller based on the active disturbance rejection control (ADRC) method is designed to solve the drawbacks previously given. Because the ADRC controller is separate from the mathematical model of the controlled plant, the control algorithm has the ability to complete disturbance estimation and compensation. Some factors, such as all external disturbances, uncertainty factors, the inaccuracy of the identification model and different kinds of IPMCs, have little effect on controlling the output block force of the IPMC. Furthermore, we use the particle swarm optimization algorithm to adjust ADRC parameters so that the IPMC actuator can approach the desired block force with unknown external disturbances. Simulations and experimental examples validate the effectiveness of the ADRC controller.

Metallosalen-Based Ionic Porous Polymers as Bifunctional Catalysts for the Conversion of CO2 into Valuable Chemicals.

PubMed

Luo, Rongchang; Chen, Yaju; He, Qian; Lin, Xiaowei; Xu, Qihang; He, Xiaohui; Zhang, Wuying; Zhou, Xiantai; Ji, Hongbing

2017-04-10

A series of new metallosalen-based ionic porous organic polymers (POPs) were synthesized for the first time using a simple unique strategy based on the free-radical copolymerization reaction. Various techniques were used to characterize the physicochemical properties of these catalysts. These well-designed materials endowed high surface area, hierarchical porous structures, and enhanced CO 2 /N 2 adsorptive selectivity. Moreover, these POPs having both metal centers (Lewis acid) and ionic units (nucleophile) could serve as bifunctional catalysts in the catalytic conversion of CO 2 into high value-added chemicals without any additional co-catalyst under mild and solvent-free conditions, for example, CO 2 /epoxides cycloaddition and Nformylation of amines from CO 2 and hydrosilanes. The results demonstrated that the irregular porous structure was very favorable for the diffusion of substrates and products, and the microporous structural property resulted in the enrichment of CO 2 near the catalytic centers in the CO 2 -involved transformations. Additionally, the superhydrophobic property could not only enhance the chemoselectivity of products but also promote the stability and recyclability of catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lowering the operational temperature of all-solid-state lithium polymer cell with highly conductive and interfacially robust solid polymer electrolytes

NASA Astrophysics Data System (ADS)

Aldalur, Itziar; Martinez-Ibañez, Maria; Piszcz, Michal; Rodriguez-Martinez, Lide M.; Zhang, Heng; Armand, Michel

2018-04-01

Novel solid polymer electrolytes (SPEs), comprising of comb polymer matrix grafted with soft and disordered polyether moieties (Jeffamine®) and lithium bis(fluorosulfonyl)imide (LiFSI) are investigated in all-solid-state lithium metal (Li°) polymer cells. The LiFSI/Jeffamine-based SPEs are fully amorphous at room temperature with glass transitions as low as ca. -55 °C. They show higher ionic conductivities than conventional poly(ethylene oxide) (PEO)-based SPEs at ambient temperature region, and good electrochemical compatibility with Li° electrode. These exceptional properties enable the operational temperature of Li° | LiFePO4 cells to be decreased from an elevated temperature (70 °C) to room temperature. Those results suggest that LiFSI/Jeffamine-based SPEs can be promising electrolyte candidates for developing safe and high performance all-solid-state Li° batteries.

Fe3O4/cyclodextrin polymer nanocomposites for selective heavy metals removal from industrial wastewater.

PubMed

Badruddoza, Abu Zayed M; Shawon, Zayed Bin Zakir; Tay, Wei Jin Daniel; Hidajat, Kus; Uddin, Mohammad Shahab

2013-01-02

In this work, carboxymethyl-β-cyclodextrin (CM-β-CD) polymer modified Fe(3)O(4) nanoparticles (CDpoly-MNPs) was synthesized for selective removal of Pb(2+), Cd(2+), Ni(2+) ions from water. This magnetic adsorbent was characterized by TEM, FTIR, XPS and VSM. The adsorption of all studied metal ions onto CDpoly-MNPs was found to be dependent on pH, ionic strength, and temperature. Batch adsorption equilibrium was reached in 45 min and maximum uptakes for Pb(2+), Cd(2+) and Ni(2+) in non-competitive adsorption mode were 64.5, 27.7 and 13.2 mg g(-1), respectively at 25 °C. Adsorption data were fitted well to Langmuir isotherm and pseudo-second-order models for kinetic study. The polymer grafted on MNPs enhanced the adsorption capacity because of the complexing abilities of the multiple hydroxyl and carboxyl groups in polymer backbone with metal ions. In competitive adsorption experiments, CDpoly-MNPs could preferentially adsorb Pb(2+) ions with an affinity order of Pb(2+)>Cd(2+)>Ni(2+) which can be explained by hard and soft acids and bases (HASB) theory. Furthermore, we explored the recyclability of CDpoly-MNPs. Copyright © 2012 Elsevier Ltd. All rights reserved.

Mixed system of Eudragit s-100 with a designed amphipathic peptide: control of interfacial elasticity by solution composition.

PubMed

Dexter, Annette F; Malcolm, Andrew S; Zeng, Biyun; Kennedy, Debora; Middelberg, Anton P J

2008-04-01

We report an interfacially active system based on an informational peptide surfactant mixed with an oppositely charged polyelectrolyte. The 21-residue cationic peptide, AM1, has previously been shown to respond reversibly to pH and metal ions at fluid interfaces, forming elastic films that can be rapidly switched to collapse foams or emulsions on demand. Here we report the reversible association of AM1 with the methacrylate-based anionic polymer Eudragit S-100. The strength of the association, in bulk aqueous solution, is modulated by added metal ions and by ionic strength. Addition of zinc ions to the peptide-polymer system promotes complex formation and phase separation, while addition of a chelating agent reverses the association. The addition of salt weakens peptide-polymer interactions in the presence or absence of zinc. At the air-water interface, Eudragit S-100 forms an elastic mixed film with AM1 in the absence of metal, under conditions where the peptide alone does not show interfacial elasticity. When zinc is present, the elasticity of the mixed film is increased, but the rate of interfacial adsorption slows due to formation of peptide-polymer complexes in bulk solution. An understanding of these interactions can be used to identify favorable foam-forming conditions in the mixed system.

Super Soft All-Ethylene Oxide Polymer Electrolyte for Safe All-Solid Lithium Batteries

PubMed Central

Porcarelli, Luca; Gerbaldi, Claudio; Bella, Federico; Nair, Jijeesh Ravi

2016-01-01

Here we demonstrate that by regulating the mobility of classic −EO− based backbones, an innovative polymer electrolyte system can be architectured. This polymer electrolyte allows the construction of all solid lithium-based polymer cells having outstanding cycling behaviour in terms of rate capability and stability over a wide range of operating temperatures. Polymer electrolytes are obtained by UV-induced (co)polymerization, which promotes an effective interlinking between the polyethylene oxide (PEO) chains plasticized by tetraglyme at various lithium salt concentrations. The polymer networks exhibit sterling mechanical robustness, high flexibility, homogeneous and highly amorphous characteristics. Ambient temperature ionic conductivity values exceeding 0.1 mS cm−1 are obtained, along with a wide electrochemical stability window (>5 V vs. Li/Li+), excellent lithium ion transference number (>0.6) as well as interfacial stability. Moreover, the efficacious resistance to lithium dendrite nucleation and growth postulates the implementation of these polymer electrolytes in next generation of all-solid Li-metal batteries working at ambient conditions. PMID:26791572

Super Soft All-Ethylene Oxide Polymer Electrolyte for Safe All-Solid Lithium Batteries

NASA Astrophysics Data System (ADS)

Porcarelli, Luca; Gerbaldi, Claudio; Bella, Federico; Nair, Jijeesh Ravi

2016-01-01

Here we demonstrate that by regulating the mobility of classic -EO- based backbones, an innovative polymer electrolyte system can be architectured. This polymer electrolyte allows the construction of all solid lithium-based polymer cells having outstanding cycling behaviour in terms of rate capability and stability over a wide range of operating temperatures. Polymer electrolytes are obtained by UV-induced (co)polymerization, which promotes an effective interlinking between the polyethylene oxide (PEO) chains plasticized by tetraglyme at various lithium salt concentrations. The polymer networks exhibit sterling mechanical robustness, high flexibility, homogeneous and highly amorphous characteristics. Ambient temperature ionic conductivity values exceeding 0.1 mS cm-1 are obtained, along with a wide electrochemical stability window (>5 V vs. Li/Li+), excellent lithium ion transference number (>0.6) as well as interfacial stability. Moreover, the efficacious resistance to lithium dendrite nucleation and growth postulates the implementation of these polymer electrolytes in next generation of all-solid Li-metal batteries working at ambient conditions.

Membrane separation of ionic liquid solutions

DOEpatents

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.

Sensorless position estimator applied to nonlinear IPMC model

NASA Astrophysics Data System (ADS)

Bernat, Jakub; Kolota, Jakub

2016-11-01

This paper addresses the issue of estimating position for an ionic polymer metal composite (IPMC) known as electro active polymer (EAP). The key step is the construction of a sensorless mode considering only current feedback. This work takes into account nonlinearities caused by electrochemical effects in the material. Owing to the recent observer design technique, the authors obtained both Lyapunov function based estimation law as well as sliding mode observer. To accomplish the observer design, the IPMC model was identified through a series of experiments. The research comprises time domain measurements. The identification process was completed by means of geometric scaling of three test samples. In the proposed design, the estimated position accurately tracks the polymer position, which is illustrated by the experiments.

Development of PVA based micro-porous polymer electrolyte by a novel preferential polymer dissolution process

NASA Astrophysics Data System (ADS)

Subramania, A.; Kalyana Sundaram, N. T.; Sukumar, N.

A micro-porous polymer electrolyte based on PVA was obtained from PVA-PVC based polymer blend film by a novel preferential polymer dissolution technique. The ionic conductivity of micro-porous polymer electrolyte increases with increase in the removal of PVC content. Finally, the effect of variation of lithium salt concentration is studied for micro-porous polymer electrolyte of high ionic conductivity composition. The ionic conductivity of the micro-porous polymer electrolyte is measured in the temperature range of 301-351 K. It is observed that a 2 M LiClO 4 solution of micro-porous polymer electrolyte has high ionic conductivity of 1.5055 × 10 -3 S cm -1 at ambient temperature. Complexation and surface morphology of the micro-porous polymer electrolytes are studied by X-ray diffraction and SEM analysis. TG/DTA analysis informs that the micro-porous polymer electrolyte is thermally stable upto 277.9 °C. Chronoamperommetry and linear sweep voltammetry studies were made to find out lithium transference number and stability of micro-porous polymer electrolyte membrane, respectively. Cyclic voltammetry study was performed for carbon/micro-porous polymer electrolyte/LiMn 2O 4 cell to reveal the compatibility and electrochemical stability between electrode materials.

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

NASA Astrophysics Data System (ADS)

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.

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

PubMed

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.

Systematic computational and experimental investigation of lithium-ion transport mechanisms in polyester-based polymer electrolytes

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

Webb, Michael A.; Jung, Yukyung; Pesko, Danielle M.

Understanding the mechanisms of lithium-ion transport in polymers is crucial for the design of polymer electrolytes. We combine modular synthesis, electrochemical characterization, and molecular simulation to investigate lithium-ion transport in a new family of polyester-based polymers and in poly(ethylene oxide) (PEO). Theoretical predictions of glass-transition temperatures and ionic conductivities in the polymers agree well with experimental measurements. Interestingly, both the experiments and simulations indicate that the ionic conductivity of PEO, relative to the polyesters, is far higher than would be expected from its relative glass-transition temperature. The simulations reveal that diffusion of the lithium cations in the polyesters proceeds viamore » a different mechanism than in PEO, and analysis of the distribution of available cation solvation sites in the various polymers provides a novel and intuitive way to explain the experimentally observed ionic conductivities. This work provides a platform for the evaluation and prediction of ionic conductivities in polymer electrolyte materials.« less

Systematic computational and experimental investigation of lithium-ion transport mechanisms in polyester-based polymer electrolytes

DOE PAGES

Webb, Michael A.; Jung, Yukyung; Pesko, Danielle M.; ...

2015-07-10

Understanding the mechanisms of lithium-ion transport in polymers is crucial for the design of polymer electrolytes. We combine modular synthesis, electrochemical characterization, and molecular simulation to investigate lithium-ion transport in a new family of polyester-based polymers and in poly(ethylene oxide) (PEO). Theoretical predictions of glass-transition temperatures and ionic conductivities in the polymers agree well with experimental measurements. Interestingly, both the experiments and simulations indicate that the ionic conductivity of PEO, relative to the polyesters, is far higher than would be expected from its relative glass-transition temperature. The simulations reveal that diffusion of the lithium cations in the polyesters proceeds viamore » a different mechanism than in PEO, and analysis of the distribution of available cation solvation sites in the various polymers provides a novel and intuitive way to explain the experimentally observed ionic conductivities. This work provides a platform for the evaluation and prediction of ionic conductivities in polymer electrolyte materials.« less

Systematic Computational and Experimental Investigation of Lithium-Ion Transport Mechanisms in Polyester-Based Polymer Electrolytes

PubMed Central

2015-01-01

Understanding the mechanisms of lithium-ion transport in polymers is crucial for the design of polymer electrolytes. We combine modular synthesis, electrochemical characterization, and molecular simulation to investigate lithium-ion transport in a new family of polyester-based polymers and in poly(ethylene oxide) (PEO). Theoretical predictions of glass-transition temperatures and ionic conductivities in the polymers agree well with experimental measurements. Interestingly, both the experiments and simulations indicate that the ionic conductivity of PEO, relative to the polyesters, is far higher than would be expected from its relative glass-transition temperature. The simulations reveal that diffusion of the lithium cations in the polyesters proceeds via a different mechanism than in PEO, and analysis of the distribution of available cation solvation sites in the various polymers provides a novel and intuitive way to explain the experimentally observed ionic conductivities. This work provides a platform for the evaluation and prediction of ionic conductivities in polymer electrolyte materials. PMID:27162971

Morphological and electromechanical characterization of ionic liquid/Nafion polymer composites

NASA Astrophysics Data System (ADS)

Bennett, Matthew; Leo, Donald

2005-05-01

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

Simulation of polymer translocation through protein channels

PubMed Central

Muthukumar, M.; Kong, C. Y.

2006-01-01

A modeling algorithm is presented to compute simultaneously polymer conformations and ionic current, as single polymer molecules undergo translocation through protein channels. The method is based on a combination of Langevin dynamics for coarse-grained models of polymers and the Poisson–Nernst–Planck formalism for ionic current. For the illustrative example of ssDNA passing through the α-hemolysin pore, vivid details of conformational fluctuations of the polymer inside the vestibule and β-barrel compartments of the protein pore, and their consequent effects on the translocation time and extent of blocked ionic current are presented. In addition to yielding insights into several experimentally reported puzzles, our simulations offer experimental strategies to sequence polymers more efficiently. PMID:16567657

Recent Advances in Fast Ion Conducting Materials and Devices - Proceedings of the 2nd Asian Conference on Solid State Ionics

NASA Astrophysics Data System (ADS)

Chowdari, B. V. R.; Liu, Qingguo; Chen, Liquan

The Table of Contents for the book is as follows: * Preface * Invited Papers * Recent Trends in Solid State Ionics * Theoretical Aspects of Fast Ion Conduction in Solids * Chemical Bonding and Intercalation Processes in Framework Structures * Extra-Large Near-Electrode Regions and Diffusion Length on the Solid Electrolyte-Electrode Interface as Studied by Photo-EMF Method * Frequency Response of Glasses * XPS Studies on Ion Conducting Glasses * Characterization of New Ambient Temperature Lithium Polymer-Electrolyte * Recent Development of Polymer Electrolytes: Solid State Voltammetry in Polymer Electrolytes * Secondary Solid State Batteries: From Material Properties to Commercial Development * Silver Vanadium Oxide Bronze and its Applications for Electrochemical Devices * Study on β''-Alumina Solid Electrolyte and β Battery in SIC * Materials for Solid Oxide Fuel Cells * Processing for Super Superionic Ceramics * Hydrogen Production Using Oxide Ionic or Protonic Conductor * Ionically Conductive Sulfide-Based Lithium Glasses * Relation of Conductivity to Structure and Structural Relaxation in Ion-Conducting Glasses * The Mechanism of Ionic Conductivity in Glass * The Role of Synthesis and Structure in Solid State Ionics - Electrodes to Superconductors * Electrochromism in Spin-Coated Thin Films from Peroxo-Poly tungstate Solutions * Electrochemical Studies on High Tc Superconductors * Multivalence Fast Ionic Conductors - Montmorillonites * Contributed Papers * Volt-Ampere Characteristics and Interface Charge Transport in Solid Electrolytes * Internal Friction of Silver Chalcogenides * Thermal Expansion of Ionic and Superionic Solids * Improvement of PEO-LiCF3SO3 Complex Electrolytes Using Additives * Ionic Conductivity of Modified Poly (Methoxy Polyethylene Glycol Methacrylate) s-Lithium Salt Complexes * Solid Polymer Electrolytes of Crosslinked Polyethylene Glycol and Lithium Salts * Single Ionic Conductors Prepared by in Situ Polymerization of Methacrylic Acid Alkali Metal Salts in Polyethylene Oxide * Redox Behavior of Alkyl Viologens in Ion Conductive Polymer Solid * Ionic Conductivity of Interpenetrating Polymer Networks Containing LiClO4 * Electrochemical Behaviors of Porphyrins Incorporated into Solid Polymer Electrolytes * Lithium Ion Conducting Polymer Electrolytes * Electrochemical Synthesis of Polyaniline Thin Film * Electrochemical Aspect of Polyaniline Electrode in Aqueous Electrolyte * Mixed Cation Effect in Epoxy Resin - PEO-IPN Containing Perchlorate Salts * Conductivity, Raman and IR Studies on the Doped PEO-PPG Polymer Blends * Proton Conducting Polymeric Electrolytes from Poly (Ethyleneoxide) System * Surface Structure of Polymer Solid Ionic Conductors Based on Segmented Polyether Polyurethaneureas * Study on Addition Products of LiI and Diethylene Glycol etc. * Solid State Rechargeable Battery Using Paper Form Copper Ion Conductive Solid Electrolyte * Characterization of Electrode/Electrolyte Interfaces in Battery Li/PVAC-Li-Mont./Li1+xV3O8 by AC Impedance Method * Investigation on Reversibility of Vanadium Oxide Cathode Materials in Solid-State Battery * Preparation and Characterization of Silver Boromolybdate Solid State Batteries * The Electric Properties of the Trinary Cathode Material and its Application in Magnisium Solid State Cell * Electrical Properties and Phase Relation of Na2Mo0.1S0.9O4 Doped with Rare Earth Sulfate * New Electrochemical Probe for Rapid Determination of Silicon Concentration in Hot Metals * A New Theoretical EMF Expression for SOx(x = 2, 3) Sensors Based on Na2SO4 Solid Electrolyte * Evaluation of the Electrochemical SOx(x = 2, 3) Sensor with a Tubular Nasicon Electrolyte * The Response Time of a Modified Oxygen Sensor Using Zirconia Electrolyte * Preparation, Characteristics and Sintering Behavior of MgO-PSZ Powder * Reaction between La0.9MnO3 and Yttria Doped Zirconia * Development of the Extended-Life Oxygen Sensor of Caβ''-Al2O3 * Caβ''-Al2O3 Ultra-Low Oxygen Sensor * Measurement of Sulfur Concentration with Zirconia-Based Electrolyte Cell in Molten Iron * Influence of SO2 on the Conductivity of Calcia Stabilized Zirconia * Reactions between YSZ and La1-xCaxMnO3 as a Cathode for SOFC * Preparation and Electrical Properties of Lithium β''-Alumina * Influence of Lithia Content on Properties of β''-Alumina Ceramics * Electrical Conductivity of Solid Solutions of Na2SO4 with Na2SeO4 * Effect of Antagonist XO42- = MoO42- and WO42- Ion Substitution on the Electrical Conductivity of Li2SO4 : Li2CO3 Eutectic System * Study on the Electrical Properties and Structure of Multicrystal Materials Li5+xGe1-xCrxV3O12 * Preliminary Study on Synthesis of Silver Zirconium Silicophosphates by Sol - Gel Process * Sodium Ion Conduction in Iron(III) Exchanged Y Zeolite * Electrical Properties of V5O9+x (x = 0, 1) and CuxV5O9.1 * Electrical Properties of the Tetragonal ZrO2 Stabilized with CeO2, CeO2 + Gd2O3 * Study of Preparation and Ionic Conduction of Doped Barium Cerate Perovskite * Preparing Fine Alumina Powder by Homogeneous Precipitation Method for Fabricating β''-Al2O3 * Amorphous Lithium Ion Conductors in Li2S-SiS2-LiBO2 System * Mixed Alkali Effect of Glass Super Ionic Conductors * Electrical Property and Phase Separation, Crystallization Behavior of A Cu+-Conducting Glass * Investigation of Phase Separation and Crystallization for 0.4CuI-0.3 Cu2O-0.3P2O5 Glass by SEM and XRD * Study on the Lithium Solid Electrolytes of Li3N-LiX(X = F, Cl, Br, I)-B2O3 Ternary Systems * Synthesis and Characterization of the Li2O : P2O5 : WO3 Glasses * The Electrochromic Properties of Electrodeposited Ni-O Films in Nonaqueous Electrolytes * All Solid-State WO3-MnO2 Based Electrochromic Window * Electrochromism in Nickel Oxide Films * E S R of X-Irradiated Melt Quenched Li2SO4 * Mixed-Alkali Effect in the Li2O-Na2O-TeO2 Glass System * Electrical and Thermal Studies on Silver Tellurite Glasses * Late Entries (Invited Papers) * Proton Conducting Polymers * Light Scattering Studies on Superionic Conductor YSZ * Development of Thin Film Surface Modified Solid State Electrochemical Gas Sensors * Author Index * List of Participants

Correlating morphology to dc conductivity in polymerized ionic liquids

NASA Astrophysics Data System (ADS)

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

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

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

NASA Astrophysics Data System (ADS)

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

2015-09-01

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.

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

NASA Astrophysics Data System (ADS)

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.

Single-ion triblock copolymer electrolytes based on poly(ethylene oxide) and methacrylic sulfonamide blocks for lithium metal batteries

NASA Astrophysics Data System (ADS)

Porcarelli, Luca; Aboudzadeh, M. Ali; Rubatat, Laurent; Nair, Jijeesh R.; Shaplov, Alexander S.; Gerbaldi, Claudio; Mecerreyes, David

2017-10-01

Single-ion conducting polymer electrolytes represent the ideal solution to reduce concentration polarization in lithium metal batteries (LMBs). This paper reports on the synthesis and characterization of single-ion ABA triblock copolymer electrolytes comprising PEO and poly(lithium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethylsulfonyl)imide) blocks, poly(LiMTFSI). Block copolymers are prepared by reversible addition-fragmentation chain transfer polymerization, showing low glass transition temperature (-55 to 7 °C) and degree of crystallinity (51-0%). Comparatively high values of ionic conductivity are obtained (up to ≈ 10-4 S cm-1 at 70 °C), combined with a lithium-ion transference number close to unity (tLi+ ≈ 0.91) and a 4 V electrochemical stability window. In addition to these promising features, solid polymer electrolytes are successfully tested in lithium metal cells at 70 °C providing long lifetime up to 300 cycles, and stable charge/discharge cycling at C/2 (≈100 mAh g-1).

Molecular dynamics simulation of polymer electrolytes based on poly(ethylene oxide) and ionic liquids. II. Dynamical properties.

PubMed

Costa, Luciano T; Ribeiro, Mauro C C

2007-10-28

Dynamical properties of polymer electrolytes based on poly(ethylene oxide) (PEO) and ionic liquids of 1-alkyl-3-methylimidazolium cations were calculated by molecular dynamics simulations with previously proposed models [L. T. Costa and M. C. Ribeiro, J. Chem. Phys. 124, 184902 (2006)]. The effect of changing the ionic liquid concentration, temperature, and the 1-alkyl-chain lengths, [1,3-dimethylimidazolium]PF(6) and [1-butyl-3-methylimidazolium]PF(6) ([dmim]PF(6) and [bmim]PF(6)), was investigated. Cation diffusion coefficient is higher than those of anion and oxygen atoms of PEO chains. Ionic mobility in PEO[bmim]PF(6) is higher than in PEO[dmim]PF(6), so that the ionic conductivity kappa of the former is approximately ten times larger than the latter. The ratio between kappa and its estimate from the Nernst-Einstein equation kappa/kappa(NE), which is inversely proportional to the strength of ion pairs, is higher in ionic liquid polymer electrolytes than in polymer electrolytes based on inorganic salts with Li(+) cations. Calculated time correlation functions corroborate previous evidence from the analysis of equilibrium structure that the ion pairs in ionic liquid polymer electrolytes are relatively weak. Structural relaxation at distinct spatial scales is revealed by the calculation of the intermediate scattering function at different wavevectors. These data are reproduced with stretched exponential functions, so that temperature and wavevector dependences of best fit parameters can be compared with corresponding results for polymer electrolytes containing simpler ions.

Ionic Liquids as a Medium for Ionic Chain Polymerizations: An Environmentally Responsible Approach to Macromolecular Synthesis with Controlled Architecture

DTIC Science & Technology

2004-09-16

published in non peer-reviewed journals: 1. Gross, SM, Hamilton JL. "Polymer Gels for Use in Lithium Polymer Batteries", Nebraska Academy of Science...a process for the anionic polymerization of styrene and methyl methacrylate in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ...Current polymer electrolyte composites used for these applications typically comprise polyethers with ethylene carbonate solvents containing lithium

Structure and Dynamics Ionic Block co-Polymer Melts: Computational Study

NASA Astrophysics Data System (ADS)

Aryal, Dipak; Perahia, Dvora; Grest, Gary S.

Tethering ionomer blocks into co-polymers enables engineering of polymeric systems designed to encompass transport while controlling structure. Here the structure and dynamics of symmetric pentablock copolymers melts are probed by fully atomistic molecular dynamics simulations. The center block consists of randomly sulfonated polystyrene with sulfonation fractions f = 0 to 0.55 tethered to a hydrogenated polyisoprene (PI), end caped with poly(t-butyl styrene). We find that melts with f = 0.15 and 0.30 consist of isolated ionic clusters whereas melts with f = 0.55 exhibit a long-range percolating ionic network. Similar to polystyrene sulfonate, a small number of ionic clusters slow the mobility of the center of mass of the co-polymer, however, formation of the ionic clusters is slower and they are often intertwined with PI segments. Surprisingly, the segmental dynamics of the other blocks are also affected. NSF DMR-1611136; NERSC; Palmetto Cluster Clemson University; Kraton Polymers US, LLC.

Ionic conductivity of β-cyclodextrin-polyethylene-oxide/alkali-metal-salt complex.

PubMed

Yang, Ling-Yun; Fu, Xiao-Bin; Chen, Tai-Qiang; Pan, Li-Kun; Ji, Peng; Yao, Ye-Feng; Chen, Qun

2015-04-20

Highly conductive, crystalline, polymer electrolytes, β-cyclodextrin (β-CD)-polyethylene oxide (PEO)/LiAsF6 and β-CD-PEO/NaAsF6 , were prepared through supramolecular self-assembly of PEO, β-CD, and LiAsF6 /NaAsF6 . The assembled β-CDs form nanochannels in which the PEO/X(+) (X=Li, Na) complexes are confined. The nanochannels provide a pathway for directional motion of the alkali metal ions and, at the same time, separate the cations and the anions by size exclusion. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication of composite membranes using copper metal organic framework for energy application

NASA Astrophysics Data System (ADS)

Gahlot, Swati; Rajput, Abhishek; Kulshrestha, Vaibhav

2018-04-01

Present manuscript deals with the synthesis of nanocomposite polymer electrolyte membrane (PEM) based on copper based metal organic framework (Cu-MOF) and sulfonated poly ether sulfone (SPES) for fuel cell application. Prepared material and composite membrane has been analyzed through various techniques. Structural and thermal characterization of prepared material has been carried out through XRD, FTIR and TGA technique. Measurement shows the successful synthesis of MOF and also confirms the thermal stability. Prepared membranes shows good physicochemical properties and good ionic conductivity which can be utilized as PEM for fuel cell application.

Self-doped microphase separated block copolymer electrolyte

DOEpatents

Mayes, Anne M.; Sadoway, Donald R.; Banerjee, Pallab; Soo, Philip; Huang, Biying

2002-01-01

A polymer electrolyte includes a self-doped microphase separated block copolymer including at least one ionically conductive block and at least one second block that is immiscible in the ionically conductive block, an anion immobilized on the polymer electrolyte and a cationic species. The ionically conductive block provides a continuous ionically conductive pathway through the electrolyte. The electrolyte may be used as an electrolyte in an electrochemical cell.

Synthesis and characterization of ionomers as polymer electrolytes for energy conversion devices

NASA Astrophysics Data System (ADS)

Oh, Hyukkeun

Single-ion conducting electrolytes present a unique alternative to traditional binary salt conductors used in lithium-ion batteries. Secondary lithium batteries are considered as one of the leading candidates to replace the combustible engines in automotive technology, however several roadblocks are present which prevent their widespread commercialization. Power density, energy density and safety properties must be improved in order to enable the current secondary lithium battery technology to compete with existing energy technologies. It has been shown theoretically that single-ion electrolytes can eliminate the salt concentration gradient and polarization loss in the cell that develops in a binary salt system, resulting in substantial improvements in materials utilization for high power and energy densities. While attempts to utilize single-ion conducting electrolytes in lithium-ion battery systems have been made, the low ionic conductivities prevented the successful operation of the battery cells in ambient conditions. This work focuses on designing single-ion conducting electrolytes with high ionic conductivities and electrochemical and mechanical stability which enables the stable charge-discharge performance of battery cells. Perfluorosulfonate ionomers are known to possess exceptionally high ionic conductivities due to the electron-withdrawing effect caused by the C-F bonds which stabilizes the negative charge of the anion, leading to a large number of free mobile cations. The effect of perfluorinated sulfonic acid side chains on transport properties of proton exchange membrane polymers was examinated via a comparison of three ionomers, having different side chain structures and a similar polymer backbone. The three different side chain structures were aryl-, pefluoro alkyl-, and alkyl-sulfonic acid groups, respectively. All ionomers were synthesized and characterized by 1H and 19F NMR. A novel ionomer synthesized with a pendant perfluorinated sulfonic acid group and a poly(ether ether ketone) backbone showed the highest proton conductivity and proton diffusion coefficient among the three ionomers, demonstrating the effect of the perfluorinated side chains. The proton conductivity of the novel ionomer was comparable to that of Nafion over a wide humidity range and temperature. A lithium perfluorosulfonate ionomer based on aromatic poly(arylene ether)s with pendant lithium perfluoroethyl sulfonates was prepared by ion exchange of the perlfuorosulfonic acid ionomer, and subsequently incoroporated into a lithium-ion battery cell as a single-ion conducting electrolyte. The microporous polymer film saturated with organic carbonates exhibited a nearly unity Li + transfer number, high ionic conductivity (e.g. > 10-3 S m-1 at room temperature) over a wide range of temperatures, high electrochemical stability, and excellent mechanical properties. Excellent cyclability with almost identical charge and discharge capacities have been demonstrated at ambient temperature in the batteries assembled from the prepared single-ion conductors. The mechanical stability of the polymer film was attributed to the rigid polymer backbone which was largely unaffected by the presence of plasticizing organic solvents, while the porous channels with high concentration of the perfluorinated side chains resulted in high ionic conductivity. The expected high charge-rate performance was not achieved, however, due to the high interfacial impedance present between the polymer electrolyte and the electrodes. Several procedural modifications were employed in order to decrease the interfacial impedance of the battery cell. The poly(arylene ether) based ionomer was saturated with an ionic liquid mixture, in order to explore the possibility of its application as a safe, inflammable electrolyte. A low-viscosity ionic liquid with high ionic conductivity, 1-butyl-3-methylimidazolium thiocyanate which has never been successfully utilized as an electrolyte for lithium-ion batteries was incorporated into a battery cell as a solvent mixture with propylene carbonate and lithium bis(trifluoromethane)sulfonimide impregnated in a free-standing hybrid electrolyte film. Outstanding ionic conductivity was achieved and the lithium half cell comprising a LTO cathode and a lithium metal anode separated by the solid polymer electrolyte showed good cyclability at room temperature and even at 0°C. The presence of a sufficient amount of propylene carbonate, which resulted in flammability of the polymer electrolyte, was discovered to be critical in the electrochemical stability of the polymer electrolyte.

A solid state actuator based on polypyrrole (PPy) and a solid electrolyte NBR working in air

NASA Astrophysics Data System (ADS)

Cho, Misuk; Nam, Jaedo; Choi, Hyouk Ryeol; Koo, Jachoon; Lee, Youngkwan

2005-05-01

The solid polymer electrolyte based conducting polymer actuator was presented. In the preparation of acutuator module, an ionic liquid impregnated a synthetic rubber (NBR) and PPy were used as a solid polymer electrolyte and conducting polymer, respectively. An ionic liquid, 1-butyl-3-methylimidazolium bis (trifluoromethyl sulfonyl)imide (BMITFSI) is gradually dispersed into the NBR film and the conducting polymer, PPy was synthesized on the surface of NBR. The ionic conductivity of new type solid polymer electrolyte as a function of the immersion time was investigated. The cyclic voltammetry responsed and the redox switching dynamics of PEDOT in NBR matrix were studied. The displacement of the actuator was measured by laser beam.

Role of succinonitrile in improving ionic conductivity of sodium-ion conductive polymer electrolyte

NASA Astrophysics Data System (ADS)

Nair, Manjula G.; Mohapatra, Saumya R.

2018-05-01

Sodium ion conducting solid polymer electrolytes were prepared using poly (ethylene oxide) (PEO) as polymer matrix, sodium perchlorate (NaClO4) as salt and succinonitrile (SN) as a plasticizer by solution casting technique. By blending a plastic crystal such as succinonitrile (SN) with PEO-NaClO4 electrolyte system, we aimed at improving the ionic conductivity by weakening the ether oxygen-Na+ interactions. The XRD and FTIR studies revealed structural and micro-structural changes in the blended electrolytes which aids in improving ionic conductivity. Also, DSC measurements showed improved segmental motion in the blended polymer electrolytes due to plasticizing effect of SN. The maximum ionic conductivity observed at room temperature is 1.13×10-5 S cm-1 merely for 7 wt. % of SN, which is one order higher than pure polymer-salt complex. The thermo-gravimetric analysis (TGA) suggests that blending of SN with polymer electrolyte had no detrimental effect on its thermal stability.

Preparation and properties of chitosan-metal complex: Some factors influencing the adsorption capacity for dyes in aqueous solution.

PubMed

Rashid, Sadia; Shen, Chensi; Yang, Jing; Liu, Jianshe; Li, Jing

2018-04-01

Chitosan-metal complexes have been widely studied in wastewater treatment, but there are still various factors in complex preparation which are collectively responsible for improving the adsorption capacity need to be further studied. Thus, this study investigates the factors affecting the adsorption ability of chitosan-metal complex adsorbents, including various kinds of metal centers, different metal salts and crosslinking degree. The results show that the chitosan-Fe(III) complex prepared by sulfate salts exhibited the best adsorption efficiency (100%) for various dyes in very short time duration (10min), and its maximum adsorption capacity achieved 349.22mg/g. The anion of the metal salt which was used in preparation played an important role to enhance the adsorption ability of chitosan-metal complex. SO 4 2- ions not only had the effect of crosslinking through electrostatic interaction with amine group of chitosan polymer, but also could facilitate the chelation of metal ions with chitosan polymer during the synthesis process. Additionally, the pH sensitivity and the sensitivity of ionic environment for chitosan-metal complex were analyzed. We hope that these factors affecting the adsorption of the chitosan-metal complex can help not only in optimizing its use but also in designing new chitosan-metal based complexes. Copyright © 2017. Published by Elsevier B.V.

Removal of total cyanide in coking wastewater during a coagulation process: significance of organic polymers.

PubMed

Shen, Jian; Zhao, He; Cao, Hongbin; Zhang, Yi; Chen, Yongsheng

2014-02-01

Whether a cationic organic polymer can remove more total cyanide (TCN) than a non-ionic organic polymer during the same flocculation system has not been reported previously. In this study, the effects of organic polymers with different charge density on the removal mechanisms of TCN in coking wastewater are investigated by polyferric sulfate (PFS) with a cationic organic polymer (PFS-C) or a non-ionic polymer (PFS-N). The coagulation experiments results show that residual concentrations of TCN (Fe(CN)6(3-)) after PFS-C flocculation (TCN < 0.2 mg/L) are much lower than that after PFS-N precipitation. This can be attributed to the different TCN removal mechanisms of the individual organic polymers. To investigate the roles of organic polymers, physical and structural characteristics of the flocs are analyzed by FT-IR, XPS, TEM and XRD. Owing to the presence of N+ in PFS-C, Fe(CN)6(3-) and negative flocs (Fe(CN)6(3-) adsorbed on ferric hydroxides) can be removed via charge neutralization and electrostatic patch flocculation by the cationic organic polymer. However, non-ionic N in PFS-N barely reacts with cyanides through sweeping or bridging, which indicates that the non-ionic polymer has little influence on TCN removal.

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

PubMed

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

2016-01-01

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

Enhanced photophysics of conjugated polymers

DOEpatents

Chen, Liaohai [Argonne, IL; Xu, Su [Santa Clara, CA; McBranch, Duncan [Santa Fe, NM; Whitten, David [Santa Fe, NM

2003-05-27

The addition of oppositely charged surfactant to fluorescent ionic conjugated polymer forms a polymer-surfactant complex that exhibits at least one improved photophysical property. The conjugated polymer is a fluorescent ionic polymer that typically has at least one ionic side chain or moiety that interacts with the specific surfactant selected. The photophysical property improvements may include increased fluorescence quantum efficiency, wavelength-independent emission and absorption spectra, and more stable fluorescence decay kinetics. The complexation typically occurs in a solution of a polar solvent in which the polymer and surfactant are soluble, but it may also occur in a mixture of solvents. The solution is commonly prepared with a surfactant molecule:monomer repeat unit of polymer ratio ranging from about 1:100 to about 1:1. A polymer-surfactant complex precipitate is formed as the ratio approaches 1:1. This precipitate is recoverable and usable in many forms.

Ion-Containing Polymers: Ionomers.

ERIC Educational Resources Information Center

Bazuin, C. G.; Eisenberg, A.

1981-01-01

Demonstrates how the incorporation of relatively low amounts of ionic material into nonionic polymers affects the structure and properties of these polymers. The extent to which properties are altered depends on dielectric constant of the backbone, position and type of ionic group, counterion type, ion concentration, and degree of neutralization.…

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

DTIC Science & Technology

2008-08-01

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

Surface and Electrochemical Properties of Polymer Brush-Based Redox Poly(Ionic Liquid).

PubMed

Bui-Thi-Tuyet, Van; Trippé-Allard, Gaëlle; Ghilane, Jalal; Randriamahazaka, Hyacinthe

2016-10-26

Redox-active poly(ionic liquid) poly(3-(2-methacryloyloxy ethyl)-1-(N-(ferrocenylmethyl) imidazolium bis(trifluoromethylsulfonyl)imide deposited onto electrode surfaces has been prepared using surface-initiated atom transfer radical polymerization SI-ATRP. The process starts by electrochemical immobilization of initiator layer, and then methacrylate monomer carrying ferrocene and imidazolium units is polymerized in ionic liquid media via SI-ATRP process. The surfaces analyses of the polymer exhibit a well-defined polymer brushlike structure and confirm the presence of ferrocene and ionic moieties within the film. Furthermore, the electrochemical investigations of poly(redox-active ionic liquid) in different media demonstrate that the electron transfer is not restricted by the rate of counterion migration into/out of the polymer. The attractive electrochemical performance of these materials is further demonstrated by performing electrochemical measurement, of poly(ferrocene ionic liquid), in solvent-free electrolyte. The facile synthesis of such highly ordered electroactive materials based ionic liquid could be useful for the fabrication of nanostructured electrode suitable for performing electrochemistry in solvent free electrolyte. We also demonstrate possible applications of the poly(FcIL) as electrochemically reversible surface wettability system and as electrochemical sensor for the catalytic activity toward the oxidation of tyrosine.

Characterization and modeling of ionic polymeric smart materials as artificial muscles and robotic swimming structures

NASA Astrophysics Data System (ADS)

Mojarrad, Mehran

2001-07-01

In this dissertation document, a thorough review and investigation of works in connection with the ionic polymeric gels as artificial muscles and electrically controllable polymeric network structures were performed. Where possible, comparisons were made with biological muscles and applications in marine propulsion using such polymeric materials were investigated. Furthermore, methods of fabrication of several chemically active ionic polymeric gel muscles such as PolyAcryloNitrile (PAN), Poly(2-Acrylamido-2-Methyl-1-PropaneSulfonic) acid (PAMPS), and PolyAcrylic-acid-bis-AcrylaMide (PAAM) as well as a new class of electrically active composite muscle such as Ion-Exchange-Metal-Composites (IEMC) or Ionic Polymer Metal Composites (IPMC) materials are introduced and investigated that resulted in two US patents regarding their fabrication and application capabilities as actuators and sensors. In this research, various forms of the IPMC fabrication were explored and reported. In addition, characterization of PAN muscles, bundling and encapsulation were investigated. Conversion of chemical to electrical artificial muscles were also investigated using chemical plating techniques as well as physical vapor deposition methods of the pH-activated muscles like PAN fibers. Experimental methods were devised to characterize contraction, expansion, and bending of various actuators using isometric, isoionic, and isotonic characterization methods. Several apparatuses for modeling and testing of the various artificial muscles were built to show the viability of the application of both chemoactive and electroactive muscles. Furthermore PAN fiber muscles in different configurations such as spring-loaded fiber bundles, biceps, triceps, ribbon type muscles, and segmented fiber bundles were fabricated to make a variety of actuators. Additionally, swimming robotic structures and associated hardware were built to incorporate IPMC as biomimetic propulsion fin actuators. In addition, various configuration of IPMC such as linear actuators and multiplayer actuators were fabricated and evaluated for load and sensing capability. Theories associated with ionic polymer gels electrodynamics and chemodynamics were proposed, analyzed and modeled for the manufactured material. Futhermore, theoretical models of swimming structures were developed and compared with biological fish propulsion models and dynamically evaluated for robotic applications.

Fullerene reinforced ionic polymer transducer

NASA Astrophysics Data System (ADS)

Jung, J. H.; Cheng, T. H.; Oh, I. K.

2009-07-01

Novel fullerene reinforced nano-composite transducers based on nafion were developed inorder to improve the ionic polymer metal composite transducer. The fullerene reinforced nano-composite membranes were fabricated by recasting method with 0.1 and 0.5 weight percentage of a Fullerenes. Stress-Strain tests showed tremendous increase in stiffness and modulus of the nano-composite membranes even at these minute concentrations of Fullerenes. Ionic exchange capacity analysis and proton conductivity test were performed to calculate the electrical property of the composite films. Water uptake was measured to understand the liquid adsorbing characteristics of the membranes. Also, tip displacement of the nano-composite membrane transducer was investigated under AC excitations with various magnitudes and frequencies. Furthermore, the generated energy was measured from external sinusoidal physical input vibration with several displacements and frequencies by using a mechanical shaker. As a result, the fullerene reinforced nanocomposite membrane based on nafion shows higher stiffness and Young's modulus than that of pure nafion membrane. Also, the nano-composite membrane had better water uptake and proton conductivity than the pure membrane. Fullerene reinforced nano-composite membrane transducer actuates to a much larger deformations than pure nafion membrane transducer. The developed membrane transducer dissipates more energy from the physical input vibration than that of unfilled(or virgin) Nafion membrane transducer.

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

PubMed

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

2017-09-04

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

Synthesis of electroactive ionic liquids for flow battery applications

DOEpatents

Anderson, Travis Mark; Ingersoll, David; Staiger, Chad; Pratt, Harry

2015-09-01

The present disclosure is directed to synthesizing metal ionic liquids with transition metal coordination cations, where such metal ionic liquids can be used in a flow battery. A cation of a metal ionic liquid includes a transition metal and a ligand coordinated to the transition metal.

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

NASA Astrophysics Data System (ADS)

Boddohi, Soheil; Killingsworth, Christopher; Kipper, Matt

2008-03-01

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

Molecular dynamics simulation of low dielectric constant polymer electrolytes

NASA Astrophysics Data System (ADS)

Wheatle, Bill; Lynd, Nathaniel; Ganesan, Venkat

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

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

NASA Astrophysics Data System (ADS)

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.

Polymer electrolyte based on crosslinked poly(glycidyl methacrylate) and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

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

Fei, Beatrice Wong Chui; Hanifah, Sharina Abu; Ahmad, Azizan

2015-09-25

Polymer electrolytes based on crosslinked poly(glycidyl methacrylate) as polymer host and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BmimTFSI) as incorporated salt were prepared by in-situ photopolymerization technique. The complexes with different mass ratio of glycidyl methacrylate (GMA) monomer to BmimTFSI were investigated. The ionic conductivity of the polymer electrolyte was increased and reach the highest value of 7.50 × 10{sup −4} S cm{sup −1} at the ratio of 3:7 (GMA: BmimTFSI). The interaction between the polymer host and ionic liquid was proved by Attenuated Total Reflectance-Fourier Transformation Infra-Red Spectroscopy (ATR-FTIR). Meanwhile, the X-ray diffraction analysis shows the amorphousity of the polymer electrolyte film increasemore » with the ionic liquid ratio.« less

Physical Properties of Substituted Imidazolium Based Ionic Liquids Gel Electrolytes

NASA Astrophysics Data System (ADS)

Sutto, Thomas E.; De Long, Hugh C.; Trulove, Paul C.

2002-11-01

The physical properties of solid gel electrolytes of either polyvinylidene diflurohexafluoropropylene or a combination of polyvinylidene hexafluoropropylene and polyacrylic acid, and the molten salts 1-ethyl-3-methylimidazolium tetrafluoroborate, 1,2-dimethyl-3-n-propylimidazolium tetrafluoroborate, and the new molten salts 1,2-dimethyl-3-n-butylimidazolium tetrafluoroborate, and 1,2-dimethyl-3-n-butylimidazolium hexafluorophosphate were characterized by temperature dependent ionic conductivity measurements for both the pure molten salt and of the molten salt with 0.5 M Li+ present. Ionic conductivity data indicate that for each of the molten salts, the highest concentration of molten salt allowable in a single component polymer gel was 85%, while gels composed of 90%molten salt were possible when using both polyvinylidene hexafluorophosphate and polyacrylic acid. For polymer gel composites prepared using lithium containing ionic liquids, the optimum polymer gel composite consisted of 85% of the 0.5 M Li+/ionic liquid, 12.75% polyvinylidene hexafluoropropylene, and 2.25% poly (1-carboxyethylene). The highest ionic conductivity observed was for the gel containing 90%1-ethyl-3-methyl-imidazolium tetrafluoroborate, 9.08 mS/cm. For the lithium containing ionic liquid gels, their ionic conductivity ranged from 1.45 to 0.05 mS/cm, which is comparable to the value of 0.91 mS/cm, observed for polymer composite gels containing 0.5 M LiBF4 in propylene carbonate.

Modelling compression sensing in ionic polymer metal composites

NASA Astrophysics Data System (ADS)

Volpini, Valentina; Bardella, Lorenzo; Rodella, Andrea; Cha, Youngsu; Porfiri, Maurizio

2017-03-01

Ionic polymer metal composites (IPMCs) consist of an ionomeric membrane, including mobile counterions, sandwiched between two thin noble metal electrodes. IPMCs find application as sensors and actuators, where an imposed mechanical loading generates a voltage across the electrodes, and, vice versa, an imposed electric field causes deformation. Here, we present a predictive modelling approach to elucidate the dynamic sensing response of IPMCs subject to a time-varying through-the-thickness compression (‘compression sensing’). The model relies on the continuum theory recently developed by Porfiri and co-workers, which couples finite deformations to the modified Poisson-Nernst-Planck (PNP) system governing the IPMC electrochemistry. For the ‘compression sensing’ problem we establish a perturbative closed-form solution along with a finite element (FE) solution. The systematic comparison between these two solutions is a central contribution of this study, offering insight on accuracy and mathematical complexity. The method of matched asymptotic expansions is employed to find the analytical solution. To this end, we uncouple the force balance from the modified PNP system and separately linearise the PNP equations in the ionomer bulk and in the boundary layers at the ionomer-electrode interfaces. Comparison with FE results for the fully coupled nonlinear system demonstrates the accuracy of the analytical solution to describe IPMC sensing for moderate deformation levels. We finally demonstrate the potential of the modelling scheme to accurately reproduce experimental results from the literature. The proposed model is expected to aid in the design of IPMC sensors, contribute to an improved understanding of IPMC electrochemomechanical response, and offer insight into the role of nonlinear phenomena across mechanics and electrochemistry.

Elucidating interactions of ionic liquids with polymer films using confocal Raman spectroscopy.

PubMed

Schäfer, Thomas; Di Paolo, Roberto E; Franco, Ricardo; Crespo, João G

2005-05-28

We report on the molecular interactions between room-temperature ionic liquids (RTILs) and Nafion and PDMS membranes, proving that in contact with these polymers RTILs behave like electrolytes rather than solvents.

Dynamic curvature sensing employing ionic-polymer-metal composite sensors

NASA Astrophysics Data System (ADS)

Bahramzadeh, Yousef; Shahinpoor, Mohsen

2011-09-01

A dynamic curvature sensor is presented based on ionic-polymer-metal composite (IPMC) for curvature monitoring of deployable/inflatable dynamic space structures. Monitoring the curvature variation is of high importance in various engineering structures including shape monitoring of deployable/inflatable space structures in which the structural boundaries undergo a dynamic deployment process. The high sensitivity of IPMCs to the applied deformations as well as its flexibility make IPMCs a promising candidate for sensing of dynamic curvature changes. Herein, we explore the dynamic response of an IPMC sensor strip with respect to controlled curvature deformations subjected to different forms of input functions. Using a specially designed experimental setup, the voltage recovery effect, phase delay, and rate dependency of the output voltage signal of an IPMC curvature sensor are analyzed. Experimental results show that the IPMC sensor maintains the linearity, sensitivity, and repeatability required for curvature sensing. Besides, in order to describe the dynamic phenomena such as the rate dependency of the IPMC sensor, a chemo-electro-mechanical model based on the Poisson-Nernst-Planck (PNP) equation for the kinetics of ion diffusion is presented. By solving the governing partial differential equations the frequency response of the IPMC sensor is derived. The physical model is able to describe the dynamic properties of the IPMC sensor and the dependency of the signal on rate of excitations.

Impedance analysis on PVA/PVP: GO blend nanocomposite polymer films

NASA Astrophysics Data System (ADS)

Rao, M. C.; Basha, S. K. Shahenoor; Kumar, B. Ranjit

2018-05-01

Nanocomposite polymer films have been prepared by doping Graphene oxide (GO) in PVA/PVP blend polymers by solution cast technique. AC conductivity studies were performed on to the prepared nanocomposite films and the maximum ionic conductivity is found to be 6.13x10-4 Scm-1 for (0.30:0.3) wt% of nanocomposite polymer film at room temperature. The maximum ionic conductivity of nanocomposite polymer films of PVA/PVP: GO holds great promise in potential applications.

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

NASA Astrophysics Data System (ADS)

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

2013-06-01

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

Lithium ion conducting ionic electrolytes

DOEpatents

Angell, C.A.; Xu, K.; Liu, C.

1996-01-16

A liquid, predominantly lithium-conducting, ionic electrolyte is described which has exceptionally high conductivity at temperatures of 100 C or lower, including room temperature. It comprises molten lithium salts or salt mixtures in which a small amount of an anionic polymer lithium salt is dissolved to stabilize the liquid against recrystallization. Further, a liquid ionic electrolyte which has been rubberized by addition of an extra proportion of anionic polymer, and which has good chemical and electrochemical stability, is described. This presents an attractive alternative to conventional salt-in-polymer electrolytes which are not cationic conductors. 4 figs.

Lithium ion conducting ionic electrolytes

DOEpatents

Angell, C. Austen; Xu, Kang; Liu, Changle

1996-01-01

A liquid, predominantly lithium-conducting, ionic electrolyte is described which has exceptionally high conductivity at temperatures of 100.degree. C. or lower, including room temperature. It comprises molten lithium salts or salt mixtures in which a small amount of an anionic polymer lithium salt is dissolved to stabilize the liquid against recrystallization. Further, a liquid ionic electrolyte which has been rubberized by addition of an extra proportion of anionic polymer, and which has good chemical and electrochemical stability, is described. This presents an attractive alternative to conventional salt-in-polymer electrolytes which are not cationic conductors.

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

PubMed

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.

Response surface method (RSM) for optimization of ionic conductivity of membranes polymer electrolyte poly (vinylidene fluoride) (PVDF) with polyvinyl pyrrolidone (PVP) as pore forming agent

NASA Astrophysics Data System (ADS)

Dyartanti, E. R.; Susanto, H.; Widiasa, I. N.; Purwanto, A.

2017-06-01

The Membranes Polymer Gel Electrolyte (MPGEs) based poly (vinylidene fluoride) (PVDF) was prepared by a phase inversion method using polyvinyl pyrrolidone (PVP) as a pore-forming agent and N, N-dimethyl acetamide (DMAc) as a solvent and water as non solvet. The membranes were then soaked in 1 M lithium hexafluorophosphate (LiPF6) in ethylene carbonate (EC) / dimethyl carbonate (DMC) / Diethyl carbonate (DEC) (4:2:4 %vol) solution in order to prepare polymer electrolyte membranes. The MPEGs PVDF/PVP/Nanoclay was applied using central composite design (CCD) experimental design to obtain a quantitative relationship between selected membranes prepared parameters namely (PVDF, PVP as pore forming agent and nanoclay filler concentration) and Ionic conductivity MPEGs. The model was used to find the optimum ionic conductivity from polymer electrolyte membranes. The polymer electrolyte membranes show good ionic conductivity on the order of 6.3 - 8.7 x 10-3 S cm-1 at the ambient temperatures. The ionic conductivity tended to increase with PVP and nanoclay concentration and decrease with PVDF composition. The model predicted the maximum ionic conductivity of 8.47 x 10-3 S cm-1 when the PVDF, PVP and nanoclay concentration were set at 8.01 %, 8.04 % and 10.12%, respectively. The first section in your paper.

Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes

DOE PAGES

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

2018-10-02

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

Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes

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

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

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

Removal of toxic metal ions from landfill leachate by complementary sorption and transport across polymer inclusion membranes.

PubMed

Zawierucha, Iwona; Kozlowski, Cezary; Malina, Grzegorz

2013-10-01

In this study, performance of a lab-scale two-step treatment system was evaluated for removal of toxic metal ions from landfill leachate. The technology of polymer inclusion membranes (PIMs) was the first step, while the second step of the treatment system was based on sorption on impregnated resin. The PIMs were synthesized from cellulose triacetate as a support, macrocyclic compound i.e. alkyl derivative of resorcinarene as a ionic carrier and o-nitrophenyl pentyl ether as a plasticizer. The transport experiments through PIM were carried out in a permeation cell, in which the membrane film was tightly clamped between two cell compartments. The sorption tests were carried out using a column filled with a resin impregnated with resorcinarene derivative. The obtained results show the good performance with respect to the removal of heavy metals from landfill leachate with the overall removal efficiency of 99%, 88% and 55% for Pb(II), Cd(II) and Zn(II) ions, respectively. Moreover the contents of metal ions in the leachate sample after treatment system were below permissible limit for wastewater according to the Polish Standards. Copyright © 2012 Elsevier Ltd. All rights reserved.

Nano-sponge ionic liquid-polymer composite electrolytes for solid-state lithium power sources

NASA Astrophysics Data System (ADS)

Liao, Kang-Shyang; Sutto, Thomas E.; Andreoli, Enrico; Ajayan, Pulickel; McGrady, Karen A.; Curran, Seamus A.

Solid polymer gel electrolytes composed of 75 wt.% of the ionic liquid, 1- n-butyl-2,3-dimethylimidazolium bis-trifluoromethanesulfonylimide with 1.0 M lithium bis-trifluoromethanesulfonylimide and 25 wt.% poly(vinylidenedifluoro-hexafluoropropene) are characterized as the electrolyte/separator in solid-state lithium batteries. The ionic conductivity of these gels ranges from 1.5 to 2.0 mS cm -1, which is several orders of magnitude more conductive than any of the more commonly used solid polymers, and comparable to the best solid gel electrolytes currently used in industry. TGA indicates that these polymer gel electrolytes are thermally stable to over 280 °C, and do not begin to thermally decompose until over 300 °C; exhibiting a significant advancement in the safety of lithium batteries. Atomic force microscopy images of these solid thin films indicate that these polymer gel electrolytes have the structure of nano-sponges, with a sub-micron pore size. For these thin film batteries, 150 charge-discharge cycles are run for Li xCoO 2 where x is cycled between 0.95 down to 0.55. Minimal internal resistance effects are observed over the charging cycles, indicating the high ionic conductivity of the ionic liquid solid polymer gel electrolyte. The overall cell efficiency is approximately 98%, and no significant loss in battery efficiency is observed over the 150 cycles.

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

PubMed

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.

Highly Selective Ionic Block Copolymer Membranes

DTIC Science & Technology

2010-11-10

Multicomponent Diffusion and Sorption in an Ionic Polymer Membrane We recently measured the diffusion and sorption of methanol/water mixtures in Nafion (most...methanol feed concentration (17 M). Figure 1 shows one experiment where hydrated Nafion was exposed to a 2 M methanol/water liquid mixture resulting...copolymer membranes revealed several surprising results. Contrary to what has been observed in most ionic polymer membranes (e.g., Nafion ), the proton

A Synopsis of Interfacial Phenomena in Lithium-Based Polymer Electrolyte Electrochemical Cells

NASA Technical Reports Server (NTRS)

Baldwin, Richard S.; Bennett, William R.

2007-01-01

The interfacial regions between electrode materials, electrolytes and other cell components play key roles in the overall performance of lithium-based batteries. For cell chemistries employing lithium metal, lithium alloy or carbonaceous materials (i.e., lithium-ion cells) as anode materials, a "solid electrolyte interphase" (SEI) layer forms at the anode/electrolyte interface, and the properties of this "passivating" layer significantly affect the practical cell/battery quality and performance. A thin, ionically-conducting SEI on the electrode surface can beneficially reduce or eliminate undesirable side reactions between the electrode and the electrolyte, which can result in a degradation in cell performance. The properties and phenomena attributable to the interfacial regions existing at both anode and cathode surfaces can be characterized to a large extent by electrochemical impedance spectroscopy (EIS) and related techniques. The intention of the review herewith is to support the future development of lithium-based polymer electrolytes by providing a synopsis of interfacial phenomena that is associated with cell chemistries employing either lithium metal or carbonaceous "composite" electrode structures which are interfaced with polymer electrolytes (i.e., "solvent-free" as well as "plasticized" polymer-binary salt complexes and single ion-conducting polyelectrolytes). Potential approaches to overcoming poor cell performance attributable to interfacial effects are discussed.

Application of the solubility parameter concept to the design of chemiresistor arrays

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

Hughes, R.C.; Yelton, W.G.; Ricco, A.J.

1998-04-01

Arrays of unheated chemically sensitive resistors (chemiresistors) can serve as extremely small, low power consumption sensors with simple read out electronics. Most work has focused on the exotic polymeric organic metals, but here the authors report new results on carbon loaded polymer composites, as well as polymeric ionic conductors. They use the solubility parameter concept to understand and categorize the chemiresistor responses and, in particular, they compare chemiresistors fabricated from polyisobutylene (PIB) to results from PIB coated acoustic wave sensors.

Clustering effects in ionic polymers: Molecular dynamics simulations.

PubMed

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

2015-08-01

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

Proximity and touch sensing using deformable ionic conductors (Conference Presentation)

NASA Astrophysics Data System (ADS)

Madden, John D. W.; Dobashi, Yuta; Sarwar, Mirza S.; Preston, Eden C.; Wyss, Justin K. M.; Woehling, Vincent; Nguyen, Tran-Minh-Giao; Plesse, Cedric; Vidal, Frédéric; Naficy, Sina; Spinks, Geoffrey M.

2017-04-01

There is increasing interest in creating bendable and stretchable electronic interfaces that can be worn or applied to virtually any surface. The electroactive polymer community is well placed to add value by incorporating sensors and actuators. Recent work has demonstrated transparent dielectric elastomer actuation as well as pressure, stretch or touch sensing. Here we present two alternative forms of sensing. The first uses ionically conductive and stretchable gels as electrodes in capacitive sensors that detect finger proximity. In this case the finger acts as a third electrode, reducing capacitance between the two gel electrodes as it approaches, which can be detected even during bending and stretching. Very light finger touch is readily detected even during deformation of the substrate. Lateral resolution is achieved by creating a sensor array. In the second approach, electrodes placed beneath a salt containing gel are able to detect ion currents generated by the deformation of the gel. In this approach, applied pressure results in ion currents that create a potential difference around the point of contact, leading to a voltage and current in the electrodes without any need for input electrical energy. The mechanism may be related to effects seen in ionomeric polymer metal composites (IPMCs), but with the response in plane rather than through the thickness of the film. Ultimately, these ionically conductive materials that can also be transparent and actuate, have the potential to be used in wearable devices.

High ionic conductivity P(VDF-TrFE)/PEO blended polymer electrolytes for solid electrochromic devices.

PubMed

Nguyen, Chien A; Xiong, Shanxin; Ma, Jan; Lu, Xuehong; Lee, Pooi See

2011-08-07

Solid polymer electrolytes with excellent ionic conductivity (above 10(-4) S cm(-1)), which result in high optical modulation for solid electrochromic (EC) devices are presented. The combination of a polar host matrix poly(vinylidene fluoride-trifluoroethylene) P(VDF-TrFE) and a solid plasticized of a low molecular weight poly(ethylene oxide) (PEO) (M(w)≤ 20,000) blended polymer electrolyte serves to enhance both the dissolution of lithium salt and the ionic transport. Calorimetric measurement shows a reduced crystallization due to a better intermixing of the polymers with small molecular weight PEO. Vibrational spectroscopy identifies the presence of free ions and ion pairs in the electrolytes with PEO of M(w)≤ 8000. The ionic dissolution is improved using PEO as a plasticizer when compared to liquid propylene carbonate, evidently shown in the transference number analysis. Ionic transport follows the Arrhenius equation with a low activation energy (0.16-0.2 eV), leading to high ionic conductivities. Solid electrochromic devices fabricated with the blended P(VDF-TrFE)/PEO electrolytes and polyaniline show good spectroelectrochemical performance in the visible (300-800 nm) and near-infrared (0.9-2.4 μm) regions with a modulation up to 60% and fast switching speed of below 20 seconds. The successful introduction of the solid polymer electrolytes with its best harnessed qualities helps to expedite the application of various electrochemical devices. This journal is © the Owner Societies 2011

Superior Blends Solid Polymer Electrolyte with Integrated Hierarchical Architectures for All-Solid-State Lithium-Ion Batteries.

PubMed

Zhang, Dechao; Zhang, Long; Yang, Kun; Wang, Hongqiang; Yu, Chuang; Xu, Di; Xu, Bo; Wang, Li-Min

2017-10-25

Exploration of advanced solid electrolytes with good interfacial stability toward electrodes is a highly relevant research topic for all-solid-state batteries. Here, we report PCL/SN blends integrating with PAN-skeleton as solid polymer electrolyte prepared by a facile method. This polymer electrolyte with hierarchical architectures exhibits high ionic conductivity, large electrochemical windows, high degree flexibility, good flame-retardance ability, and thermal stability (workable at 80 °C). Additionally, it demonstrates superior compatibility and electrochemical stability toward metallic Li as well as LiFePO 4 cathode. The electrolyte/electrode interfaces are very stable even subjected to 4.5 V at charging state for long time. The LiFePO 4 /Li all-solid-state cells based on this electrolyte deliver high capacity, outstanding cycling stability, and superior rate capability better than those based on liquid electrolyte. This solid polymer electrolyte is eligible for next generation high energy density all-solid-state batteries.

A soft biomolecule actuator based on a highly functionalized bacterial cellulose nano-fiber network with carboxylic acid groups.

PubMed

Wang, Fan; Jeon, Jin-Han; Park, Sukho; Kee, Chang-Doo; Kim, Seong-Jun; Oh, Il-Kwon

2016-01-07

Upcoming human-related applications such as soft wearable electronics, flexible haptic systems, and active bio-medical devices will require bio-friendly actuating materials. Here, we report a soft biomolecule actuator based on carboxylated bacterial cellulose (CBC), ionic liquid (IL), and poly (3,4-ethylenedioxythiophene)-poly(styrenesulfonate) ( PSS) electrodes. Soft and biocompatible polymer-IL composites were prepared via doping of CBC with ILs. The highly conductive PSS layers were deposited on both sides of the CBC-IL membranes by a dip-coating technique to yield a sandwiched actuator system. Ionic conductivity and ionic exchange capacity of the CBC membrane can be increased up to 22.8 times and 1.5 times compared with pristine bacterial cellulose (BC), respectively, resulting in 8 times large bending deformation than the pure BC actuators with metallic electrodes in an open air environment. The developed CBC-IL actuators show significant progress in the development of biocompatible and soft actuating materials with quick response, low operating voltage and comparatively large bending deformation.

Polymer gel electrolytes for application in aluminum deposition and rechargeable aluminum ion batteries

DOE PAGES

Sun, Xiao -Guang; Fang, Youxing; Jiang, Xueguang; ...

2015-10-22

Polymer gel electrolyte using AlCl3 complexed acrylamide as functional monomer and ionic liquids based on acidic mixture of 1-ethyl-3-methylimidazolium chloride (EMImCl) and AlCl 3 as plasticizer has been successfully prepared for the first time by free radical polymerization. Aluminum deposition is successfully obtained with a polymer gel membrane contianing 80 wt% ionic liquid. As a result, the polymer gel membranes are also good candidates for rechargeable aluminum ion batteries.

Hybrid Nanoparticles as Oil Lubricant Additives for Friction and Wear Reduction

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

Zhao, Bin; Dai, Sheng; Qu, Jun

A new class of organic-inorganic/metallic hybrid nanoparticles (NPs), including oil-soluble polymer brush-grafted metal oxide NPs and organic-modified metallic NPs, was developed and used as oil lubricant additives for friction and wear reduction to improve engine energy efficiency. The tribological properties of these hybrid NPs in polyalphaolefin (PAO) base oil were investigated by high contact stress ball-on-flat reciprocating sliding tribological tests at 100 oC. Using surface-initiated “living”/controlled radical polymerization from initiator- or chain transfer agent-functionalized metal oxide (silica and titania) NPs, we synthesized a series of hairy NPs and systematically studied the effects of molecular weight and chemical composition of graftedmore » polymer brushes on oil dispersibility, stability, and lubrication properties of hairy NPs in PAO. In addition, several types of organic-modified metallic NPs, including silver and palladium NPs, were synthesized by using thiol compounds and ionic liquids (ILs) as ligands. Significant reductions in friction (up to 40%) and wear volume (up to 90%) were achieved by using PAO mixed with hairy NPs or organic-modified metal NPs compared to PAO base oil. Moreover, a positive effect on lubricating performance was observed when oil-soluble hairy silica NPs and an IL were used simultaneously as additives for PAO for friction reduction. The lubrication mechanisms of these hybrid NPs were elucidated by both experimental and simulation studies.« less

Electrical, structural, thermal and electrochemical properties of corn starch-based biopolymer electrolytes.

PubMed

Liew, Chiam-Wen; Ramesh, S

2015-06-25

Biopolymer electrolytes containing corn starch, lithium hexafluorophosphate (LiPF6) and ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate (BmImPF6) are prepared by solution casting technique. Temperature dependence-ionic conductivity studies reveal Vogel-Tamman-Fulcher (VTF) relationship which is associated with free volume theory. Ionic liquid-based biopolymer electrolytes show lower glass transition temperature (Tg) than ionic liquid-free biopolymer electrolyte. X-ray diffraction (XRD) studies demonstrate higher amorphous region of ionic liquid-added biopolymer electrolytes. In addition, the potential stability window of the biopolymer electrolyte becomes wider and stable up to 2.9V. Conclusively, the fabricated electric double layer capacitor (EDLC) shows improved electrochemical performance upon addition of ionic liquid into the biopolymer electrolyte. The specific capacitance of EDLC based on ionic liquid-added polymer electrolyte is relatively higher than that of ionic liquid-free polymer electrolyte as depicted in cyclic voltammogram. Copyright © 2015 Elsevier Ltd. All rights reserved.

A dual-ion imprinted polymer embedded in sol-gel matrix for the ultra trace simultaneous analysis of cadmium and copper.

PubMed

Bali Prasad, Bhim; Jauhari, Darshika; Verma, Archana

2014-03-01

In simultaneous determination of group of elements, there are inter-metallic interactions which result in a non-linear relationship between the peak current and ionic concentration for each of the element, at bare (unmodified) electrode. To resolve this problem, we have resorted, for the first time, to develop a modified pencil graphite electrode using a typical ion imprinted polymer network (dual-ion imprinted polymer embedded in sol-gel matrix (inorganic-organic hybrid nano-material)) for the simultaneous analysis of a binary mixture of Cd(II) and Cu(II) ions, without any complication of inter-metallic interactions and competitive bindings, in real samples. The adequate resolution of differential pulse anodic stripping voltammetry peaks by 725 mV (cf, 615 mV with unmodified electrode), without any cross-reactivity and the stringent detection limits as low as, 0.050 and 0.034 ng mL(-1) (S/N=3) for Cd(II) and Cu(II) ions, respectively by the proposed sensor can be considered useful for the primitive diagnosis of several chronic diseases in clinical settings. Copyright © 2013 Elsevier B.V. All rights reserved.

Lithium Fast-Ion Conductors: Polymer Based Materials.

DTIC Science & Technology

1987-05-30

significant ambient temperature ionic conductivities. Some of the -aterials may be of interest in other contexts. A study of lithium tetra...This work was a search for lithium-containing materials with ambient temperature ionic conductivities of 10- 5 (ohm-cm) " or larger. The work began with...1-8). The discovery of solids, e.g., sodium.8-alumina(l), and polymer-salt complexes, e.g., (PEO) 8 LiCIO 4 (3), with ionic conductivities approaching

The Electrolyte Factor in O2 Reduction Electrocatalysis

DTIC Science & Technology

1993-04-23

molecule thick and does not seem to interfere with 02 and water/proton transport at this interface. This layer resembles a self-ordered Langmuir - Blodgett ... liquid electrolyte from within the polymer is in contact with the catalyst and completes the ionic circuit between the ionic conducting polymer and the...the free energy of adsorption of H2 0 and ionic components because of the lower effective dielectric constant in the electrolyte phase immediately

Immobilization of yeast cells with ionic hydrogel carriers by adhesion-multiplication.

PubMed

Zhaoxin, L; Fujimura, T

2000-12-01

The mixture of an ionic monomer, 2-acrylamido 2-methylpropanesulfonic acid (TBAS), and a series of poly(ethylene glycol) dimethacrylate (nG) monomers were copolymerized with 60Co gamma-rays, and the produced ionic hydrogel polymers were used for immobilization of yeast cells. The cells were adhered onto the surface of the hydrogel polymers and intruded into the interior of the polymers with growing. The immobilized yeast cells with these hydrogel polymers had higher ethanol productivity than that of free cells. The yield of ethanol with poly(TBAS-14G) carrier was the highest and increased by 3.5 times compared to the free cells. It was found that the ethanol yield increased with the increase of glycol number in poly(ethylene glycol) dimethacrylate. The state of the immobilized cells was observed with microscope, and it was also found that the difference in the ethanol productivity is mainly due to the difference in the internal structure and properties of polymer carrier, such as surface charge, hydrophilicity, and swelling ability of polymer carrier.

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

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

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

Highly Conductive Ionic-Liquid Gels Prepared with Orthogonal Double Networks of a Low-Molecular-Weight Gelator and Cross-Linked Polymer.

PubMed

Kataoka, Toshikazu; Ishioka, Yumi; Mizuhata, Minoru; Minami, Hideto; Maruyama, Tatsuo

2015-10-21

We prepared a heterogeneous double-network (DN) ionogel containing a low-molecular-weight gelator network and a polymer network that can exhibit high ionic conductivity and high mechanical strength. An imidazolium-based ionic liquid was first gelated by the molecular self-assembly of a low-molecular-weight gelator (benzenetricarboxamide derivative), and methyl methacrylate was polymerized with a cross-linker to form a cross-linked poly(methyl methacrylate) (PMMA) network within the ionogel. Microscopic observation and calorimetric measurement revealed that the fibrous network of the low-molecular-weight gelator was maintained in the DN ionogel. The PMMA network strengthened the ionogel of the low-molecular-weight gelator and allowed us to handle the ionogel using tweezers. The orthogonal DNs produced ionogels with a broad range of storage elastic moduli. DN ionogels with low PMMA concentrations exhibited high ionic conductivity that was comparable to that of a neat ionic liquid. The present study demonstrates that the ionic conductivities of the DN and single-network, low-molecular-weight gelator or polymer ionogels strongly depended on their storage elastic moduli.

Rapid Polymer Transport in a Single Nanometer-Scale Pore

NASA Astrophysics Data System (ADS)

Kasianowicz, J. J.

1998-03-01

Protein ion channels are nanometer-scale pores that control the transport of ions and polymers across cell membranes. We compared the ability of charged and nonelectrolyte linear polymers to partition into a single channel reconstituted into a planar lipid bilayer membrane. The entry of each polymer (e.g. monodisperse length single-stranded homopolymeric RNA1 or poly(ethylene glycol)2,3) into the pore caused characteristic transient decreases in the channel's ionic conductance. The ionic current blockades yield detailed information about the physical properties of the polymers and the pore. The biological and technological significance of the results will be discussed.

Clustering effects in ionic polymers: Molecular dynamics simulations

DOE PAGES

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

2015-08-18

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

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

PubMed

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.

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

NASA Astrophysics Data System (ADS)

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.

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

NASA Astrophysics Data System (ADS)

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.

A biomimetic underwater vehicle actuated by waves with ionic polymer-metal composite soft sensors.

PubMed

Shen, Qi; Wang, Tianmiao; Kim, Kwang J

2015-09-28

The ionic polymer-metal composite (IPMC) is a soft material based actuator and sensor and has a promising potential in underwater application. This paper describes a hybrid biomimetic underwater vehicle that uses IPMCs as sensors. Propelled by the energy of waves, this underwater vehicle does not need an additional energy source. A physical model based on the hydrodynamics of the vehicle was developed, and simulations were conducted. Using the Poisson-Nernst-Planck system of equations, a physics model for the IPMC sensor was proposed. For this study, experimental apparatus was developed to conduct hydrodynamic experiments for both the underwater vehicle and the IPMC sensors. By comparing the experimental and theoretical results, the speed of the underwater vehicle and the output of the IPMC sensors were well predicted by the theoretical models. A maximum speed of 1.08 × 10(-1) m s(-1) was recorded experimentally at a wave frequency of 1.6 Hz. The peak output voltage of the IPMC sensor was 2.27 × 10(-4) V, recorded at 0.8 Hz. It was found that the speed of the underwater vehicle increased as the wave frequency increased and the IPMC output decreased as the wave frequency increased. Further, the energy harvesting capabilities of the underwater vehicle hosting the IPMCs were tested. A maximum power of 9.50 × 10(-10) W was recorded at 1.6 Hz.

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

PubMed Central

Aoyagi, Wataru; Omiya, Masaki

2016-01-01

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. PMID:28773599

Ionic Liquid-Modified Thermosets and Their Nanocomposites: Dispersion, Exfoliation, Degradation, and Cure

NASA Astrophysics Data System (ADS)

Throckmorton, James A.

This dissertation explores the application of a room temperature ionic liquid (RTIL) to problems in the chemistry, processing, and modification of thermosetting polymers. In particular, the solution properties and reaction chemistry of 1-ethyl-3-methyl imidazolium dicyanamide (EMIM-DCN) are applied to problems of nanoparticle dispersion and processing, graphite exfoliation, cyanate ester (CE) cure, and the environmental degradation of CEs. Nanoparticle Dispersion: Nanocomposite processing can be simplified by using the same compound as both a nanoparticle solvent and an initiator for polymerization. This dual-function molecule can be designed both for solvent potential and reaction chemistry. EMIM-DCN, previously shown by our lab to act as an epoxy initiator, is used in the synthesis of silica and acid expanded graphite composites. These composites are then characterized for particle dispersion and physical properties. Individual particle dispersion of silica nanocomposites is shown, and silica nanocomposites at low loading show individual particle dispersion and improved modulus and fracture toughness. GNP nanocomposites show a 70% increase in modulus along with a 10-order of magnitude increase in electrical conductivity at 6.5 vol%, and an electrical percolation threshold of 1.7 vol%. Direct Graphite Exfoliation By Laminar Shear: This work presents a laminar-shear alternative to chemical processing and chaotic flow-fields for the direct exfoliation of graphite and the single-pot preparation of nanocomposites. Additionally, we develop the theory of laminar flow through a 3-roll mill, and apply that theory to the latest developments in the theory of graphite interlayer shear. The resulting nanocomposite shows low electrical percolation (0.5 vol%) and low thickness (1-3 layer) graphite/graphene flakes. Additionally, the effect of processing conditions by rheometry and comparison with solvent-free conditions reveal the interactions between processing and matrix properties and provide insight into the theory of the chemical and physical exfoliation of graphite crystals and the resulting polymer matrix dispersion. Cyanate Ester Cure: Dicyanamide-containing ionic liquids decrease the cure temperature of bi- and tri-functional CEs. During the cure reaction, the dicyanamide anion completely reacts and is incorporated into the triazine network. The cure effect was found in many dicyanamide-containing ionic liquids with diverse cations. This invention creates a novel, ionic thermoset polymer. The dicyanamide initiator provides an alternative to metal and hydroxyl catalysts (which have been shown to accelerate degradation and possess human and environmental toxicity). Additionally, the ionic character of the new polymer, rare among thermosets, lends itself to future research and novel applications. RTIL initiation also paves the way to new CE technologies, including RTIL-CE nanocomposites, prepared by graphite exfoliation and nanocomposite dispersion techniques developed herin.

Two-site ionic labeling with pyranine: implications for structural dynamics studies of polymers and polypeptides by time-resolved fluorescence anisotropy.

PubMed

Sharma, Jai; Tleugabulova, Dina; Czardybon, Wojciech; Brennan, John D

2006-04-26

Time-resolved fluorescence anisotropy (TRFA) is widely used to study dynamic motions of biomolecules in a variety of environments. However, depolarization due to rapid side chain motions often complicates the interpretation of anisotropy decay data and interferes with the accurate observation of segmental motions. Here, we demonstrate a new method for two-point ionic labeling of polymers and biomolecules that have appropriately spaced amino groups using the fluorescent probe 8-hydroxyl-1,3,6-trisulfonated pyrene (pyranine). TRFA analysis shows that such labeling provides a more rigid attachment of the fluorophore to the macromolecule than the covalent or single-point ionic labeling of amino groups, leading to time-resolved anisotropy decays that better reflect the backbone motion of the labeled polymer segment. Optimal coupling of pyranine to biomolecule dynamics is shown to be obtained for appropriately spaced Arg groups, and in such cases the ionic binding is stable up to 150 mM ionic strength. TRFA was used to monitor the behavior of pyranine-labeled poly(allylamine) (PAM) and poly-d-lysine (PL) in sodium silicate derived sol-gel materials and revealed significant restriction of backbone motion upon entrapment for both polymers, an observation that was not readily apparent in a previous study with entrapped fluorescein-labeled PAM and PL. The implications of these findings for fluorescence studies of polymer and biomolecule dynamics are discussed.

Composite gel polymer electrolyte for lithium ion batteries

NASA Astrophysics Data System (ADS)

Naderi, Roya

Composite gel polymer electrolyte (CGPE) films, consisting of poly (vinylidene fluoride-hexafluoropropylene) (PVdF-HFP) as the membrane, DMF and PC as solvent and plasticizing agent, mixture of charge modified TiO2 and SiO 2 nano particles as ionic conductors, and LiClO4+LiPF 6 as lithium salts were fabricated. Following the work done by Li et al., CGPE was coated on an O2-plasma treated trilayer polypropylene-polyethylene-polypropylene membrane separator using solution casting technique in order to improve the adhesive properties of gel polymer electrolyte to the separator membrane and its respective ionic conductivity due to decreasing the bulk resistance. In acidic CGPE with, the mixture of acid treated TiO2 and neutral SiO2 nano particles played the role of the charge modified nano fillers with enhanced hydroxyl groups. Likely, the mixture of neutral TiO 2 nano particles with basic SiO2 prepared through the hydrolization of tetraethyl orthosilicate (TEOS) provided a more basic environment due to the residues of NH4OH (Ammonium hydroxide) catalyst. The O2 plasma treated separator was coated with the solution of PVDF-HFP: modified nano fillers: Organic solvents with the mixture ratio of 0.1:0.01:1. After the evaporation of the organic solvents, the dried coated separator was soaked in PC-LiClO4+LiPF6 in EC: DMC:DEC (4:2:4 in volume) solution (300% wt. of PVDF-HFP) to form the final CGPE. Lim et al. has reported the enhanced ionic conductivity of 9.78*10-5 Scm-1 in an acidic composite polystyrene-Al2O3 solid electrolyte system with compared to that of basic and neutral in which the ionic conductivity undergoes an ion hopping process in solid interface rather than a segmental movement of ions through the plasticized polymer chain . Half-cells with graphite anode and Li metal as reference electrode were then assembled and the electrochemical measurements and morphology examinations were successfully carried out. Half cells demonstrated a considerable change in their electrochemical performance upon the enhancement of acidic properties of the CGPE, gaining the reversible specific capacity of 314 mAh.g-1 in acidic CGPE vs. 247 mAh.g-1 in basic CGPE C/20 after 33 cycles. The CGPE exhibited submicron pore size while the ionic conductivities were in order of 10-3 and 10-5 Scm-1 with and without modified nano-fillers respectively.

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

NASA Astrophysics Data System (ADS)

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

2016-05-01

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

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

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

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

2016-05-06

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

Mussel-inspired histidine-based transient network metal coordination hydrogels

PubMed Central

Fullenkamp, Dominic E.; He, Lihong; Barrett, Devin G.; Burghardt, Wesley R.; Messersmith, Phillip B.

2013-01-01

Transient network hydrogels cross-linked through histidine-divalent cation coordination bonds were studied by conventional rheologic methods using histidine-modified star poly(ethylene glycol) (PEG) polymers. These materials were inspired by the mussel, which is thought to use histidine-metal coordination bonds to impart self-healing properties in the mussel byssal thread. Hydrogel viscoelastic mechanical properties were studied as a function of metal, pH, concentration, and ionic strength. The equilibrium metal-binding constants were determined by dilute solution potentiometric titration of monofunctional histidine-modified methoxy-PEG and were found to be consistent with binding constants of small molecule analogs previously studied. pH-dependent speciation curves were then calculated using the equilibrium constants determined by potentiometric titration, providing insight into the pH dependence of histidine-metal ion coordination and guiding the design of metal coordination hydrogels. Gel relaxation dynamics were found to be uncorrelated with the equilibrium constants measured, but were correlated to the expected coordination bond dissociation rate constants. PMID:23441102

Synthesis and Compatibility of Ionic Liquid Containing Rod-Coil Polyimide Gel Electrolytes with Lithium Metal Electrodes

NASA Technical Reports Server (NTRS)

Tigelaar, Dean M.; Palker, Allyson E.; Meador, Mary Ann B.; Bennett, William R.

2008-01-01

A highly cross-linked polyimide-polyethylene oxide copolymer has been synthesized that is capable of holding large volumes of liquid component, simultaneously maintaining good dimensional stability. An amine end capped oligomer was made that was imidized in solution, followed by reaction with a triisocyanate in the presence of desired additives at ambient temperature. Polymer films are able to hold over 4 times their weight in room temperature ionic liquid RTIL or carbonate solvent. Electrolytes were studied that contained varying amounts of RTIL, lithium trifluoromethanesulfonimide LiTFSi, and alumina nanoparticles. Electrochemical stability of these electrolytes with lithium metal electrodes was studied by galvanic cycling and impedance spectroscopy. Improved cycling stability and decreased interfacial resistance were observed when increasing amounts of RTIL and LiTFSi were added. The addition of small amounts of alumina further decreased interfacial resistance by nearly an order of magnitude. During the course of the study, cycling stability increased from less than 3 to greater than 1000 h at 60 C and 0.25 mA/cm2 current density.

Ionic Liquids as Extraction Media for Metal Ions

NASA Astrophysics Data System (ADS)

Hirayama, Naoki

In solvent extraction separation of metal ions, recently, many researchers have investigated possible use of hydrophobic ionic liquids as extraction media instead of organic solvents. Ionic liquids are salts of liquid state around room temperature and can act not only as solvents but also as ion-exchangers. Therefore, the extraction mechanism of metal ions into ionic liquids is complicated. This review presents current overview and perspective on evaluation of nature of hydrophobic ionic liquids as extraction media for metal ions.

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

PubMed Central

Raoov, Muggundha; Mohamad, Sharifah; Abas, Mhd Radzi

2014-01-01

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). PMID:24366065

Reversible and strong immobilization of proteins by ionic exchange on supports coated with sulfate-dextran.

PubMed

Fuentes, Manuel; Pessela, Benevides C C; Maquiese, Jorgette V; Ortiz, Claudia; Segura, Rosa L; Palomo, Jose M; Abian, Olga; Torres, Rodrigo; Mateo, Cesar; Fernández-Lafuente, Roberto; Guisán, J M

2004-01-01

New and strong ionic exchange resins have been prepared by the simple and rapid ionic adsorption of anionic polymers (sulfate-dextran) on porous supports activated with the opposite ionic group (DEAE/MANAE). Ionic exchange properties of such composites were strongly dependent on the size of the ionic polymers as well as on the conditions of the ionic coating of the solids with the ionic polymers (optimal conditions were 400 mg of sulfate-dextran 5000 kDa per gram of support). Around 80% of the proteins contained in crude extracts from Escherichia coli and Acetobacter turbidans could be adsorbed on these porous composites even at pH 7. This interaction was stronger than that using conventional carboxymethyl cellulose (CMC) and even others such as supports coated with aspartic-dextran polymer. By means of the sequential use of the new supports and supports coated with polyethyleneimine (PEI), all proteins from crude extracts could be immobilized. In fact, a large percentage (over 50%) could be immobilized on both supports. Finally, some industrially relevant enzymes (beta-galactosidases from Aspergillus oryzae, Kluyveromyces lactis, and Thermussp. strain T2, lipases from Candida antarctica A and B, Candida rugosa, Rhizomucor miehei, and Rhyzopus oryzae and bovine pancreas trypsin and chymotrypsin) have been immobilized on these supports with very high activity recoveries and immobilization rates. After enzyme inactivation, the protein could be fully desorbed from the support, and then the support could be reused for several cycles. Moreover, in some instances the enzyme stability was significantly improved, mainly in the presence of organic solvents, perhaps as a consequence of the highly hydrophilic microenvironment of the support.

Reliability of high strain ionomeric polymer transducers fabricated using the direct assembly process

NASA Astrophysics Data System (ADS)

Akle, Barbar; Nawshin, Saila; Leo, Donald

2007-04-01

Ionomeric polymer transducers have received considerable attention in the past several years. These actuators, sometimes referred to as artificial muscles, have the ability to generate large bending strain and moderate stress at low applied voltages. As sensors, ionic polymer transducers generate an electric response due to mechanical strain. Typically, ionic polymer transducers are composed of Nafion-117 membranes with platinum electrodes and are saturated with water diluents. Recently the authors have developed a novel fabrication technique called the direct assembly process (DAP), which allowed improved control of the electrode morphology and composition. The DAP consists of spraying two high surface area metal-ionomer electrodes on a Nafion membrane. The benefits of the DAP process over previous methods is the ability to control the thickness of the electrode, the ability to control the composition of the electrode layer of the transducer, and the ability for it to be used with a wide variety of diluents. In past work we have demonstrated that platinum, ruthenium dioxide, and single-walled carbon nanotubes can be used as electrode material with diluents such as water, formamide, and ionic liquids. In this work we will present a reliability study of transducers fabricated using the DAP. Water-hydrated transducers dehydrate and stop moving within 5 min while operating in air under the application of ± 2 V. Ionic liquid based transducers are demonstrated to operate in air for over 400 000 cycles with little loss in performance, and are reliable up to 1 million cycles with a performance loss of less than 43%. The main source of degradation is the adhesion of the conductive surface to the high surface area electrode. This is enhanced in this study by using a PUU linking polymer that has good adhesion properties to gold. Large voltage and large strain are proven to decrease the life of the transducer. Formamide based samples are stable for 3 days under a 1 V actuation signal, while they are only reliable for 3-4 h under a 2 V actuation signal. Solvent evaporation is the main reason for degradation in formamide samples and it is increased at 2 V, indicating some electrochemical activity at such high voltages. Finally the initial drop in performance and the fluctuation in the generated strain are shown to be due to the loss of humidity absorbed from ambient air and the fluctuation in this ambient humidity, respectively.

Plasma membranes modified by plasma treatment or deposition as solid electrolytes for potential application in solid alkaline fuel cells.

PubMed

Reinholdt, Marc; Ilie, Alina; Roualdès, Stéphanie; Frugier, Jérémy; Schieda, Mauricio; Coutanceau, Christophe; Martemianov, Serguei; Flaud, Valérie; Beche, Eric; Durand, Jean

2012-07-30

In the highly competitive market of fuel cells, solid alkaline fuel cells using liquid fuel (such as cheap, non-toxic and non-valorized glycerol) and not requiring noble metal as catalyst seem quite promising. One of the main hurdles for emergence of such a technology is the development of a hydroxide-conducting membrane characterized by both high conductivity and low fuel permeability. Plasma treatments can enable to positively tune the main fuel cell membrane requirements. In this work, commercial ADP-Morgane® fluorinated polymer membranes and a new brand of cross-linked poly(aryl-ether) polymer membranes, named AMELI-32®, both containing quaternary ammonium functionalities, have been modified by argon plasma treatment or triallylamine-based plasma deposit. Under the concomitant etching/cross-linking/oxidation effects inherent to the plasma modification, transport properties (ionic exchange capacity, water uptake, ionic conductivity and fuel retention) of membranes have been improved. Consequently, using plasma modified ADP-Morgane® membrane as electrolyte in a solid alkaline fuel cell operating with glycerol as fuel has allowed increasing the maximum power density by a factor 3 when compared to the untreated membrane.

Plasma Membranes Modified by Plasma Treatment or Deposition as Solid Electrolytes for Potential Application in Solid Alkaline Fuel Cells

PubMed Central

Reinholdt, Marc; Ilie, Alina; Roualdès, Stéphanie; Frugier, Jérémy; Schieda, Mauricio; Coutanceau, Christophe; Martemianov, Serguei; Flaud, Valérie; Beche, Eric; Durand, Jean

2012-01-01

In the highly competitive market of fuel cells, solid alkaline fuel cells using liquid fuel (such as cheap, non-toxic and non-valorized glycerol) and not requiring noble metal as catalyst seem quite promising. One of the main hurdles for emergence of such a technology is the development of a hydroxide-conducting membrane characterized by both high conductivity and low fuel permeability. Plasma treatments can enable to positively tune the main fuel cell membrane requirements. In this work, commercial ADP-Morgane® fluorinated polymer membranes and a new brand of cross-linked poly(aryl-ether) polymer membranes, named AMELI-32®, both containing quaternary ammonium functionalities, have been modified by argon plasma treatment or triallylamine-based plasma deposit. Under the concomitant etching/cross-linking/oxidation effects inherent to the plasma modification, transport properties (ionic exchange capacity, water uptake, ionic conductivity and fuel retention) of membranes have been improved. Consequently, using plasma modified ADP-Morgane® membrane as electrolyte in a solid alkaline fuel cell operating with glycerol as fuel has allowed increasing the maximum power density by a factor 3 when compared to the untreated membrane. PMID:24958295

Characterization of chitosan-starch blend based biopolymer electrolyte doped with ammonium nitrate

NASA Astrophysics Data System (ADS)

Shaffie, Ahmad Hakimi; Khiar, Azwani Sofia Ahmad

2018-06-01

Polymer electrolyte is an ionic conductor formed by dissolving salt in polymer host. In this work, starch/chitosan blend based polymer electrolyte was prepared with different weight percentage of Ammonium Nitrate (NH4NO3) via solution casting technique. The film was characterized by impedance spectroscopy HIOKI 3531- 01 LCR Hi-Tester to measure its ionic conductivity over a wide range of frequency between 50Hz-5MHz and at ambient temperature. Sample with 35 wt% of NH4NO3 shows the highest conductivity of (6.34 ± 1.52) = 10-7 Scm-1. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy were used to correlate the ionic conductivity results.

Microwave-Assisted Syntheses in Recyclable Ionic Liquids: Photoresists Based on Renewable Resources

PubMed Central

Petit, Charlotte; Luef, Klaus P; Edler, Matthias; Griesser, Thomas; Kremsner, Jennifer M; Stadler, Alexander; Grassl, Bruno; Reynaud, Stéphanie; Wiesbrock, Frank

2015-01-01

The copoly(2-oxazoline) pNonOx80-stat-pDc=Ox20 can be synthesized from the cationic ring-opening copolymerization of 2-nonyl-2-oxazoline NonOx and 2-dec-9′-enyl-2-oxazoline Dc=Ox in the ionic liquid n-hexyl methylimidazolium tetrafluoroborate under microwave irradiation in 250 g/batch quantities. The polymer precipitates upon cooling, enabling easy recovery of the polymer and the ionic liquid. Both monomers can be obtained from fatty acids from renewable resources. pNonOx80-stat-pDc=Ox20 can be used as polymer in a photoresist (resolution of 1 μm) based on UV-induced thiol–ene reactions. PMID:26354027

Investigation of Proton Conductivity of Cation-Exchanged, Sulfonated Poly(b-Styrene-b-Isobutylene-b-Styrene) Membranes

DTIC Science & Technology

2009-09-01

solvents. Similar behavior was observed for Nafion -117 (also a polymer with ionic SO3H clusters) by other researchers (14). Results shown in this...pattern was only valid for ionic S-SIBS membranes exchanged with cations; neither acid form of SIBS-97-H nor Nafion -117 fell on this line. In order...10  vi INTENTIONALLY LEFT BLANK. 1 1. Introduction Research in ionic polymers has been gaining popularity in the scientific community

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

PubMed

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.

Insulator to metal transition in WO 3 induced by electrolyte gating

DOE PAGES

Leng, X.; Pereiro, J.; Strle, J.; ...

2017-07-03

Tungsten oxide and its associated bronzes (compounds of tungsten oxide and an alkali metal) are well known for their interesting optical and electrical characteristics. We have modified the transport properties of thin WO 3 films by electrolyte gating using both ionic liquids and polymer electrolytes. We are able to tune the resistivity of the gated film by more than five orders of magnitude, and a clear insulator-to-metal transition is observed. To clarify the doping mechanism, we have performed a series of incisive operando experiments, ruling out both a purely electronic effect (charge accumulation near the interface) and oxygen-related mechanisms. Wemore » propose instead that hydrogen intercalation is responsible for doping WO 3 into a highly conductive ground state and provide evidence that it can be described as a dense polaronic gas.« less

Investigations of the ex situ ionic conductivities at 30 degrees C of metal-cation-free quaternary ammonium alkaline anion-exchange membranes in static atmospheres of different relative humidities.

PubMed

Varcoe, John R

2007-03-28

This article presents the first systematic study of the effect of Relative Humidity (RH) on the water content and hydroxide ion conductivity of quaternary ammonium-based Alkaline Anion-Exchange Membranes (AAEMs). These AAEMs have been developed specifically for application in alkaline membrane fuel cells, where conductivities of >0.01 S cm(-1) are mandatory. When fully hydrated, an ETFE-based radiation-grafted AAEM exhibited a hydroxide ion conductivity of 0.030 +/- 0.005 S cm(-1) at 30 degrees C without additional incorporation of metal hydroxide salts; this is contrary to the previous wisdom that anion-exchange membranes are very low in ionic conductivity and represents a significant breakthrough for metal-cation-free alkaline ionomers. Desirably, this AAEM also showed increased dimensional stability on full hydration compared to a Nafion-115 proton-exchange membrane; this dimensional stability is further improved (with no concomitant reduction in ionic conductivity) with a commercial AAEM of similar density but containing additional cross-linking. However, all of the AAEMs evaluated in this study demonstrated unacceptably low conductivities when the humidity of the surrounding static atmospheres was reduced (RH = 33-91%); this highlights the requirement for continued AAEM development for operation in H(2)/air fuel cells with low humidity gas supplies. Preliminary investigations indicate that the activation energies for OH(-) conduction in these quaternary ammonium-based solid polymer electrolytes are typically 2-3 times higher than for H(+) conduction in acidic Nafion-115 at all humidities.

Helium Nanodroplet Isolation and Infrared Spectroscopy of the Isolated Ion-Pair 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

DTIC Science & Technology

2013-09-01

Use in Lithium Metal-Polymer Electrolyte Batteries. J. Electrochem. Soc. 2005, 152, A978-A983.     4. Henderson, W. A.; Shin, J. H.; Passerini, S...Chen, L. Q.; Hu, Y. S.; Li, H.; Huang, X. J. Novel Room Temperature Molten Salt Electrolyte Based on Litfsi and Acetamide for Lithium Batteries...the Structure of Ionic Liquid 1-Ethyl-3- Methylimidazolium Hexafluorophosphate . Chinese J. Struc. Chem. 2005, 24, 576-580.     37. Liu, K. H.; Pu, M

Flexible thin-film battery based on solid-like ionic liquid-polymer electrolyte

NASA Astrophysics Data System (ADS)

Li, Qin; Ardebili, Haleh

2016-01-01

The development of high-performance flexible batteries is imperative for several contemporary applications including flexible electronics, wearable sensors and implantable medical devices. However, traditional organic liquid-based electrolytes are not ideal for flexible batteries due to their inherent safety and stability issues. In this study, a non-volatile, non-flammable and safe ionic liquid (IL)-based polymer electrolyte film with solid-like feature is fabricated and incorporated in a flexible lithium ion battery. The ionic liquid is 1-Ethyl-3-methylimidazolium dicyanamide (EMIMDCA) and the polymer is composed of poly(vinylidene fluoride-co-hexafluoropropene) (PVDF-HFP). The electrolyte exhibits good thermal stability (i.e. no weight loss up to 300 °C) and relatively high ionic conductivity (6 × 10-4 S cm-1). The flexible thin-film lithium ion battery based on solid-like electrolyte film is encapsulated using a thermal-lamination process and demonstrates excellent electrochemical performance, in both flat and bent configurations.

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

PubMed

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

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

NASA Technical Reports Server (NTRS)

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 environment of a few Torrs and temperatures of the order of - 140 degrees Celsius. These muscles are shown to work quite well in such harsh cryogenic environments and thus present a great potential as sensors and actuators that can operate at cryogenic temperatures.

Harnessing Poly(ionic liquid)s for Sensing Applications.

PubMed

Guterman, Ryan; Ambrogi, Martina; Yuan, Jiayin

2016-07-01

The interest in poly(ionic liquid)s for sensing applications is derived from their strong interactions to a variety of analytes. By combining the desirable mechanical properties of polymers with the physical and chemical properties of ILs, new materials can be created. The tunable nature of both ionic liquids and polymers allows for incredible diversity, which is exemplified in their broad applicability. In this article we examine the new field of poly(ionic liquid) sensors by providing a detailed look at the current state-of-the-art sensing devices for solvents, gases, biomolecules, pH, and anions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Block copolymers from ionic liquids for the preparation of thin carbonaceous shells

PubMed Central

Hanif, Sadaf; Oschmann, Bernd; Spetter, Dmitri; Tahir, Muhammad Nawaz; Tremel, Wolfgang

2017-01-01

This paper describes the controlled radical polymerization of an ionic-liquid monomer by RAFT polymerization. This allows the control over the molecular weight of ionic liquid blocks in the range of 8000 and 22000 and of the block-copolymer synthesis. In this work we focus on block copolymers with an anchor block. They can be used to control the formation of TiO2 nanoparticles, which are functionalized thereafter with a block of ionic-liquid polymer. Pyrolysis of these polymer functionalized inorganic nanoparticles leads to TiO2 nanoparticles coated with a thin carbonaceous shell. Such materials may, e.g., be interesting as battery materials. PMID:28904612

Block copolymers from ionic liquids for the preparation of thin carbonaceous shells.

PubMed

Hanif, Sadaf; Oschmann, Bernd; Spetter, Dmitri; Tahir, Muhammad Nawaz; Tremel, Wolfgang; Zentel, Rudolf

2017-01-01

This paper describes the controlled radical polymerization of an ionic-liquid monomer by RAFT polymerization. This allows the control over the molecular weight of ionic liquid blocks in the range of 8000 and 22000 and of the block-copolymer synthesis. In this work we focus on block copolymers with an anchor block. They can be used to control the formation of TiO 2 nanoparticles, which are functionalized thereafter with a block of ionic-liquid polymer. Pyrolysis of these polymer functionalized inorganic nanoparticles leads to TiO 2 nanoparticles coated with a thin carbonaceous shell. Such materials may, e.g., be interesting as battery materials.

Transports of ionic liquids in ionic polymer conductor network composite actuators

NASA Astrophysics Data System (ADS)

Liu, Yang; Liu, Sheng; Lin, Junhong; Wang, Dong; Jain, Vaibhav; Montazami, Reza; Heflin, James R.; Li, Jing; Madsen, Louis; Zhang, Q. M.

2010-04-01

We investigate the influence of ionic liquids on the electromechanical performance of Ionic Polymer Conductor Network Composite (IPCNC) bending actuators. Two imidazolium ionic liquids (ILs) with one cation, which is 1-ethyl-3- methylimidazolium ([EMI+]), and two different anions, which are tetrafluoroborate ([BF4-]) and trifluoromethanesulfonate ([Tf-]), are chosen for the study. By combining the time domain electric and electromechanical responses, we developed a new model that describes the ion transports in IPCNC actuators. The time constant of excess cation and anion migration in various composite electrodes are deduced: 6s and 25s in RuO2/Nafion; 7.9s and 36.3s in RuO2/Aquivion; 4.8s and 53s in Au/PAH, respectively. NMR is also applied to provide quantitative measures of self-diffusion coefficients independently for IL anions and cations both in pure ILs and in ILs absorved into ionomers. All the results indicate that the motion of cation, in the studied pure ionic liquids, polymer matrix and conductor network composites, is faster than that of anion. Moreover, the CNC morphology is playing a crucial role in determining the ion transport in the porous electrodes.

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

PubMed

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

2017-05-01

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

High-flux ionic diodes, ionic transistors and ionic amplifiers based on external ion concentration polarization by an ion exchange membrane: a new scalable ionic circuit platform.

PubMed

Sun, Gongchen; Senapati, Satyajyoti; Chang, Hsueh-Chia

2016-04-07

A microfluidic ion exchange membrane hybrid chip is fabricated using polymer-based, lithography-free methods to achieve ionic diode, transistor and amplifier functionalities with the same four-terminal design. The high ionic flux (>100 μA) feature of the chip can enable a scalable integrated ionic circuit platform for micro-total-analytical systems.

Synthesis and application of ion-imprinted polymer nanoparticles for the extraction and preconcentration of copper ions in environmental water samples.

PubMed

Roushani, Mahmoud; Abbasi, Shahryar; Khani, Hossein

2015-04-01

Novel Cu(II) ion-imprinted polymers (Cu-IIP) nanoparticles were prepared by using Cu(II) ion-thiosemicarbazide complex as the template molecule and methacrylic acid, ethylene glycol dimethacrylate (EGDMA), and 2,2'azobisisobutyronitrile (AIBN) as the functional monomer, cross-linker, and the radical initiator, respectively. The synthesized polymer nanoparticles were characterized by using infrared spectroscopy (IR), thermo gravimetric analysis (TGA), X-ray diffraction (XRD), and scanning electron microscopic (SEM) techniques. Some parameters such as pH, weight of the polymer, adsorption time, elution time, eluent type, and eluent volume which affect the extraction efficiency of the polymer were studied. In the proposed method, the maximum sorbent capacity of the ion-imprinted polymer was calculated to be 38.8 mg g(-1). The preconcentration factor, relative standard deviation, and limit of detection of the method were found to be 80, 1.7%, and 0.003 μg mL(-1), respectively. The prepared ion-imprinted polymer nanoparticles have an increased selectivity toward Cu(II) ions over a range of competing metal ions with the same charge and similar ionic radius. The method was applied to the determination of ultra trace levels of Cu2+ in environmental water samples with satisfactory results.

Decoupling Mechanical and Ion Transport Properties in Polymer Electrolyte Membranes

NASA Astrophysics Data System (ADS)

McIntosh, Lucas D.

Polymer electrolytes are mixtures of a polar polymer and salt, in which the polymer replaces small molecule solvents and provides a dielectric medium so that ions can dissociate and migrate under the influence of an external electric field. Beginning in the 1970s, research in polymer electrolytes has been primarily motivated by their promise to advance electrochemical energy storage and conversion devices, such as lithium ion batteries, flexible organic solar cells, and anhydrous fuel cells. In particular, polymer electrolyte membranes (PEMs) can improve both safety and energy density by eliminating small molecule, volatile solvents and enabling an all-solid-state design of electrochemical cells. The outstanding challenge in the field of polymer electrolytes is to maximize ionic conductivity while simultaneously addressing orthogonal mechanical properties, such as modulus, fracture toughness, or high temperature creep resistance. The crux of the challenge is that flexible, polar polymers best-suited for polymer electrolytes (e.g., poly(ethylene oxide)) offer little in the way of mechanical robustness. Similarly, polymers typically associated with superior mechanical performance (e.g., poly(methyl methacrylate)) slow ion transport due to their glassy polymer matrix. The design strategy is therefore to employ structured electrolytes that exhibit distinct conducting and mechanically robust phases on length scales of tens of nanometers. This thesis reports a remarkably simple, yet versatile synthetic strategy---termed polymerization-induced phase separation, or PIPS---to prepare PEMs exhibiting an unprecedented combination of both high conductivity and high modulus. This performance is enabled by co-continuous, isotropic networks of poly(ethylene oxide)/ionic liquid and highly crosslinked polystyrene. A suite of in situ, time-resolved experiments were performed to investigate the mechanism by which this network morphology forms, and it appears to be tied to the disordered structure observed in diblock polymer melts near the order-disorder transition. In the resulting solid PEMs, the conductivity and modulus are both high, exceeding the 1 mS/cm and approaching the 1 GPa metrics, respectively, often cited for lithium-metal batteries. In the final chapter, an alternative synthetic route to generate nanostructured PEMs is presented. This strategy relies on the formation of a thermodynamically stable network morphology exhibited by a triblock terpolymer prepared with crosslinking moieties along the backbone. Although the mechanical properties of the resulting PEM are excellent, the conductivity is found to be somewhat limited by network defects that result from the solvent-casting procedure.

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

PubMed

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

2009-05-15

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

Surface polymerization of (3,4-ethylenedioxythiophene) probed by in situ scanning tunneling microscopy on Au(111) in ionic liquids

NASA Astrophysics Data System (ADS)

Ahmad, Shahzada; Carstens, Timo; Berger, Rüdiger; Butt, Hans-Jürgen; Endres, Frank

2011-01-01

The electropolymerization of 3,4-ethylenedioxythiophene (EDOT) to poly(3,4-ethylenedioxythiophene) (PEDOT) was investigated in the air and water-stable ionic liquids 1-hexyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate [HMIm]FAP and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide [EMIm]TFSA. In situscanning tunnelling microscopy (STM) results show that the electropolymerization of EDOT in the ionic liquid can be probed on the nanoscale. In contrast to present understanding, it was observed that the EDOT can be oxidised in ionic liquids well below its oxidation potential and the under potential growth of polymer was visualized by in situSTM. These results serve as the first study to confirm the under potential growth of conducting polymers in ionic liquids. Furthermore, ex situmicroscopy measurements were performed. Quite a high current of 670 nA was observed on the nanoscale by conductive scanning force microscopy (CSFM).The electropolymerization of 3,4-ethylenedioxythiophene (EDOT) to poly(3,4-ethylenedioxythiophene) (PEDOT) was investigated in the air and water-stable ionic liquids 1-hexyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate [HMIm]FAP and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide [EMIm]TFSA. In situscanning tunnelling microscopy (STM) results show that the electropolymerization of EDOT in the ionic liquid can be probed on the nanoscale. In contrast to present understanding, it was observed that the EDOT can be oxidised in ionic liquids well below its oxidation potential and the under potential growth of polymer was visualized by in situSTM. These results serve as the first study to confirm the under potential growth of conducting polymers in ionic liquids. Furthermore, ex situmicroscopy measurements were performed. Quite a high current of 670 nA was observed on the nanoscale by conductive scanning force microscopy (CSFM). Electronic supplementary information (ESI) available: In situ image of PEDOT in [HMIm]FAP and in situ studies of PEDOT grown in [EMIm]TFSA and redox behavior of PEDOT. See DOI: 10.1039/c0nr00579g

Fabrication of fiber supported ionic liquids and methods of use

DOEpatents

Luebke, David R; Wickramanayake, Shan

2013-02-26

One or more embodiments relates to the production of a fabricated fiber having an asymmetric polymer network and having an immobilized liquid such as an ionic liquid within the pores of the polymer network. The process produces the fabricated fiber in a dry-wet spinning process using a homogenous dope solution, providing significant advantage over current fabrication methods for liquid-supporting polymers. The fabricated fibers may be effectively utilized for the separation of a chemical species from a mixture based on the selection of the polymer, the liquid, and the solvent utilized in the dope.

Sulfonated Copper Phthalocyanine/Sulfonated Polysulfone Composite Membrane for Ionic Polymer Actuators with High Power Density and Fast Response Time.

PubMed

Kwon, Taehoon; Cho, Hyeongrae; Lee, Jang-Woo; Henkensmeier, Dirk; Kang, Youngjong; Koo, Chong Min

2017-08-30

Ionic polymer composite membranes based on sulfonated poly(arylene ether sulfone) (SPAES) and copper(II) phthalocyanine tetrasulfonic acid (CuPCSA) are assembled into bending ionic polymer actuators. CuPCSA is an organic filler with very high sulfonation degree (IEC = 4.5 mmol H + /g) that can be homogeneously dispersed on the molecular scale into the SPAES membrane, probably due to its good dispersibility in SPAES-containing solutions. SPAES/CuPCSA actuators exhibit larger ion conductivity (102 mS cm -1 ), tensile modulus (208 MPa), strength (101 MPa), and strain (1.21%), exceptionally faster response to electrical stimuli, and larger mechanical power density (3028 W m -3 ) than ever reported for ion-conducting polymer actuators. This outstanding actuation performance of SPAES/CuPCSA composite membrane actuators makes them attractive for next-generation transducers with high power density, which are currently developed, e.g., for underwater propulsion and endoscopic surgery.

Dynamics of water in sulfonated poly(phenylene) membranes

NASA Astrophysics Data System (ADS)

Osti, Naresh; Etampawala, Thusitha; Shrestha, Umesh; Perahia, Dvora; Cornelius, Christopher

2011-03-01

The dynamics of water in networks formed by highly rigid ionic polymers, sulfonated poly(phenylene) as observed by quasi elastic neutron scattering (QENS) is presented. These rigid ionic polymers have potential as effective ion exchange membranes with impact on a large number of applications from water purification to clean energy, where its rigidity distinguishes it from other ionic polymers. Its transport characteristics are affected by its rigidness as well as by direct interactions with the solvent. Our QENS studies as a function of sulfonation levels, temperature and solvent content have shown that on the time scale of the measurement, the polymers are rigid. While macroscopically all samples swell, and transport water, the water molecules appear locally rather confined. Water however remind non-frozen to subzero temperatures. The results will be discussed in view of theoretical models including continues diffusion and hopping of solvent molecules.

Exploring pH-Sensitive Hydrogels Using an Ionic Soft Contact Lens: An Activity Using Common Household Materials

ERIC Educational Resources Information Center

Chen, Yueh-Huey; He, Yu-Chi; Yaung, Jing-Fun

2014-01-01

Hydrogels of the so-called smart polymers or environment-sensitive polymers are important modern biomaterials. Herein, we describe a hands-on activity to explore the pH-responsive characteristics of hydrogels using a commercially available ionic soft contact lens that is a hydrogel of poly(2-hydroxyethyl methacrylate-"co"-methacrylic…

Water dynamics in rigid ionomer networks.

PubMed

Osti, N C; Etampawala, T N; Shrestha, U M; Aryal, D; Tyagi, M; Diallo, S O; Mamontov, E; Cornelius, C J; Perahia, D

2016-12-14

The dynamics of water within ionic polymer networks formed by sulfonated poly(phenylene) (SPP), as revealed by quasi-elastic neutron scattering (QENS), is presented. These polymers are distinguished from other ionic macromolecules by their rigidity and therefore in their network structure. QENS measurements as a function of temperature as the fraction of ionic groups and humidity were varied have shown that the polymer molecules are immobile while absorbed water molecules remain dynamic. The water molecules occupy multiple sites, either bound or loosely constrained, and bounce between the two. With increasing temperature and hydration levels, the system becomes more dynamic. Water molecules remain mobile even at subzero temperatures, illustrating the applicability of the SPP membrane for selective transport over a broad temperature range.

High-flux ionic diodes, ionic transistors and ionic amplifiers based on external ion concentration polarization by an ion exchange membrane: a new scalable ionic circuit platform†

PubMed Central

Sun, Gongchen; Senapati, Satyajyoti

2016-01-01

A microfluidic-ion exchange membrane hybrid chip is fabricated by polymer-based, lithography-free methods to achieve ionic diode, transistor and amplifier functionalities with the same four-terminal design. The high ionic flux (> 100 μA) feature of the chip can enable a scalable integrated ionic circuit platform for micro-total-analytical systems. PMID:26960551

High elastic modulus polymer electrolytes

DOEpatents

Balsara, Nitash Pervez; Singh, Mohit; Eitouni, Hany Basam; Gomez, Enrique Daniel

2013-10-22

A polymer that combines high ionic conductivity with the structural properties required for Li electrode stability is useful as a solid phase electrolyte for high energy density, high cycle life batteries that do not suffer from failures due to side reactions and dendrite growth on the Li electrodes, and other potential applications. The polymer electrolyte includes a linear block copolymer having a conductive linear polymer block with a molecular weight of at least 5000 Daltons, a structural linear polymer block with an elastic modulus in excess of 1.times.10.sup.7 Pa and an ionic conductivity of at least 1.times.10.sup.-5 Scm.sup.-1. The electrolyte is made under dry conditions to achieve the noted characteristics.

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

PubMed

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

2015-06-01

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

Property enchancement of polyimide films by way of the incorporation of lanthanide metal ions

NASA Technical Reports Server (NTRS)

Thompson, David W.

1993-01-01

Lanthanide metal ions were incorporated into the polyimide derived from 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 1,3-bis(aminophenoxy) benzene (APB) in an attempt to produce molecular level metal-polymer composites. The lanthanide series of metal ions (including aluminum, scandium, and yttrium) provide discrete and stable metal ions in the 3+ oxidation state. Throughout the series there is a uniform variation in ionic size ranging from 50 pm for aluminum to a maximum of 103.4 pm for cerium and gradually decreasing again to 84.8 pm for lutetium. The high charge-to-size ratio for these ions as well as the ability to obtain large coordination numbers makes them excellent candidates for interacting with the polymer substructure. The distinct lack of solubility of simple lanthanide salts such as the acetates and halides has made it difficult to obtain metal ions distributed in the polymer framework as discrete ions or metal complexes rather than microcomposites of metal clusters. (Lanthanum nitrates are quite soluble, but the presence of the strongly oxidizing nitrate ion leads to serious degradation of the polymer upon thermal curing. This work was successful at extending the range of soluble metals salts by using chelating agents derived from the beta-diketones dipivaloylmethane, dibenzoylmethane, trifluoroacetylacetone, and hexafluoroacetylacetone. Metal acetates which are insoluble in dimethylacetamide dissolve readily in the presence of the diketones. Addition of the polyimide yields a homogeneous resin which is then cast into a clear film. Upon curing clear films were obtained with the dibenzoylmethane and trifluoroacetylacetone ligands. The dipavaloylmethane precipitates the metal during the film casting process, and hexafluoroacetylacetone gives cured films which are deformed and brittle. These clear films are being evaluated for the effect of the metal ions on the coefficient of thermal expansion, resistance to atomic oxygen, and on selective gas permeability. Much more commonly than above, polyimide films are prepared by casting the film as the poly(amic acid) precursor which is then converted to the imidized form during the thermal cure cycle. Very limited success was achieved in the past in adding lanthanide metal ions to the amide precursors because of gellation and lack of solubility. With the use of the diketone ligands cited above, the solubility and gellation problems were overcome. However, the films after curing were clear but unacceptably brittle. Attempts to overcome this cure embrittlement problem are in progress.

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

NASA Astrophysics Data System (ADS)

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.

Quantification of amino acids and peptides in an ionic liquid based aqueous two-phase system by LC-MS analysis.

PubMed

Oppermann, Sebastian; Oppermann, Christina; Böhm, Miriam; Kühl, Toni; Imhof, Diana; Kragl, Udo

2018-04-25

Aqueous two-phase systems (ATPS) occur by the mixture of two polymers or a polymer and an inorganic salt in water. It was shown that not only polymers but also ionic liquids in combination with inorganic cosmotrophic salts are able to build ATPS. Suitable for the formation of ionic liquid-based ATPS systems are hydrophilic water miscible ionic liquids. To understand the driving force for amino acid and peptide distribution in IL-ATPS at different pH values, the ionic liquid Ammoeng 110™ and K 2 HPO 4 have been chosen as a test system. To quantify the concentration of amino acids and peptides in the different phases, liquid chromatography and mass spectrometry (LC-MS) technologies were used. Therefore the peptides and amino acids have been processed with EZ:faast™-Kit from Phenomenex for an easy and reliable quantification method even in complex sample matrices. Partitioning is a surface-dependent phenomenon, investigations were focused on surface-related amino acid respectively peptide properties such as charge and hydrophobicity. Only a very low dependence between the amino acids or peptides hydrophobicity and the partition coefficient was found. Nevertheless, the presented results show that electrostatic respectively ionic interactions between the ionic liquid and the amino acids or peptides have a strong impact on their partitioning behavior.

Rechargeable aluminum batteries with conducting polymers as positive electrodes

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

Hudak, Nicholas S.

2013-12-01

This report is a summary of research results from an Early Career LDRD project con-ducted from January 2012 to December 2013 at Sandia National Laboratories. Demonstrated here is the use of conducting polymers as active materials in the posi-tive electrodes of rechargeable aluminum-based batteries operating at room tempera-ture. The battery chemistry is based on chloroaluminate ionic liquid electrolytes, which allow reversible stripping and plating of aluminum metal at the negative elec-trode. Characterization of electrochemically synthesized polypyrrole films revealed doping of the polymers with chloroaluminate anions, which is a quasi-reversible reac-tion that facilitates battery cycling. Stable galvanostatic cycling of polypyrrole andmore » polythiophene cells was demonstrated, with capacities at near-theoretical levels (30-100 mAh g -1) and coulombic efficiencies approaching 100%. The energy density of a sealed sandwich-type cell with polythiophene at the positive electrode was estimated as 44 Wh kg -1, which is competitive with state-of-the-art battery chemistries for grid-scale energy storage.« less

An empirical study into the effect of long term storage (-36±2 °C) of electron-beamed ETFE on the properties of radiation-grafted alkaline anion-exchange membranes

NASA Astrophysics Data System (ADS)

Kizewski, Jamie Peter; Mudri, Nurul H.; Varcoe, John R.

2013-08-01

The application of alkaline anion-exchange membranes (AAEM) in solid alkaline fuel cells is growing in prominence mainly due to enhanced tolerance to carbon dioxide, compared to alkaline fuel cells containing aqueous electrolytes, and the potential for using non precious metal catalysts. Radiation grafting is a common methodology for the production of functional polymers and membranes. This statistical study examines the synthesis of radiation grafted AAEMs that are formed from electron beam irradiated poly(ethylene-co-tetrafluoroethylene), EB-ETFE. It is shown that EB-ETFE can be cold stored for at least 16 months and still be used to produce ionically conductive AAEMs. The limitations of routine measurements of properties, such as dimensional increases, ion-exchange capacity, water uptakes and ionic conductivities, are also highlighted.

Applications of Ionic Liquids for the Development of Optical Chemical Sensors and Biosensors.

PubMed

Muginova, Svetlana V; Myasnikova, Dina A; Kazarian, Sergei G; Shekhovtsova, Tatiana N

2017-01-01

This paper reviews the primary literature reporting the use of ionic liquids (ILs) in optical sensing technologies. The optical chemical sensors that have been developed with the assistance of ILs are classified according to the type of resultant material. Key aspects of applying ILs in such sensors are revealed and discussed. They include using ILs as solvents for the synthesis of sensor matrix materials; additives in polymer matrices; matrix materials; modifiers of the surfaces; and multifunctional sensor components. The operational principles, design, texture, and analytical characteristics of the offered sensors for determining CO 2 , O 2 , metal ions, CN - , and various organic compounds are critically discussed. The key advantages and disadvantages of using ILs in optical sensing technologies are defined. Finally, the applicability of the described materials for chemical analysis is evaluated, and possibilities for their further modernization are outlined.

Interplay of Transport and Morphology in Nanostructured Ion-Containing Polymers

NASA Astrophysics Data System (ADS)

Park, Moon Jeong

The global energy crisis and an increase in environmental pollution in the recent years have drawn the attention of the scientific community to develop innovative ways to improve energy storage and find more efficient methods of transporting the energy. Polymers containing charged species that show high ionic conductivity and good mechanical integrity are the essential components of these energy storage and transport systems. In this talk, first, I will present a fundamental understanding of the thermodynamics and transport in ion-containing block copolymers with a focus on the structure-property relationships. Tailoring the intermolecular interactions between the polymer matrix and the embedded charges appeared to be vital for controlling the transport properties. Particularly, the achievement of well-defined self-assembled morphologies with three-dimensional symmetries has proven to facilitate fast ion transport by constructing less tortuous ion-conducting pathways. Examples of attained morphologies include disorder, lamellae, gyroid, Fddd, hexagonal cylinder, body-centered cubic, face-centered cubic, and A15 phases. Second, various strategies for accessing high cation transference number as well as improved ionic conductivity from ionic-containing polymers are enclosed; (1) the inclusion of terminal ionic units as a new means to control the nanoscale morphologies and the transport efficiency of block copolymer electrolytes and (2) the addition of zwitterions that offered a polar medium close to water, and accordingly increased the charge density and ionic conductivity. The obtained knowledge on polymer electrolytes could be used in a wide range of emerging nanotechnologies such as fuel cells, lithium batteries, and electro-active actuators.

High performance photolithographically-patterned polymer thin-film transistors gated with an ionic liquid/poly(ionic liquid) blend ion gel

NASA Astrophysics Data System (ADS)

Thiburce, Q.; Porcarelli, L.; Mecerreyes, D.; Campbell, A. J.

2017-06-01

We demonstrate the fabrication of polymer thin-film transistors gated with an ion gel electrolyte made of the blend of an ionic liquid and a polymerised ionic liquid. The ion gel exhibits a high stability and ionic conductivity, combined with facile processing by simple drop-casting from solution. In order to avoid parasitic effects such as high hysteresis, high off-currents, and slow switching, a fluorinated photoresist is employed in order to enable high-resolution orthogonal patterning of the polymer semiconductor over an area that precisely defines the transistor channel. The resulting devices exhibit excellent characteristics, with an on/off ratio of 106, low hysteresis, and a very large transconductance of 3 mS. We show that this high transconductance value is mostly the result of ions penetrating the polymer film and doping the entire volume of the semiconductor, yielding an effective capacitance per unit area of about 200 μF cm-2, one order of magnitude higher than the double layer capacitance of the ion gel. This results in channel currents larger than 1 mA at an applied gate bias of only -1 V. We also investigate the dynamic performance of the devices and obtain a switching time of 20 ms, which is mostly limited by the overlap capacitance between the ion gel and the source and drain contacts.

Ion Conduction in Polymerized Ionic Liquids with Different Pendant Groups

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

Fan, Fei; Wang, Yangyang; Hong, Tao

2015-07-17

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

An Electrochemical NO2 Sensor Based on Ionic Liquid: Influence of the Morphology of the Polymer Electrolyte on Sensor Sensitivity

PubMed Central

Kuberský, Petr; Altšmíd, Jakub; Hamáček, Aleš; Nešpůrek, Stanislav; Zmeškal, Oldřich

2015-01-01

A systematic study was carried out to investigate the effect of ionic liquid in solid polymer electrolyte (SPE) and its layer morphology on the characteristics of an electrochemical amperometric nitrogen dioxide sensor. Five different ionic liquids were immobilized into a solid polymer electrolyte and key sensor parameters (sensitivity, response/recovery times, hysteresis and limit of detection) were characterized. The study revealed that the sensor based on 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][N(Tf)2]) showed the best sensitivity, fast response/recovery times, and low sensor response hysteresis. The working electrode, deposited from water-based carbon nanotube ink, was prepared by aerosol-jet printing technology. It was observed that the thermal treatment and crystallinity of poly(vinylidene fluoride) (PVDF) in the solid polymer electrolyte influenced the sensitivity. Picture analysis of the morphology of the SPE layer based on [EMIM][N(Tf)2] ionic liquid treated under different conditions suggests that the sensor sensitivity strongly depends on the fractal dimension of PVDF spherical objects in SPE. Their deformation, e.g., due to crowding, leads to a decrease in sensor sensitivity. PMID:26569248

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

PubMed

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

2011-06-28

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

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

PubMed

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.

Comparison of the influence of polyaspartic acid and polylysine functional groups on the adsorption at the Cr2O3-Aqueous polymer solution interface

NASA Astrophysics Data System (ADS)

Ostolska, Iwona; Wiśniewska, Małgorzata

2014-08-01

Polyamino acids are a group of synthesized polymers obtained by polymerization of a given kind of amino acid monomer. Because of high biodegradability of this class of polymers, they can be used as flocculation or stabilization agents in the environmental aspects. Therefore determination of their influence on the stability of the aqueous suspension of metal oxides is important. An influence of different functional groups of polyamino acids, their molecular weight and concentration on the adsorption at the chromium (III) oxide (Cr2O3)-aqueous solution interface was determined. Experiments were carried out for four values of solution pH varying from 3 to 10 (3, 4, 7.6 and 10, respectively). Two polymers were used: anionic polyaspartic acid (ASP) of 6800 and 27,000 as well as polylysine (LYS) of 4900 and 33,000 molecular weights. Changes of surface charge density of colloidal Cr2O3 in the presence and in the absence of macromolecular substances were determined using potentiometric titration. In these studies the influence of the concentration and molecular weight of the ionic polymers on the pHpzc value was determined. Additionally, due to the lack of appropriate literature data, potentiometric titration of the selected polymers was performed to determine pKa values.

Nanostructure enhanced ionic transport in fullerene reinforced solid polymer electrolytes.

PubMed

Sun, Che-Nan; Zawodzinski, Thomas A; Tenhaeff, Wyatt E; Ren, Fei; Keum, Jong Kahk; Bi, Sheng; Li, Dawen; Ahn, Suk-Kyun; Hong, Kunlun; Rondinone, Adam J; Carrillo, Jan-Michael Y; Do, Changwoo; Sumpter, Bobby G; Chen, Jihua

2015-03-28

Solid polymer electrolytes, such as polyethylene oxide (PEO) based systems, have the potential to replace liquid electrolytes in secondary lithium batteries with flexible, safe, and mechanically robust designs. Previously reported PEO nanocomposite electrolytes routinely use metal oxide nanoparticles that are often 5-10 nm in diameter or larger. The mechanism of those oxide particle-based polymer nanocomposite electrolytes is under debate and the ion transport performance of these systems is still to be improved. Herein we report a 6-fold ion conductivity enhancement in PEO/lithium bis(trifluoromethanesulfonyl) imide (LiTFSI)-based solid electrolytes upon the addition of fullerene derivatives. The observed conductivity improvement correlates with nanometer-scale fullerene crystallite formation, reduced crystallinities of both the (PEO)6:LiTFSI phase and pure PEO, as well as a significantly larger PEO free volume. This improved performance is further interpreted by enhanced decoupling between ion transport and polymer segmental motion, as well as optimized permittivity and conductivity in bulk and grain boundaries. This study suggests that nanoparticle induced morphological changes, in a system with fullerene nanoparticles and no Lewis acidic sites, play critical roles in their ion conductivity enhancement. The marriage of fullerene derivatives and solid polymer electrolytes opens up significant opportunities in designing next-generation solid polymer electrolytes with improved performance.

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

NASA Astrophysics Data System (ADS)

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.

Enhanced proton transport in nanostructured polymer electrolyte/ionic liquid membranes under water-free conditions.

PubMed

Kim, Sung Yeon; Kim, Suhan; Park, Moon Jeong

2010-10-05

Proton exchange fuel cells (PEFCs) have the potential to provide power for a variety of applications ranging from electronic devices to transportation vehicles. A major challenge towards economically viable PEFCs is finding an electrolyte that is both durable and easily passes protons. In this article, we study novel anhydrous proton-conducting membranes, formed by incorporating ionic liquids into synthetic block co-polymer electrolytes, poly(styrenesulphonate-b-methylbutylene) (S(n)MB(m)), as high-temperature PEFCs. The resulting membranes are transparent, flexible and thermally stable up to 180 °C. The increases in the sulphonation level of S(n)MB(m) co-polymers (proton supplier) and the concentration of the ionic liquid (proton mediator) produce an overall increase in conductivity. Morphology effects were studied by X-ray scattering and electron microscopy. Compared with membranes having discrete ionic domains (including Nafion 117), the nanostructured membranes revealed over an order of magnitude increase in conductivity with the highest conductivity of 0.045 S cm(-1) obtained at 165 °C.

TiO2 as conductivity enhancer in PVdF-HFP polymer electrolyte system

NASA Astrophysics Data System (ADS)

Bhattacharya, Shreya; Manojkumar Ubarhande, Radha; Usha Rani, M.; Shanker Babu, Ravi; Arunkumar, R.

2017-11-01

Composite polymer electrolytes were prepared by incorporating inorganic filler TiO2 into PVdF-HFP-PMMA-EC-LiClO4 system. The electrolyte films were prepared by solvent casting technique. The effect of inorganic filler on the conductivity of the blended polymer electrolyte was studied and it is found that there is a considerable increase in ionic conductivity 1.296 × 10-3 S/cm-1 on the addition of TiO2. X-ray diffraction (XRD) study elucidate the increase in amorphous nature of the polymer electrolyte. This tendency of the polymer electrolyte could be the reason behind the increase in ionic conductivity. Fourier transform infrared spectroscopy (FTIR) spectra show the occurrence of complexation and interaction among the components.

LASER APPLICATIONS AND OTHER TOPICS IN QUANTUM ELECTRONICS: Holographic sensors for diagnostics of solution components

NASA Astrophysics Data System (ADS)

Kraiskii, A. V.; Postnikov, V. A.; Suitanov, T. T.; Khamidulin, A. V.

2010-02-01

The properties of holographic sensors of two types are studied. The sensors are based on a three-dimensional polymer-network matrix of copolymers of acrylamide, acrylic acid (which are sensitive to the medium acidity and bivalent metal ions) and aminophenylboronic acid (sensitive to glucose). It is found that a change in the ionic composition of a solution results in changes in the distance between layers and in the diffraction efficiency of holograms. Variations in the shape of spectral lines, which are attributed to the inhomogeneity of a sensitive layer, and nonmonotonic changes in the emulsion thickness and diffraction efficiency were observed during transient processes. The composition of the components of a hydrogel medium is selected for systems which can be used as a base for glucose sensors with the mean holographic response in the region of physiological glucose concentration in model solutions achieving 40 nm/(mmol L-1). It is shown that the developed holographic sensors can be used for the visual and instrumental determination of the medium acidity, alcohol content, ionic strength, bivalent metal salts and the quality of water, in particular, for drinking.

Dielectric relaxation dynamics and AC conductivity scaling of metal-organic framework (MOF-5) based polymer electrolyte nanocomposites incorporated with ionic liquid

NASA Astrophysics Data System (ADS)

Dutta, Rituraj; Kumar, A.

2017-10-01

Dielectric relaxation dynamics and AC conductivity scaling of a metal-organic framework (MOF-5) based poly (vinylidene fluoride-co-hexafluoropropylene) (PVdf-HFP) incorporated with 1-Butyl-3-methylimidazolium hexafluorophosphate have been studied over a frequency range of 40 Hz-5 MHz and in the temperature range of 300 K-380 K. High values of dielectric permittivity (~{{\\varepsilon }\\prime} ) having strong dispersion are obtained at low frequency because of interfacial polarization. The real part of the dielectric modulus spectra (M‧) shows no prominent peak, whereas the imaginary part (M″) shows certain peaks, with a reduction in relaxation time (τ) that can be attributed to a non-Debye relaxation mechanism. The spectra also depict both concentration- and temperature-independent scaling behavior. The power law dependent variation of AC conductivity follows the jump relaxation model and reveals activated ion hopping over diffusion barriers. The value of the frequency exponent is observed to decrease with increasing concentration of ionic liquid, indicating the forward hopping of ions in the relaxation process. The AC conductivity scaling curves at different temperatures also depict the temperature-independent relaxation dynamics.

"Washing-out" ionic liquids from polyethylene glycol to form aqueous biphasic systems.

PubMed

Tomé, Luciana I N; Pereira, Jorge F B; Rogers, Robin D; Freire, Mara G; Gomes, José R B; Coutinho, João A P

2014-02-14

The molecular-level mechanisms behind the formation of aqueous biphasic systems (ABS) composed of ionic liquids (ILs) and polymers are hitherto not completely understood. For the first time, it is herein shown that polymer-IL-based ABS are a result of a "washing-out" phenomenon, and not of a salting-out effect of the IL over the polymer as assumed in the past few years. Novel evidence is herein provided by experimental results combined with molecular dynamics (MD) simulations and density functional theory (DFT) calculations.

Application of Ionic Liquids in Hydrometallurgy

PubMed Central

Park, Jesik; Jung, Yeojin; Kusumah, Priyandi; Lee, Jinyoung; Kwon, Kyungjung; Lee, Churl Kyoung

2014-01-01

Ionic liquids, low temperature molten salts, have various advantages manifesting themselves as durable and environmentally friendly solvents. Their application is expanding into various fields including hydrometallurgy due to their unique properties such as non-volatility, inflammability, low toxicity, good ionic conductivity, and wide electrochemical potential window. This paper reviews previous literatures and our recent results adopting ionic liquids in extraction, synthesis and processing of metals with an emphasis on the electrolysis of active/light, rare earth, and platinum group metals. Because the research and development of ionic liquids in this area are still emerging, various, more fundamental approaches are expected to popularize ionic liquids in the metal manufacturing industry. PMID:25177864

Ultra-high-rate pseudocapacitive energy storage in two-dimensional transition metal carbides

NASA Astrophysics Data System (ADS)

Lukatskaya, Maria R.; Kota, Sankalp; Lin, Zifeng; Zhao, Meng-Qiang; Shpigel, Netanel; Levi, Mikhael D.; Halim, Joseph; Taberna, Pierre-Louis; Barsoum, Michel W.; Simon, Patrice; Gogotsi, Yury

2017-08-01

The use of fast surface redox storage (pseudocapacitive) mechanisms can enable devices that store much more energy than electrical double-layer capacitors (EDLCs) and, unlike batteries, can do so quite rapidly. Yet, few pseudocapacitive transition metal oxides can provide a high power capability due to their low intrinsic electronic and ionic conductivity. Here we demonstrate that two-dimensional transition metal carbides (MXenes) can operate at rates exceeding those of conventional EDLCs, but still provide higher volumetric and areal capacitance than carbon, electrically conducting polymers or transition metal oxides. We applied two distinct designs for MXene electrode architectures with improved ion accessibility to redox-active sites. A macroporous Ti3C2Tx MXene film delivered up to 210 F g-1 at scan rates of 10 V s-1, surpassing the best carbon supercapacitors known. In contrast, we show that MXene hydrogels are able to deliver volumetric capacitance of ˜1,500 F cm-3 reaching the previously unmatched volumetric performance of RuO2.

Role of salt concentration in blend polymer for energy storage conversion devices

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

Arya, Anil; Sharma, A. L., E-mail: alsharmaiitkgp@gmail.com; Sadiq, M.

2016-05-06

Solid Polymer Electrolytes (SPE) are materials of considerable interest worldwide, which serves dual purpose of electrolyte and separator between electrode compartments in renewable energy conversion/storage devices such as; high energy density batteries, electrochromic display devices, and supercapacitors. Polymer blend electrolytes are prepared for various concentration of salt (Ö/Li) with the constant ratio (0.5 gm) of each PEO and PAN polymers (blend polymer) using solution casting technique. Solid polymeric ionic conductor as a separator is the ultimate substitute to eliminate the drawback related to liquid and gel polymer ionic conductors. In the present work, solid polymer electrolyte film consisting of PEO,more » PAN and LiPF{sub 6} are examined for various concentration of lithium salt by keeping PEO/PAN blend ratio as a constant with a view to optimize the dominant salt concentration which could give the maximum conductivity at ambient temperature.« less

Electrochemical and structural characterization of polymer gel electrolytes based on a PEO copolymer and an imidazolium-based ionic liquid for dye-sensitized solar cells.

PubMed

Freitas, Flavio S; de Freitas, Jilian N; Ito, Bruno I; De Paoli, Marco-A; Nogueira, Ana F

2009-12-01

Polymer electrolytes based on mixtures of poly(ethylene oxide-co-propylene oxide) and 1-methyl-3-propyl-imidazolium iodide (MPII) were investigated, aiming at their application in dye-sensitized solar cells (DSSC). The interactions between the copolymer and the ionic liquid were analyzed by infrared spectroscopy and (1)H NMR. The results show interactions between the ether oxygen in the polymer and the hydrogen in the imidazolium cations. The ionic conductivities, electrochemical behaviors, and thermal properties of the electrolytes containing different concentrations of MPII were investigated. The electrolyte containing 70 wt % MPII presented the highest ionic conductivity (2.4 x 10(-3) S cm(-1)) and a diffusion coefficient of 1.9 x 10(-7) cm(2) s(-1). The influence of LiI addition to the electrolytes containing different concentrations of MPII was also investigated. The DSSC assembled with the electrolyte containing 70 wt % MPII showed an efficiency of 3.84% at 100 mW cm(-2). The stability of the devices for a period of 30 days was also evaluated using sealed cells. The devices assembled with the electrolyte containing less ionic liquid showed to be more stable.

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

Leng, X.; Pereiro, J.; Strle, J.

Tungsten oxide and its associated bronzes (compounds of tungsten oxide and an alkali metal) are well known for their interesting optical and electrical characteristics. We have modified the transport properties of thin WO 3 films by electrolyte gating using both ionic liquids and polymer electrolytes. We are able to tune the resistivity of the gated film by more than five orders of magnitude, and a clear insulator-to-metal transition is observed. To clarify the doping mechanism, we have performed a series of incisive operando experiments, ruling out both a purely electronic effect (charge accumulation near the interface) and oxygen-related mechanisms. Wemore » propose instead that hydrogen intercalation is responsible for doping WO 3 into a highly conductive ground state and provide evidence that it can be described as a dense polaronic gas.« less

Advances in sensing and biosensing of bisphenols: A review.

PubMed

Dhanjai; Sinha, Ankita; Wu, Lingxia; Lu, Xianbo; Chen, Jiping; Jain, Rajeev

2018-01-15

Bisphenols (BPs) are well known endocrine disrupting chemicals (EDCs) that cause adverse effects on the environment, biotic life and human health. BPs have been studied extensively because of an increasing concern for the safety of the environment and for human health. They are major raw materials for manufacturing polycarbonates, thermal papers and epoxy resins and are considered hazardous environmental contaminants. A vast array of sensors and biosensors have been developed for the sensitive screening of BPs based on carbon nanomaterials (carbon nanotubes, fullerenes, graphene and graphene oxide), quantum dots, metal and metal oxide nanocomposites, polymer nanocomposites, metal organic frameworks, ionic liquids and molecularly imprinted polymers. This review is devoted mainly to a variety of sensitive, selective and reliable sensing and biosensing methods for the detection of BPs using electrochemistry, fluorescence, colorimetry, surface plasmon resonance, luminescence, ELISAs, circular dichroism, resonance Rayleigh scattering and adsorption techniques in plastic products, food samples, food packaging, industrial wastes, pharmaceutical products, human body fluids and many other matrices. It summarizes the advances in sensing and biosensing methods for the detection of BPs since 2010. Furthermore, the article discusses challenges and future perspectives in the development of novel sensing methods for the detection of BP analogs. Copyright © 2017 Elsevier B.V. All rights reserved.

Soft nanoparticles: nano ionic networks of associated ionic polymers

DOE PAGES

Aryal, Dipak; Grest, Gary S.; Perahia, Dvora

2017-01-01

Directing the formation of nanostructures that serve as building blocks of membranes presents an immense step towards engineering controlled polymeric ion transport systems. Here, using the exquisite atomic detail captured by molecular dynamics simulations, we follow the assembly of a co-polymer that consists of polystyrene sulfonate tethered symmetrically to hydrophobic blocks, realizing a new type of long lived solvent-responsive soft nanoparticle.

Final Report for DE-FG02-93ER14376,Ionic Transport in Electrochemical Media

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

J. W. Halley

This project was a molecular dynamics study of the relevant issues associated with the structure and transport of lithium in polymer electrolytes such as polyethylene oxide(PEO). In close collaboration with quantum chemist Larry Curtiss and neutron scatterers David Lee Price and Marie-Louise Saboungi at Argonne, we used molecular dynamics to study the local structure and dynamics and ion transport in the polymer. The studies elucidated the mechanism of Li transport in PEO, revealing that the rate limiting step is extremely sensitive to the magnitude of the torsion forces in the backbone of the polymer. Because the torsion forces are difficultmore » to manipulate chemically, this makes it easier to understand why improving the conductivity of PEO based electrolytes has proven to be very difficult. We studied the transport properties of cations in ionic liquids as possible additives to polymer membranes for batteries and fuel cells and found preliminary indications that the transport is enhanced near phase separation in acid-ionic liquid mixtures.« less

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

PubMed

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

2014-10-08

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.

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

PubMed Central

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

Non-crosslinked, amorphous, block copolymer electrolyte for batteries

DOEpatents

Mayes, Anne M.; Ceder, Gerbrand; Chiang, Yet-Ming; Sadoway, Donald R.; Aydinol, Mehmet K.; Soo, Philip P.; Jang, Young-Il; Huang, Biying

2006-04-11

Solid battery components are provided. A block copolymeric electrolyte is non-crosslinked and non-glassy through the entire range of typical battery service temperatures, that is, through the entire range of at least from about 0.degree. C. to about 70.degree. C. The chains of which the copolymer is made each include at least one ionically-conductive block and at least one second block immiscible with the ionically-conductive block. The chains form an amorphous association and are arranged in an ordered nanostructure including a continuous matrix of amorphous ionically-conductive domains and amorphous second domains that are immiscible with the ionically-conductive domains. A compound is provided that has a formula of Li.sub.xM.sub.yN.sub.zO.sub.2. M and N are each metal atoms or a main group elements, and x, y and z are each numbers from about 0 to about 1. y and z are chosen such that a formal charge on the M.sub.yN.sub.z portion of the compound is (4-x). In certain embodiments, these compounds are used in the cathodes of rechargeable batteries. The present invention also includes methods of predicting the potential utility of metal dichalgogenide compounds for use in lithium intercalation compounds. It also provides methods for processing lithium intercalation oxides with the structure and compositional homogeneity necessary to realize the increased formation energies of said compounds. An article is made of a dimensionally-stable, interpenetrating microstructure of a first phase including a first component and a second phase, immiscible with the first phase, including a second component. The first and second phases define interphase boundaries between them, and at least one particle is positioned between a first phase and a second phase at an interphase boundary. When the first and second phases are electronically-conductive and ionically-conductive polymers, respectively, and the particles are ion host particles, the arrangement is an electrode of a battery.

Composite fabrication and polymer modification using neoteric solvents

NASA Astrophysics Data System (ADS)

Eastman, Scott A.

This thesis is divided into two research initiatives: The fabrication and study of bulk, co-continuous, cellulosic-polymer composites with the aid of supercritical CO2 (SC CO2); and the study of poly(vinyl alcohol) (PVOH) modification and surface activity in ionic liquids. The first part of this thesis utilizes the tunable solubility, gas-like diffusivity, and omniphilic wettability of SC CO2 to incorporate and subsequently polymerize silicone and poly(enemer) prepolymer mixtures throughout various cellulosic substrates. Chapters two and three investigate the mechanical properties of these composites and demonstrate that nearly every resulting composite demonstrates an improved flexural modulus and energy release rate upon splitting. Fire resistance of these composites was also investigated and indicates that the heat release rate, total heat released, and char yield were significantly improved upon for all silicone composites compared to the untreated cellulosic material. Chapter four looks specifically at aspen-silicone composites for thermo-oxidative studies under applied loads in order to study the effect of silicone incorporation on the failure kinetics of aspen. The aspen-silicone composites tested under these conditions demonstrated significantly longer lifetimes under the same loading and heating conditions compared with untreated aspen. The second part of this thesis focuses on studying ionic liquids as potentially useful solvents and reaction media for poly(vinyl alcohol). Two ionic liquids (1-Butyl-3-methylimidizolium chloride and tributylethylphosphonium diethylphosphate) were found to readily dissolve PVOH. More importantly, we have demonstrated that these solvents can be used as inert reaction media for PVOH modification. Both ionic liquids were found to facilitate the quantitative esterification of PVOH, while only the phosphonium ionic liquid supports the quantitative urethanation of the polymer. In an attempt to tune the surface properties of ionic liquid/polymer solutions, PVOH was also partially esterified with low surface energy substituents. Both surface tension and surface composition of the ionic liquid/polymer solutions can be manipulated by the stoichiometric addition of low surface energy acid chlorides. This work on the modification of PVOH can be directly applied to the modification of polysaccharides such as cellulose which could have important implications from a sustainability and energy standpoint.

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

PubMed

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

2017-08-01

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

Simulation study of the lithium ion transport mechanism in ternary polymer electrolytes: the critical role of the segmental mobility.

PubMed

Diddens, Diddo; Heuer, Andreas

2014-01-30

We present an extensive molecular dynamics (MD) simulation study of the lithium ion transport in ternary polymer electrolytes consisting of poly(ethylene oxide) (PEO), lithium-bis(trifluoromethane)sulfonimide (LiTFSI), and the ionic liquid N-methyl-N-propylpyrrolidinium bis(trifluoromethane)sulfonimide (PYR13TFSI). In particular, we focus on two different strategies by which the ternary electrolytes can be devised, namely by (a) adding the ionic liquid to PEO20LiTFSI and (b) substituting the PEO chains in PEO20LiTFSI by the ionic liquid. To grasp the changes of the overall lithium transport mechanism, we employ an analytical, Rouse-based cation transport model (Maitra et al. Phys. Rev. Lett. 2007, 98, 227802), which has originally been devised for binary PEO-based electrolytes. This model distinguishes three different microscopic transport mechanisms, each quantified by an individual time scale. In the course of our analysis, we extend this mathematical description to account for an entirely new transport mechanism, namely, the TFSI-supported diffusion of lithium ions decoupled from the PEO chains, which emerges for certain stoichiometries. We find that the segmental mobility plays a decisive role in PEO-based polymer electrolytes. That is, whereas the addition of the ionic liquid to PEO20LiTFSI plasticizes the polymer network and thus also increases the lithium diffusion, the amount of free, mobile ether oxygens reduces when substituting the PEO chains by the ionic liquid, which compensates the plasticizing effect. In total, our observations allow us to formulate some general principles about the lithium ion transport mechanism in ternary polymer electrolytes. Moreover, our insights also shed light on recent experimental observations (Joost et al. Electrochim. Acta 2012, 86, 330).

Surface polymerization of (3,4-ethylenedioxythiophene) probed by in situ scanning tunneling microscopy on Au(111) in ionic liquids.

PubMed

Ahmad, Shahzada; Carstens, Timo; Berger, Rüdiger; Butt, Hans-Jürgen; Endres, Frank

2011-01-01

The electropolymerization of 3,4-ethylenedioxythiophene (EDOT) to poly(3,4-ethylenedioxythiophene) (PEDOT) was investigated in the air and water-stable ionic liquids 1-hexyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate [HMIm]FAP and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide [EMIm]TFSA. In situ scanning tunnelling microscopy (STM) results show that the electropolymerization of EDOT in the ionic liquid can be probed on the nanoscale. In contrast to present understanding, it was observed that the EDOT can be oxidised in ionic liquids well below its oxidation potential and the under potential growth of polymer was visualized by in situ STM. These results serve as the first study to confirm the under potential growth of conducting polymers in ionic liquids. Furthermore, ex situ microscopy measurements were performed. Quite a high current of 670 nA was observed on the nanoscale by conductive scanning force microscopy (CSFM).

Two Players Make a Formidable Combination: In Situ Generated Poly(acrylic anhydride-2-methyl-acrylic acid-2-oxirane-ethyl ester-methyl methacrylate) Cross-Linking Gel Polymer Electrolyte toward 5 V High-Voltage Batteries.

PubMed

Ma, Yue; Ma, Jun; Chai, Jingchao; Liu, Zhihong; Ding, Guoliang; Xu, Gaojie; Liu, Haisheng; Chen, Bingbing; Zhou, Xinhong; Cui, Guanglei; Chen, Liquan

2017-11-29

Electrochemical performance of high-voltage lithium batteries with high energy density is limited because of the electrolyte instability and the electrode/electrolyte interfacial reactivity. Hence, a cross-linking polymer network of poly(acrylic anhydride-2-methyl-acrylic acid-2-oxirane-ethyl ester-methyl methacrylate) (PAMM)-based electrolyte was introduced via in situ polymerization inspired by "shuangjian hebi", which is a statement in a traditional Chinese Kungfu story similar to the synergetic effect of 1 + 1 > 2. A poly(acrylic anhydride) and poly(methyl methacrylate)-based system is very promising as electrolyte materials for lithium-ion batteries, in which the anhydride and acrylate groups can provide high voltage resistance and fast ionic conductivity, respectively. As a result, the cross-linking PAMM-based electrolyte possesses a significant comprehensive enhancement, including electrochemical stability window exceeding 5 V vs Li + /Li, an ionic conductivity of 6.79 × 10 -4 S cm -1 at room temperature, high mechanical strength (27.5 MPa), good flame resistance, and excellent interface compatibility with Li metal. It is also demonstrated that this gel polymer electrolyte suppresses the negative effect resulting from dissolution of Mn 2+ ions at 25 and 55 °C. Thus, the LiNi 0.5 Mn 1.5 O 4 /Li and LiNi 0.5 Mn 1.5 O 4 /Li 4 Ti 5 O 12 cells using the optimized in situ polymerized cross-linking PAMM-based gel polymer electrolyte deliver stable charging/discharging profiles and excellent rate performance at room temperature and even at 55 °C. These findings suggest that the cross-linking PAMM is an intriguing candidate for 5 V class high-voltage gel polymer electrolyte toward high-energy lithium-on batteries.

Electrical and electrochemical studies on sodium ion-based gel polymer electrolytes

NASA Astrophysics Data System (ADS)

Isa, K. B. Md; Othman, L.; Hambali, D.; Osman, Z.

2017-09-01

Gel polymer electrolytes (GPEs) have captured great attention because of their unique properties such as good mechanical stability, high flexibility and high conductivity approachable to that of the liquid electrolytes. In this work, we have prepared sodium ion conducting gel polymer electrolyte (GPE) films consisting of polyvinylidenefluoride-co-hexafluoropropylene (PVdF-HFP) as a polymer host using the solution casting technique. Sodium trifluoromethane- sulfonate (NaCF3SO3) was used as an ionic salt and the mixture of ethylene carbonate (EC) and propylene carbonate (PC) as a plasticizing solvent. Impedance spectroscopy measurements were carried out to determine the ionic conductivity of the GPE films. The sample containing 20 wt.% of NaCF3SO3 salt exhibits the highest room temperature ionic conductivity of 2.50 × 10-3 S cm-1. The conductivity of the GPE films was found to depend on the salt concentration that added to the films. The ionic and cationic transference numbers of GPE films were estimated by DC polarization and the combination of AC and DC polarization method, respectively. The results had shown that both ionic and cationic transference numbers are consistent with the conductivity studies. The electrochemical stability of the GPE films was tested using linear sweep voltammetry (LSV) and the value of working voltage range appears to be high enough to be used as an electrolyte in sodium batteries. The cyclic voltammetry (CV) studies confirmed the sodium ion conduction in the GPE films.

ENZYMATIC POLYMERIZATION OF PHENOLS IN ROOM TEMPERATURE IONIC LIQUIDS

PubMed Central

Eker, Bilge; Zagorevski, Dmitri; Zhu, Guangyu; Linhardt, Robert J.; Dordick, Jonathan S.

2009-01-01

Soybean peroxidase (SBP) was used to catalyze the polymerization of phenols in room-temperature ionic liquids (RTILs). Phenolic polymers with number average molecular weights ranging from 1200 to 4100 D were obtained depending on the composition of the reaction medium and the nature of the phenol. Specifically, SBP was highly active in methylimidazolium-containing RTILs, including 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM(BF4)), and 1-butyl-3-methylpyridinium tetrafluoroborate (BMPy(BF4)) with the ionic liquid content as high as 90% (v/v); the balance being aqueous buffer. Gel permeation chromatography and MALDI-TOF analysis indicated that higher molecular weight polymers can be synthesized in the presence of higher RTIL concentrations, with selective control over polymer size achieved by varying the RTIL concentration. The resulting polyphenols exhibited high thermostability and possessed thermosetting properties. PMID:20161409

Novel Molecular Architectures Developed for Improved Solid Polymer Electrolytes for Lithium Polymer Batteries

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B.; Kinder, James D.; Bennett, William R.

2002-01-01

Lithium-based polymer batteries for aerospace applications need the ability to operate in temperatures ranging from -70 to 70 C. Current state-of-the-art solid polymer electrolytes (based on amorphous polyethylene oxide, PEO) have acceptable ionic conductivities (10-4 to 10-3 S/cm) only above 60 C. Higher conductivity can be achieved in the current systems by adding solvent or plasticizers to the solid polymer to improve ion transport. However, this can compromise the dimensional and thermal stability of the electrolyte, as well as compatibility with electrode materials. One of NASA Glenn Research Center's objectives in the PERS program is to develop new electrolytes having unique molecular architectures and/or novel ion transport mechanisms, leading to good ionic conductivity at room temperature and below without solvents or plasticizers.

Use of ionic liquids as coordination ligands for organometallic catalysts

DOEpatents

Li, Zaiwei [Moreno Valley, CA; Tang, Yongchun [Walnut, CA; Cheng,; Jihong, [Arcadia, CA

2009-11-10

Aspects of the present invention relate to compositions and methods for the use of ionic liquids with dissolved metal compounds as catalysts for a variety of chemical reactions. Ionic liquids are salts that generally are liquids at room temperature, and are capable of dissolving a many types of compounds that are relatively insoluble in aqueous or organic solvent systems. Specifically, ionic liquids may dissolve metal compounds to produce homogeneous and heterogeneous organometallic catalysts. One industrially-important chemical reaction that may be catalyzed by metal-containing ionic liquid catalysts is the conversion of methane to methanol.

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

PubMed Central

Tafur, Juan P.; Santos, Florencio; Fernández Romero, Antonio J.

2015-01-01

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. PMID:26610580

Ionic Liquids for Advanced Materials

DTIC Science & Technology

2008-12-01

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

Conjugated ionomers for photovoltaic applications: electric field driven charge separation in organic photovoltaics. Final Technical report

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

Lonergan, Mark

Final technical report for Conjugated ionomers for photovoltaic applications, electric field driven charge separation in organic photovoltaics. The central goal of the work we completed was been to understand the photochemical and photovoltaic properties of ionically functionalized conjugated polymers (conjugated ionomers or polyelectrolytes) and energy conversion systems based on them. We primarily studied two classes of conjugated polymer interfaces that we developed based either upon undoped conjugated polymers with an asymmetry in ionic composition (the ionic junction) or doped conjugated polymers with an asymmetry in doping type (the p-n junction). The materials used for these studies have primarily been themore » polyacetylene ionomers. We completed a detailed study of p-n junctions with systematically varying dopant density, photochemical creation of doped junctions, and experimental and theoretical work on charge transport and injection in polyacetylene ionomers. We have also completed related work on the use of conjugated ionomers as interlayers that improve the efficiency or organic photovoltaic systems and studied several important aspects of the chemistry of ionically functionalized semiconductors, including mechanisms of so-called "anion-doping", the formation of charge transfer complexes with oxygen, and the synthesis of new polyfluorene polyelectrolytes. We also worked worked with the Haley group at the University of Oregon on new indenofluorene-based organic acceptors.« less

Enhancing the performance of green solid-state electric double-layer capacitor incorporated with fumed silica nanoparticles

NASA Astrophysics Data System (ADS)

Chong, Mee Yoke; Numan, Arshid; Liew, Chiam-Wen; Ng, H. M.; Ramesh, K.; Ramesh, S.

2018-06-01

Solid polymer electrolyte (SPE) based on fumed silica nanoparticles as nanofillers, hydroxylethyl cellulose (HEC) as host polymer, magnesium trifluoromethanesulfonate salt and 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid is prepared by solution casting technique. The ionic conductivity, interactions of adsorbed ions on the host polymer, structural crystallinity and thermal stability are evaluated by electrochemical impedance spectroscopy (EIS), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and thermogravimetric analysis (TGA), respectively. Ionic conductivity studies at room temperature reveals that the SPE with 2 wt. % of fumed silica nanoparticles gives the highest conductivity compared to its counterpart. The XRD and FTIR studies confirm the dissolution of salt, ionic liquid and successful incorporation of fumed silica nanoparticles with host polymer. In order to examine the performance of SPEs, electric double-layer capacitor (EDLC) are fabricated by using activated carbon electrodes. EDLC studies demonstrate that SPE incorporated with 2 wt. % fumed silica nanoparticles gives high specific capacitance (25.0 F/g) at a scan rate of 5 mV/s compared to SPE without fumed silica. Additionally, it is able to withstand 71.3% of capacitance from its initial capacitance value over 1600 cycles at a current density of 0.4 A/g.

Volatile chemical reagent detector

DOEpatents

Chen, Liaohai; McBranch, Duncan; Wang, Rong; Whitten, David

2004-08-24

A device for detecting volatile chemical reagents based on fluorescence quenching analysis that is capable of detecting neutral electron acceptor molecules. The device includes a fluorescent material, a contact region, a light source, and an optical detector. The fluorescent material includes at least one polymer-surfactant complex. The polymer-surfactant complex is formed by combining a fluorescent ionic conjugated polymer with an oppositely charged surfactant. The polymer-surfactant complex may be formed in a polar solvent and included in the fluorescent material as a solution. Alternatively, the complex may be included in the fluorescent material as a thin film. The use of a polymer-surfactant complex in the fluorescent material allows the device to detect both neutral and ionic acceptor molecules. The use of a polymer-surfactant complex film allows the device and the fluorescent material to be reusable after exposing the fluorescent material to a vacuum for limited time.

Effect of surfactant species and electrophoretic medium composition on the electrophoretic behavior of neutral and water-insoluble linear synthetic polymers in nonaqueous capillary zone electrophoresis.

PubMed

Fukai, Nao; Kitagawa, Shinya; Ohtani, Hajime

2017-07-01

We have recently demonstrated the separation of neutral and water-insoluble linear synthetic polymers in nonaqueous capillary zone electrophoresis (NACZE) using a cationic surfactant of cetyltrimethylammonium chloride (CTAC). In this study, eight ionic surfactants were investigated for the separation of four synthetic polymers (polystyrene, polymethylmethacrylates, polybutadiene, and polycarbonate); only three surfactants (CTAC, dimethyldioctadecylammonium bromide, and sodium dodecylsulfate) caused their separation. The order of the interaction between the polymers and the surfactants depended on both the surfactant species and the composition of the electrophoretic medium. Their investigation revealed that the separation is majorly affected by the hydrophobic interactions between the polymers and the ionic surfactants. In addition, the electrophoretic behavior of polycarbonate suggested that electrostatic interaction also affects the selectivity of the polymers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ionic polymer-metal composite actuators based on triple-layered polyelectrolytes composed of individually functionalized layers.

PubMed

Lee, Jang-Woo; Yoo, Young-Tai; Lee, Jae Yeol

2014-01-22

Ionic polymer-metal composite (IPMC) actuators based on two types of triple-layered Nafion composite membranes were prepared via consecutive solution recasting and electroless plating methods. The triple-layered membranes are composed of a Nafion layer containing an amphiphilic organic molecule (10-camphorsulfonic acid; CSA) in the middle section (for fast and large ion conduction) and two Nafion/modified inorganic composite layers in the outer sections (for large accumulation/retention of mobile ions). For construction of the two types of IPMCs, sulfonated montmorillonite (MMT) and polypyrrole (PPy)-coated alumina fillers were incorporated into the outer layers. Both the triple-layered IPMCs exhibited 42% higher tip displacements at the maximum deflections with a negligible back-relaxation, 50-74% higher blocking forces, and more rapid responses under 3 V dc, compared with conventional single-layered Nafion-IPMCs. Improvements in cyclic displacement under a rectangular voltage input of 3 V at 1 Hz were also made in the triple-layered configurations. Compared with single-layered IPMCs consisting of the identical compositions with the respective outer composite layers, the bending rates and energy efficiencies of both the triple-layered IPMCs were significantly higher, although the blocking forces were a bit lower. These remarkable improvements were attributed to higher capacitances and Young's moduli as well as a more efficient transport of mobile ions and water through the middle layer (Nafion/CSA) and a larger accumulation/retention of the mobile species in the outer functionalized inorganic composite layers. Especially, the triple-layered IPMC with the PPy-modified alumina registered the best actuation performance among all the samples, including a viable actuation even at a low voltage of 1.5 V due to involving efficient redox reactions of PPy with the aid of hygroscopic alumina.

Selective separation of Eu{sup 3+} using polymer-enhanced ultrafiltration

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

Norton, M.V.

1994-03-01

A process to selectively remove {sup 241}Am from liquid radioactive waste was investigated as an actinide separation method applicable to Hanford and other waste sites. The experimental procedures involved removal of Eu, a nonradioactive surrogate for Am, from aqueous solutions at pH 5 using organic polymers in conjunction with ultrafiltration. Commercially available polyacrylic acid (60,000 MW) and Pacific Northwest Laboratory`s (PNL) synthesized E3 copolymer ({approximately}10,000 MW) were tested. Test solutions containing 10 {mu}g/mL of Eu were dosed vath each polymer at various concentrations in order to bind Eu (i.e., by complexation and/or cation exchange) for subsequent rejection by an ultrafiltrationmore » coupon. Test solutions were filtered with and without polymer to determine if enhanced Eu separation could be achieved from polymer treatment. Both polymers significantly increased Eu removal. Optimum concentrations were 20 {mu}g/mL of polyacrylic acid and 100 {mu}g/mL of E3 for 100% Eu rejection by the Amicon PM10 membrane at 55 psi. In addition to enhancement of removal, the polymers selectively bound Eu over Na, suggesting that selective separation of Eu was possible. This suggests that polymer-enhanced ultrafiltration is a potential process for separation of {sup 241}Am from Hanford tank waste, further investigation of binding agents and membranes effective under very alkaline and high ionic strength is warranted. This process also has potential applications for selective separation of toxic metals from industrial process streams.« less

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

NASA Astrophysics Data System (ADS)

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.

Dynamics and relaxation of charge carriers in poly(methylmethacrylate)-lithium salt based polymer electrolytes plasticized with ethylene carbonate

NASA Astrophysics Data System (ADS)

Pal, P.; Ghosh, A.

2016-07-01

In this paper, we have studied the dynamics and relaxation of charge carriers in poly(methylmethacrylate)-lithium salt based polymer electrolytes plasticized with ethylene carbonate. Structural and thermal properties have been examined using X-ray diffraction and differential scanning calorimetry, respectively. We have analyzed the complex conductivity spectra by using power law model coupled with the contribution of electrode polarization at low frequencies and high temperatures. The temperature dependence of the ionic conductivity and crossover frequency exhibits Vogel-Tammann-Fulcher type behavior indicating a strong coupling between the ionic and the polymer chain segmental motions. The scaling of the ac conductivity indicates that relaxation dynamics of charge carriers follows a common mechanism for all temperatures and ethylene carbonate concentrations. The analysis of the ac conductivity also shows the existence of a nearly constant loss in these polymer electrolytes at low temperatures and high frequencies. The fraction of free anions and ion pairs in polymer electrolyte have been obtained from the analysis of Fourier transform infrared spectra. It is observed that these quantities influence the behavior of the composition dependence of the ionic conductivity.

Dynamics and relaxation of charge carriers in poly(methylmethacrylate)-lithium salt based polymer electrolytes plasticized with ethylene carbonate

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

Pal, P.; Ghosh, A., E-mail: sspag@iacs.res.in

2016-07-28

In this paper, we have studied the dynamics and relaxation of charge carriers in poly(methylmethacrylate)-lithium salt based polymer electrolytes plasticized with ethylene carbonate. Structural and thermal properties have been examined using X-ray diffraction and differential scanning calorimetry, respectively. We have analyzed the complex conductivity spectra by using power law model coupled with the contribution of electrode polarization at low frequencies and high temperatures. The temperature dependence of the ionic conductivity and crossover frequency exhibits Vogel-Tammann-Fulcher type behavior indicating a strong coupling between the ionic and the polymer chain segmental motions. The scaling of the ac conductivity indicates that relaxation dynamicsmore » of charge carriers follows a common mechanism for all temperatures and ethylene carbonate concentrations. The analysis of the ac conductivity also shows the existence of a nearly constant loss in these polymer electrolytes at low temperatures and high frequencies. The fraction of free anions and ion pairs in polymer electrolyte have been obtained from the analysis of Fourier transform infrared spectra. It is observed that these quantities influence the behavior of the composition dependence of the ionic conductivity.« less

Role of the Strength of Drug-Polymer Interactions on the Molecular Mobility and Crystallization Inhibition in Ketoconazole Solid Dispersions.

PubMed

Mistry, Pinal; Mohapatra, Sarat; Gopinath, Tata; Vogt, Frederick G; Suryanarayanan, Raj

2015-09-08

The effects of specific drug-polymer interactions (ionic or hydrogen-bonding) on the molecular mobility of model amorphous solid dispersions (ASDs) were investigated. ASDs of ketoconazole (KTZ), a weakly basic drug, with each of poly(acrylic acid) (PAA), poly(2-hydroxyethyl methacrylate) (PHEMA), and polyvinylpyrrolidone (PVP) were prepared. Drug-polymer interactions in the ASDs were evaluated by infrared and solid-state NMR, the molecular mobility quantified by dielectric spectroscopy, and crystallization onset monitored by differential scanning calorimetry (DSC) and variable temperature X-ray diffractometry (VTXRD). KTZ likely exhibited ionic interactions with PAA, hydrogen-bonding with PHEMA, and weaker dipole-dipole interactions with PVP. On the basis of dielectric spectroscopy, the α-relaxation times of the ASDs followed the order: PAA > PHEMA > PVP. In addition, the presence of ionic interactions also translated to a dramatic and disproportionate decrease in mobility as a function of polymer concentration. On the basis of both DSC and VTXRD, an increase in strength of interaction translated to higher crystallization onset temperature and a decrease in extent of crystallization. Stronger drug-polymer interactions, by reducing the molecular mobility, can potentially delay the crystallization onset temperature as well as crystallization extent.

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

PubMed Central

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

2016-01-01

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

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

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

Praveen, D.; Damle, Ramakrishna

2016-05-23

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

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

PubMed

Liew, Chiam-Wen; Ramesh, S

2014-05-21

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.

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

PubMed Central

Liew, Chiam-Wen; Ramesh, S.

2014-01-01

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. PMID:28788662

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

PubMed

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

2012-11-01

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

Molecular and ionic mimicry and the transport of toxic metals

PubMed Central

Bridges, Christy C.; Zalups, Rudolfs K.

2008-01-01

Despite many scientific advances, human exposure to, and intoxication by, toxic metal species continues to occur. Surprisingly, little is understood about the mechanisms by which certain metals and metal-containing species gain entry into target cells. Since there do not appear to be transporters designed specifically for the entry of most toxic metal species into mammalian cells, it has been postulated that some of these metals gain entry into target cells, through the mechanisms of ionic and/or molecular mimicry, at the site of transporters of essential elements and/or molecules. The primary purpose of this review is to discuss the transport of selective toxic metals in target organs and provide evidence supporting a role of ionic and/or molecular mimicry. In the context of this review, molecular mimicry refers to the ability of a metal ion to bond to an endogenous organic molecule to form an organic metal species that acts as a functional or structural mimic of essential molecules at the sites of transporters of those molecules. Ionic mimicry refers to the ability of a cationic form of a toxic metal to mimic an essential element or cationic species of an element at the site of a transporter of that element. Molecular and ionic mimics can also be sub-classified as structural or functional mimics. This review will present the established and putative roles of molecular and ionic mimicry in the transport of mercury, cadmium, lead, arsenic, selenium, and selected oxyanions in target organs and tissues. PMID:15845419

Molecular and ionic mimicry and the transport of toxic metals

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

Bridges, Christy C.; Zalups, Rudolfs K.

Despite many scientific advances, human exposure to, and intoxication by, toxic metal species continues to occur. Surprisingly, little is understood about the mechanisms by which certain metals and metal-containing species gain entry into target cells. Since there do not appear to be transporters designed specifically for the entry of most toxic metal species into mammalian cells, it has been postulated that some of these metals gain entry into target cells, through the mechanisms of ionic and/or molecular mimicry, at the site of transporters of essential elements and/or molecules. The primary purpose of this review is to discuss the transport ofmore » selective toxic metals in target organs and provide evidence supporting a role of ionic and/or molecular mimicry. In the context of this review, molecular mimicry refers to the ability of a metal ion to bond to an endogenous organic molecule to form an organic metal species that acts as a functional or structural mimic of essential molecules at the sites of transporters of those molecules. Ionic mimicry refers to the ability of a cationic form of a toxic metal to mimic an essential element or cationic species of an element at the site of a transporter of that element. Molecular and ionic mimics can also be sub-classified as structural or functional mimics. This review will present the established and putative roles of molecular and ionic mimicry in the transport of mercury, cadmium, lead, arsenic, selenium, and selected oxyanions in target organs and tissues.« less

All Solid State Rechargeable Lithium Batteries using Block Copolymers

NASA Astrophysics Data System (ADS)

Hallinan, Daniel; Balsara, Nitash

2011-03-01

The growing need for alternative energy and increased demand for mobile technology require higher density energy storage. Existing battery technologies, such as lithium ion, are limited by theoretical energy density as well as safety issues. Other battery chemistries are promising options for dramatically increasing energy density. Safety can be improved by replacing the flammable, reactive liquids used in existing lithium-ion battery electrolytes with polymer electrolytes. Block copolymers are uniquely suited for this task because ionic conductivity and mechanical strength, both important properties in battery formulation, can be independently controlled. In this study, lithium batteries were assembled using lithium metal as negative electrode, polystyrene-b-poly(ethylene oxide) copolymer with lithium salt as electrolyte, and a positive electrode. The positive electrode consisted of polymer electrolyte for ion conduction, carbon for electron conduction, and an active material. Batteries were charged and discharged over many cycles. The battery cycling results were compared to a conventional battery chemistry.

Nanoporous carbon-based electrodes for high strain ionomeric bending actuators

NASA Astrophysics Data System (ADS)

Palmre, Viljar; Brandell, Daniel; Mäeorg, Uno; Torop, Janno; Volobujeva, Olga; Punning, Andres; Johanson, Urmas; Kruusmaa, Maarja; Aabloo, Alvo

2009-09-01

Ionic polymer metal composites (IPMCs) are electroactive material devices that bend at low applied voltage (1-4 V). Inversely, a voltage is generated when the materials are deformed, which makes them useful both as sensors and actuators. In this paper, we propose two new highly porous carbon materials as electrodes for IPMC actuators, generating a high specific area, and compare their electromechanical performance with recently reported RuO2 electrodes and conventional IPMCs. Using a direct assembly process (DAP), we synthesize ionic liquid (Emi-Tf) actuators with either carbide-derived carbon (CDC) or coconut-shell-based activated carbon-based electrodes. The carbon electrodes were applied onto ionic liquid-swollen Nafion membranes using a direct assembly process. The study demonstrates that actuators based on carbon electrodes derived from TiC have the greatest peak-to-peak strain output, reaching up to 20.4 mɛ (equivalent to>2%) at a 2 V actuation signal, exceeding that of the RuO2 electrodes by more than 100%. The electrodes synthesized from TiC-derived carbon also exhibit significantly higher maximum strain rate. The differences between the materials are discussed in terms of molecular interactions and mechanisms upon actuation in the different electrodes.

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

NASA Astrophysics Data System (ADS)

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.

Molecular dynamics simulation of the polymer electrolyte poly(ethylene oxide)/LiClO(4). II. Dynamical properties.

PubMed

Siqueira, Leonardo J A; Ribeiro, Mauro C C

2006-12-07

The dynamical properties of the polymer electrolyte poly(ethylene oxide) (PEO)LiClO(4) have been investigated by molecular dynamics simulations. The effect of changing salt concentration and temperature was evaluated on several time correlation functions. Ionic displacements projected on different directions reveal anisotropy in short-time (rattling) and long-time (diffusive) dynamics of Li(+) cations. It is shown that ionic mobility is coupled to the segmental motion of the polymeric chain. Structural relaxation is probed by the intermediate scattering function F(k,t) at several wave vectors. Good agreement was found between calculated and experimental F(k,t) for pure PEO. A remarkable slowing down of polymer relaxation is observed upon addition of the salt. The ionic conductivity estimated by the Nernst-Einstein equation is approximately ten times higher than the actual conductivity calculated by the time correlation function of charge current.

An ionic liquid-gated polymer thin film transistor with exceptionally low "on" resistance

NASA Astrophysics Data System (ADS)

Algarni, Saud A.; Althagafi, Talal M.; Smith, Patrick J.; Grell, Martin

2014-05-01

We report the ionic liquid (IL) gating of a solution processed semiconducting polymer, poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT). IL gating relies on the poor solubility of PBTTT, which requires hot chlorinated benzenes for solution processing. PBTTT, thus, resists dissolution even in IL, which otherwise rapidly dissolves semiconducting polymers. The resulting organic thin film transistors (OTFTs) display low threshold, very high carrier mobility (>3 cm2/Vs), and deliver high currents (in the order of 1 mA) at low operational voltages. Such OTFTs are interesting both practically, for the addressing of current-driven devices (e.g., organic LEDs), and for the study of charge transport in semiconducting polymers at very high carrier density.

Solid electrolyte material manufacturable by polymer processing methods

DOEpatents

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.

Preparation and electrochemical characterization of polymer electrolytes based on electrospun poly(vinylidene fluoride- co-hexafluoropropylene)/polyacrylonitrile blend/composite membranes for lithium batteries

NASA Astrophysics Data System (ADS)

Raghavan, Prasanth; Zhao, Xiaohui; Shin, Chorong; Baek, Dong-Ho; Choi, Jae-Won; Manuel, James; Heo, Min-Yeong; Ahn, Jou-Hyeon; Nah, Changwoon

Apart from PEO based solid polymer electrolytes, tailor-made gel polymer electrolytes based on blend/composite membranes of poly(vinylidene fluoride- co-hexafluoropropylene) and polyacrylonitrile are prepared by electrospinning using 14 wt% polymer solution in dimethylformamide. The membranes show uniform morphology with an average fiber diameter of 320-490 nm, high porosity and electrolyte uptake. Polymer electrolytes are prepared by soaking the electrospun membranes in 1 M lithium hexafluorophosphate in ethylene carbonate/dimethyl carbonate. Temperature dependent ionic conductivity and their electrochemical performance are studied. The blend/composite polymer electrolytes show good ionic conductivity in the range of 10 -3 S cm -1 at ambient temperature and good electrochemical performance. All the Polymer electrolytes show an anodic stability >4.6 V with stable interfacial resistance with storage time. The prototype cell shows good charge-discharge properties and stable cycle performance with comparable capacity fade compared to liquid electrolyte under the test conditions.

Highly stable noble-metal nanoparticles in tetraalkylphosphonium ionic liquids for in situ catalysis.

PubMed

Banerjee, Abhinandan; Theron, Robin; Scott, Robert W J

2012-01-09

Gold and palladium nanoparticles were prepared by lithium borohydride reduction of the metal salt precursors in tetraalkylphosphonium halide ionic liquids in the absence of any organic solvents or external nanoparticle stabilizers. These colloidal suspensions remained stable and showed no nanoparticle agglomeration over many months. A combination of electrostatic interactions between the coordinatively unsaturated metal nanoparticle surface and the ionic-liquid anions, bolstered by steric protection offered by the bulky alkylated phosphonium cations, is likely to be the reason behind such stabilization. The halide anion strongly absorbs to the nanoparticle surface, leading to exceptional nanoparticle stability in halide ionic liquids; other tetraalkylphosphonium ionic liquids with non-coordinating anions, such as tosylate and hexafluorophosphate, show considerably lower affinities towards the stabilization of nanoparticles. Palladium nanoparticles stabilized in the tetraalkylphosphonium halide ionic liquid were stable, efficient, and recyclable catalysts for a variety of hydrogenation reactions at ambient pressures with sustained activity. Aerial oxidation of the metal nanoparticles occurred over time and was readily reversed by re-reduction of oxidized metal salts. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterizations of novel polymer electrolytes

NASA Astrophysics Data System (ADS)

Chanthad, Chalathorn

Polymer electrolytes are an important component of many electrochemical devices. The ability to control the structures, properties, and functions of polymer electrolytes remains a key subject for the development of next generation functional polymers. Taking advantage of synthetic strategies is a promising approach to achieve the desired chemical structures, morphologies, thermal, mechanical, and electrochemical properties. Therefore, the major goal of this thesis is to develop synthetic methods for of novel proton exchange membranes and ion conductive membranes. In Chapter 2, new classes of fluorinated polymer- polysilsesquioxane nanocomposites have been designed and synthesized. The synthetic method employed includes radical polymerization using the functional benzoyl peroxide initiator for the telechelic fluorinated polymers with perfluorosulfonic acids in the side chains and a subsequent in-situ sol-gel condensation of the prepared triethoxylsilane-terminated fluorinated polymers with alkoxide precursors. The properties of the composite membranes have been studied as a function of the content and structure of the fillers. The proton conductivity of the prepared membranes increases steadily with the addition of small amounts of the polysilsesquioxane fillers. In particular, the sulfopropylated polysilsesquioxane based nanocomposites display proton conductivities greater than Nafion. This is attributed to the presence of pendant sulfonic acids in the fillers, which increases ion-exchange capacity and offers continuous proton transport channels between the fillers and the polymer matrix. The methanol permeability of the prepared membranes has also been examined. Lower methanol permeability and higher electrochemical selectivity than those of Nafion have been demonstrated in the polysilsesquioxane based nanocomposites. In Chapter 3, the synthesis of a new class of ionic liquid-containing triblock copolymers with fluoropolymer mid-block and imidazolium methacrylate end-blocks is described for the first time. The synthetic strategy involves the preparation of the telechelic fluoropolymers using a functional benzoyl peroxide initiator as the macro-chain transfer agent for subsequent RAFT polymerization of the imidazolium methacrylate monomer. As revealed in DSC, SAXS and dielectric relaxation spectroscopy (DRS) measurements, there was no microphase separation in the triblock copolymers, likely due to solubility of ionic liquid moieties in the fluoropolymer matrix. The anionic counterion has direct impact on the thermal properties, ionic conductivity and segmental dynamics of the polymers. The temperature dependence of the ionic conductivity is well described by the Vogel-Tamman-Fulcher model, suggesting that ion motion is closely coupled to segmental motion. In Chapter 4 and 5, new solid electrolytes for lithium cations have been synthesized by catalyzed hydrosilylation reaction involving hydrogen atoms of polysiloxane and polyhedral oligomeric silsesquioxane (POSS) and double bonds of vinyl tris17-bromo-3,6,9,12,15- pentaoxaheptadecan-1-ol silane. The obtained structures are based on branched or dendritic with ionic liquid-ethylene oxide oligomer. High room temperature ionic conductivities have been obtained in the range of 10-4-10-5 can be regarded as solid electrolytes. This is attributed to the high concentration of ions from ionic liquid moieties in the tripodand molecule, high segmental mobility, and high ion dissociation from ethylene oxide spacers. The influence of anion structures and lithium salts and concentration has been investigated.

Stochastic analysis of motor-control stability, polymer based force sensing, and optical stimulation as a preventive measure for falls

NASA Astrophysics Data System (ADS)

Landrock, Clinton K.

Falls are the leading cause of all external injuries. Outcomes of falls include the leading cause of traumatic brain injury and bone fractures, and high direct medical costs in the billions of dollars. This work focused on developing three areas of enabling component technology to be used in postural control monitoring tools targeting the mitigation of falls. The first was an analysis tool based on stochastic fractal analysis to reliably measure levels of motor control. The second focus was on thin film wearable pressure sensors capable of relaying data for the first tool. The third was new thin film advanced optics for improving phototherapy devices targeting postural control disorders. Two populations, athletes and elderly, were studied against control groups. The results of these studies clearly show that monitoring postural stability in at-risk groups can be achieved reliably, and an integrated wearable system can be envisioned for both monitoring and treatment purposes. Keywords: electro-active polymer, ionic polymer-metal composite, postural control, motor control, fall prevention, sports medicine, fractal analysis, physiological signals, wearable sensors, phototherapy, photobiomodulation, nano-optics.

Polycarbonate-based polyurethane as a polymer electrolyte matrix for all-solid-state lithium batteries

NASA Astrophysics Data System (ADS)

Bao, Junjie; Shi, Gaojian; Tao, Can; Wang, Chao; Zhu, Chen; Cheng, Liang; Qian, Gang; Chen, Chunhua

2018-06-01

Four kinds of polycarbonate-based polyurethane with 8-14 wt% hard segments content are synthesized via reactions of polycarbonatediol, hexamethylene diisocyanate and diethylene glycol. The mechanical strength of the polyurethanes increase with the increase of hard segments content. Solid polymer electrolytes composed of the polycarbonate-based polyurethanes and LiTFSI exhibits fascinating characteristics for all-solid-state lithium batteries with a high ionic conductivity of 1.12 × 10-4 S cm-1 at 80 °C, an electrochemical stability window up to 4.5 V (vs. Li+/Li), excellent mechanical strength and superior interfacial stability against lithium metal. The all-solid-state batteries using LiFePO4 cathode can deliver high discharge capacities (161, 158, 134 and 93 mAh g-1 at varied rates of 0.2, 0.5, 1 and 2 C) at 80 °C and excellent cycling performance (with 91% capacity retention after 600 cycles at 1 C). All the results indicate that such a polyurethane-based solid polymer electrolyte can be a promising candidate for all-solid-state lithium batteries.

Nanoparticle enhanced ionic liquid heat transfer fluids

DOEpatents

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

2014-08-12

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

Newton Output Blocking Force under Low-Voltage Stimulation for Carbon Nanotube-Electroactive Polymer Composite Artificial Muscles.

PubMed

Chen, I-Wen Peter; Yang, Ming-Chia; Yang, Chia-Hui; Zhong, Dai-Xuan; Hsu, Ming-Chun; Chen, YiWen

2017-02-15

This is a study on the development of carbon nanotube-based composite actuators using a new ionic liquid-doped electroactive ionic polymer. For scalable production purposes, a simple hot-pressing method was used. Carbon nanotube/ionic liquid-Nafion/carbon nanotube composite films were fabricated that exhibited a large output blocking force and a stable cycling life with low alternating voltage stimuli in air. Of particular interest and importance, a blocking force of 1.5 N was achieved at an applied voltage of 6 V. Operational durability was confirmed by testing in air for over 30 000 cycles (or 43 h). The superior actuation performance of the carbon nanotube/ionic liquid-Nafion/carbon nanotube composite, coupled with easy manufacturability, low driving voltage, and reliable operation, promises great potential for artificial muscle and biomimetic applications.

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

NASA Astrophysics Data System (ADS)

Ji, Jianying

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

High temperature lithium cells with solid polymer electrolytes

DOEpatents

Yang, Jin; Eitouni, Hany Basam; Singh, Mohit

2017-03-07

Electrochemical cells that use electrolytes made from new polymer compositions based on poly(2,6-dimethyl-1,4-phenylene oxide) and other high-softening-temperature polymers are disclosed. These materials have a microphase domain structure that has an ionically-conductive phase and a phase with good mechanical strength and a high softening temperature. In one arrangement, the structural block has a softening temperature of about 210.degree. C. These materials can be made with either homopolymers or with block copolymers. Such electrochemical cells can operate safely at higher temperatures than have been possible before, especially in lithium cells. The ionic conductivity of the electrolytes increases with increasing temperature.

Rare earth metal-containing ionic liquids

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

Prodius, Denis; Mudring, Anja-Verena

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

Rare earth metal-containing ionic liquids

DOE PAGES

Prodius, Denis; Mudring, Anja-Verena

2018-03-07

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

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

PubMed

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.

Effect of porosity and tortuosity of electrodes on carbon polymer soft actuators

NASA Astrophysics Data System (ADS)

S, Sunjai Nakshatharan; Punning, Andres; Johanson, Urmas; Aabloo, Alvo

2018-01-01

This work presents an electro-mechanical model and simulation of ionic electroactive polymer soft actuators with a porous carbon electrode, polymer membrane, and ionic liquid electrolyte. An attempt is made to understand the effects of specific properties of the porous electrodes such as porosity and tortuosity on the charge dynamics and mechanical performance of the actuator. The model uses porous electrode theory to study the electrochemical response of the system. The mechanical response of the whole laminate is attributed to the evolution of local stresses caused by diffusion of ions (diffusion-induced stresses or chemical stresses). The model indicates that in actuators with porous electrode, the diffusion coefficient of ions, conductivity of the electrodes, and ionic conductivity in both electrodes and separator are altered significantly. In addition, the model leads to an obvious deduction that the ions that are highly active in terms of mobility will dominate the whole system in terms of resulting mechanical deformation direction and rate of deformation. Finally, to validate the model, simulations are conducted using the finite element method, and the outcomes are compared with the experimental data. Significant effort has been put forward to experimentally measure the key parameters essential for the validation of the model. The results show that the model developed is able to well predict the behavior of the actuator, providing a comprehensive understanding of charge dynamics in ionic polymer actuator with porous electrodes.

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

NASA Astrophysics Data System (ADS)

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.

Structure–property study of cross-linked hydrocarbon/poly(ethylene oxide) electrolytes with superior conductivity and dendrite resistance† †Electronic supplementary information (ESI) available: Synthetic procedures, characterization data, electrochemical impedance spectra and additional SEM images. See DOI: 10.1039/c6sc01813k Click here for additional data file.

PubMed Central

Zheng, Qi; Ma, Lin; Khurana, Rachna

2016-01-01

Lithium dendrite growth is a fundamental problem that precludes the practical use of lithium metal batteries. Solid polymer electrolytes (SPEs) have been widely studied to resist the growth of lithium dendrites but the underlying mechanisms are still unclear. Most SPEs sacrifice high ionic conductivities for increased dendrite suppression performance by using components with high mechanical stiffness. We report a class of cross-linked hydrocarbon/poly(ethylene oxide) SPEs with both high ionic conductivities (approaching 1 × 10–3 S cm–1 at 25 °C) and superior dendrite suppression characteristics. A systematic structure–property study shows that the crystallinity of the hydrocarbon backbones plays a key role in regulating size and morphology of lithium dendrites, as well as the ability to suppress their growth. PMID:28451125

Porous ionic liquids: synthesis and application.

PubMed

Zhang, Shiguo; Dokko, Kaoru; Watanabe, Masayoshi

2015-07-15

Solidification of fluidic ionic liquids into porous materials yields porous ionic networks that combine the unique characteristics of ionic liquids with the common features of polymers and porous materials. This minireview reports the most recent advances in the design of porous ionic liquids. A summary of the synthesis of ordered and disordered porous ionic liquid-based nanoparticles or membranes with or without templates is provided, together with the new concept of room temperature porous ionic liquids. As a versatile platform for functional materials, porous ionic liquids have shown widespread applications in catalysis, adsorption, sensing, actuation, etc. This new research direction towards ionic liquids chemistry is still in its early stages but has great potential.

Osmotic swelling of polyacrylate hydrogels in physiological salt solutions.

PubMed

Horkay, F; Tasaki, I; Basser, P J

2000-01-01

The swelling behavior of fully neutralized sodium polyacrylate gels was investigated in aqueous solutions of alkali metal (LiCl, NaCl, KCl, CsCl) and alkaline earth metal salts (CaCl2, SrCl2, BaCl2). The total salt concentration and the ratio of monovalent to divalent cations were varied in the biologically significant range. It is found that the concentrations of both monovalent and divalent cations vary continuously and smoothly in the gel despite the abrupt change in the gel volume. The individual elastic, mixing, and ionic contributions to the free energy of the gel were separately determined as a function of the degree of network swelling to elucidate the thermodynamics of swelling. Shear modulus measurements performed at different Ca2+ concentrations suggest that Ca2+ does not form stable cross-links between the polymer chains. At low and moderate swelling ratios the concentration dependence of the shear modulus follows a power law behavior, G variation of phi n, with n = 0.34 +/- 0.03. At high swelling degrees, however, the shear modulus increases with increasing swelling. The value of the Flory-Huggins interaction parameter, chi, determined from osmotic swelling pressure and shear modulus measurements, strongly depends on the ionic composition of the equilibrium solution and increases with increasing Ca2+ concentration.

Ionic imbalance induced self-propulsion of liquid metals

PubMed Central

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

2016-01-01

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

Ionic imbalance induced self-propulsion of liquid metals.

PubMed

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

2016-08-04

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

Ionic imbalance induced self-propulsion of liquid metals

NASA Astrophysics Data System (ADS)

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

2016-08-01

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

High elastic modulus polymer electrolytes suitable for preventing thermal runaway in lithium batteries

DOEpatents

Mullin, Scott; Panday, Ashoutosh; Balsara, Nitash Pervez; Singh, Mohit; Eitouni, Hany Basam; Gomez, Enrique Daniel

2014-04-22

A polymer that combines high ionic conductivity with the structural properties required for Li electrode stability is useful as a solid phase electrolyte for high energy density, high cycle life batteries that do not suffer from failures due to side reactions and dendrite growth on the Li electrodes, and other potential applications. The polymer electrolyte includes a linear block copolymer having a conductive linear polymer block with a molecular weight of at least 5000 Daltons, a structural linear polymer block with an elastic modulus in excess of 1.times.10.sup.7 Pa and an ionic conductivity of at least 1.times.10.sup.-5 Scm.sup.-1. The electrolyte is made under dry conditions to achieve the noted characteristics. In another aspect, the electrolyte exhibits a conductivity drop when the temperature of electrolyte increases over a threshold temperature, thereby providing a shutoff mechanism for preventing thermal runaway in lithium battery cells.

Do Membranes Dream of Electric Tubes? Advanced Membranes Using Carbon Nanotube - Polymer Nanocomposites

NASA Astrophysics Data System (ADS)

de Lannoy, Charles-Francois Pedro Claude Karolek Ghislain

Membrane technologies represent an energy efficient, effective solution for treating municipal and commercial waters/wastewaters. Membranes are predominantly polymer-based and despite steady advances in polymeric materials, they continue to suffer from operational problems including biofouling and breakages. This work addresses these two disparate problems by developing novel CNT-polymer nanocomposite materials that contain variously functionalized carbon nanotubes (fCNTs) in low quantities (<0.5wt%). Several strategies have been employed to achieve highly functional CNT-polymer nanocomposite membranes including blend mixing, ionic charge association, and covalent cross-linking with monomer and oligomer constituents. These CNT-polymer nanocomposite membranes were compared to traditional polymer membranes across various properties including increased Young's Modulus, changes in surface hydrophilicity, fine control over molecular weight cut-off and flux, and surface electrical conductivity. Membranes with high surface electrical conductivity were further tested for their anti-biofouling properties. Finally, CNT stability and polymer compatibility were evaluated throughout membrane manufacture, use, and cleaning. The incorporation of CNTs mixed in bulk phase and linked through ionic associations in polymer matrices showed significant (50%) increases in Young's modulus for certain CNT functionalizations and derivatization percent. Membranes formed with high surface electrical conductivity demonstrated almost complete resistance to biofouling (> 95%) in long-term bacterially challenged experiments. CNTs and polymer mixtures that lacked covalent or ionic bonds were susceptible to significant (up to 10%) loss of CNTs during membrane non-solvent gelation and aggressive chemical cleaning treatment. Functionalized carbon nanotubes endow polymer membranes with their unique strength and electrically conductive properties. These added properties were demonstrated to greatly improve membrane operational efficiency and membrane longevity. CNT-polymer nanocomposite membranes offer low-energy, high-efficiency, and long-lifetime alternatives to traditional polymer membranes. With further advances in polymeric nanomaterials, membrane technology has the potential for wide applicability across many fields outside of water filtration and desalination.

Lithium ion intercalation in thin crystals of hexagonal TaSe2 gated by a polymer electrolyte

NASA Astrophysics Data System (ADS)

Wu, Yueshen; Lian, Hailong; He, Jiaming; Liu, Jinyu; Wang, Shun; Xing, Hui; Mao, Zhiqiang; Liu, Ying

2018-01-01

Ionic liquid gating has been used to modify the properties of layered transition metal dichalcogenides (TMDCs), including two-dimensional (2D) crystals of TMDCs used extensively recently in the device work, which has led to observations of properties not seen in the bulk. The main effect comes from the electrostatic gating due to the strong electric field at the interface. In addition, ionic liquid gating also leads to ion intercalation when the ion size of the gate electrolyte is small compared to the interlayer spacing of TMDCs. However, the microscopic processes of ion intercalation have rarely been explored in layered TMDCs. Here, we employed a technique combining photolithography device fabrication and electrical transport measurements on the thin crystals of hexagonal TaSe2 using multiple channel devices gated by a polymer electrolyte LiClO4/Polyethylene oxide (PEO). The gate voltage and time dependent source-drain resistances of these thin crystals were used to obtain information on the intercalation process, the effect of ion intercalation, and the correlation between the ion occupation of allowed interstitial sites and the device characteristics. We found a gate voltage controlled modulation of the charge density waves and a scattering rate of charge carriers. Our work suggests that ion intercalation can be a useful tool for layered materials engineering and 2D crystal device design.

Effect of Branching on Rod-coil Polyimides as Membrane Materials for Lithium Polymer Batteries

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B.; Cubon, Valerie A.; Scheiman, Daniel A.; Bennett, William R.

2003-01-01

This paper describes a series of rod-coil block co-polymers that produce easy to fabricate, dimensionally stable films with good ionic conductivity down to room temperature for use as electrolytes for lithium polymer batteries. The polymers consist of short, rigid rod polyimide segments, alternating with flexible, polyalkylene oxide coil segments. The highly incompatible rods and coils should phase separate, especially in the presence of lithium ions. The coil phase would allow for conduction of lithium ions, while the rigid rod phase would provide a high degree of dimensional stability. An optimization study was carried out to study the effect of four variables (degree of branching, formulated molecular weight, polymerization solvent and lithium salt concentration) on ionic conductivity, glass transition temperature and dimensional stability in this system.

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

NASA Astrophysics Data System (ADS)

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.

Preparation of "dummy" l-phenylalanine molecularly imprinted microspheres by using ionic liquid as a template and functional monomer.

PubMed

Li, Ji; Hu, Xiaoling; Guan, Ping; Song, Dongmen; Qian, Liwei; Du, Chunbao; Song, Renyuan; Wang, Chaoli

2015-07-07

In this study, dummy imprinting technology was employed for the preparation of l-phenylalanine-imprinted microspheres. Ionic liquids were utilized as both a "dummy" template and functional monomer, and 4-vinylpyridine and ethylene glycol dimethacrylate were used as the assistant monomer and cross-linker, respectively, for preparing a surface-imprinted polymer on poly(divinylbenzene) microspheres. By the results obtained by theoretical investigation, the interaction between the template and monomer complex was improved as compared with that between the template and the traditional l-phenylalanine-imprinted polymer. The batch experiments indicated that the imprinting factor reached 2.5. Scatchard analysis demonstrated that the obtained "dummy" molecularly imprinted microspheres exhibited an affinity of 77.4 M·10 -4 , significantly higher that of a traditional polymer directly prepared by l-phenylalanine, which is in agreement with theoretical results. Competitive adsorption experiments also showed that the molecularly imprinted polymer with the dummy template effectively isolated l-phenylalanine from l-histidine and l-tryptophan with separation factors of 5.68 and 2.68, respectively. All these results demonstrated that the polymerizable ionic liquid as the dummy template could enhance the affinity and selectivity of molecularly imprinted polymer, thereby promoting the development of imprinting technology for biomolecules. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultra-high-rate pseudocapacitive energy storage in two-dimensional transition metal carbides

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

Lukatskaya, Maria R.; Kota, Sankalp; Lin, Zifeng

In this study, the use of fast surface redox storage (pseudocapacitive) mechanisms can enable devices that store much more energy than electrical double-layer capacitors (EDLCs) and, unlike batteries, can do so quite rapidly. Yet, few pseudocapacitive transition metal oxides can provide a high power capability due to their low intrinsic electronic and ionic conductivity. Here we demonstrate that two-dimensional transition metal carbides (MXenes) can operate at rates exceeding those of conventional EDLCs, but still provide higher volumetric and areal capacitance than carbon, electrically conducting polymers or transition metal oxides. We applied two distinct designs for MXene electrode architectures with improvedmore » ion accessibility to redox-active sites. A macroporous Ti 3C 2T x MXene film delivered up to 210 F g –1 at scan rates of 10 V s –1, surpassing the best carbon supercapacitors known. In contrast, we show that MXene hydrogels are able to deliver volumetric capacitance of ~1,500 F cm –3 reaching the previously unmatched volumetric performance of RuO 2.« less

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

NASA Astrophysics Data System (ADS)

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 big yield strains, so by increasing the strain allowed on the material the power will increase dramatically, the expected values being up to a few microwatts.

Friction and wear behavior of glasses and ceramics

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1973-01-01

Adhesion, friction, and wear behavior of glasses and ionic solids are reviewed. These materials are shown to behave in a manner similar to other solids with respect to adhesion. Their friction characteristics are shown to be sensitive to environmental constituents and surface films. This sensitivity can be related to a reduction in adhesive bonding and the changes in surficial mechanical behavior associated with Rehbinder and Joffe effects. Both friction and wear properties of ionic crystalline solids are highly anisotropic. With metals in contact with ionic solids the fracture strength of the ionic solid and the shear strength in the metal and those properties that determine these will dictate which of the materials undergoes adhesive wear. The chemical activity of the metal plays an important role in the nature and strength of the adhesive interfacial bond that develops between the metal and a glass or ionic solid.

Single lithium-ion conducting solid polymer electrolytes: advances and perspectives.

PubMed

Zhang, Heng; Li, Chunmei; Piszcz, Michal; Coya, Estibaliz; Rojo, Teofilo; Rodriguez-Martinez, Lide M; Armand, Michel; Zhou, Zhibin

2017-02-06

Electrochemical energy storage is one of the main societal challenges to humankind in this century. The performances of classical Li-ion batteries (LIBs) with non-aqueous liquid electrolytes have made great advances in the past two decades, but the intrinsic instability of liquid electrolytes results in safety issues, and the energy density of the state-of-the-art LIBs cannot satisfy the practical requirement. Therefore, rechargeable lithium metal batteries (LMBs) have been intensively investigated considering the high theoretical capacity of lithium metal and its low negative potential. However, the progress in the field of non-aqueous liquid electrolytes for LMBs has been sluggish, with several seemingly insurmountable barriers, including dendritic Li growth and rapid capacity fading. Solid polymer electrolytes (SPEs) offer a perfect solution to these safety concerns and to the enhancement of energy density. Traditional SPEs are dual-ion conductors, in which both cations and anions are mobile and will cause a concentration polarization thus leading to poor performances of both LIBs and LMBs. Single lithium-ion (Li-ion) conducting solid polymer electrolytes (SLIC-SPEs), which have anions covalently bonded to the polymer, inorganic backbone, or immobilized by anion acceptors, are generally accepted to have advantages over conventional dual-ion conducting SPEs for application in LMBs. A high Li-ion transference number (LTN), the absence of the detrimental effect of anion polarization, and the low rate of Li dendrite growth are examples of benefits of SLIC-SPEs. To date, many types of SLIC-SPEs have been reported, including those based on organic polymers, organic-inorganic hybrid polymers and anion acceptors. In this review, a brief overview of synthetic strategies on how to realize SLIC-SPEs is given. The fundamental physical and electrochemical properties of SLIC-SPEs prepared by different methods are discussed in detail. In particular, special attention is paid to the SLIC-SPEs with high ionic conductivity and high LTN. Finally, perspectives on the main challenges and focus on the future research are also presented.

Flexible Polymer/Metal/Polymer and Polymer/Metal/Inorganic Trilayer Transparent Conducting Thin Film Heaters with Highly Hydrophobic Surface.

PubMed

Kang, Tae-Woon; Kim, Sung Hyun; Kim, Cheol Hwan; Lee, Sang-Mok; Kim, Han-Ki; Park, Jae Seong; Lee, Jae Heung; Yang, Yong Suk; Lee, Sang-Jin

2017-09-27

Polymer/metal/polymer and polymer/metal/inorganic trilayer-structured transparent electrodes with fluorocarbon plasma polymer thin film heaters have been proposed. The polymer/metal/polymer and polymer/metal/inorganic transparent conducting thin films fabricated on a large-area flexible polymer substrate using a continuous roll-to-roll sputtering process show excellent electrical properties and visible-light transmittance. They also exhibit water-repelling surfaces to prevent wetting and to remove contamination. In addition, the adoption of a fluorocarbon/metal/fluorocarbon film permits an outer bending radius as small as 3 mm. These films have a sheet resistance of less than 5 Ω sq -1 , sufficient to drive light-emitting diode circuits. The thin film heater with the fluorocarbon/Ag/SiN x structure exhibits excellent heating characteristics, with a temperature reaching 180 °C under the driving voltage of 13 V. Therefore, the proposed polymer/metal/polymer and polymer/metal/inorganic transparent conducting electrodes using polymer thin films can be applied in flexible and rollable displays as well as automobile window heaters and other devices.

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

Pasaribu, Marvin H., E-mail: marvin-shady88@yahoo.com; Arcana, I Made, E-mail: arcana@chem.itb.ac.id; Wahyuningrum, Deana, E-mail: deana@chem.itb.ac.id

Lithium ion battery has been currently developed and produced because it has a longer life time, high energycapacity, and the efficient use of lithium ion battery that is suitable for storing electrical energy. However, this battery has some drawbacks such as use liquid electrolytes that are prone to leakage and flammability during the battery charging process in high temperature. In this study, an ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) containing Li{sup +} ions was synthesized and combined with chitosan polymer host as a polymer electrolyte membrane for lithium-ion batteries to solve this problems. This ionic liquid was obtained from the anionmore » metathesis reaction between EMImBr and LiBF4 salt, while EMImBr was synthesized from the reaction between 1-methylimidazole and ethyl bromide utilizing Microwave Assisted Organic Synthesis (MAOS) method. The ionic liquid obtained was characterized by microstructure analysis with using NMR and FTIR spectroscopy. The polymer electrolyte membrane was characterized by analysis functional groups (FTIR), ionic conductivity (EIS), and surface morphology (SEM). The analysis results of ion conductivity by the EIS method showed the increase the ionic conductivity value of membranes from 1.30 × 10{sup −2} S cm{sup −1} for chitosan to 1.30 × 10{sup −2} S cm{sup −1} for chitosan with EMImBF4/Li{sup +}, and this result was supported by analysis the surface morphology (SEM)« less

21 CFR 888.3640 - Shoulder joint metal/metal or metal/polymer constrained cemented prosthesis.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Shoulder joint metal/metal or metal/polymer... § 888.3640 Shoulder joint metal/metal or metal/polymer constrained cemented prosthesis. (a) Identification. A shoulder joint metal/metal or metal/polymer constrained cemented prosthesis is a device...

21 CFR 888.3640 - Shoulder joint metal/metal or metal/polymer constrained cemented prosthesis.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Shoulder joint metal/metal or metal/polymer... § 888.3640 Shoulder joint metal/metal or metal/polymer constrained cemented prosthesis. (a) Identification. A shoulder joint metal/metal or metal/polymer constrained cemented prosthesis is a device...

21 CFR 888.3640 - Shoulder joint metal/metal or metal/polymer constrained cemented prosthesis.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Shoulder joint metal/metal or metal/polymer... § 888.3640 Shoulder joint metal/metal or metal/polymer constrained cemented prosthesis. (a) Identification. A shoulder joint metal/metal or metal/polymer constrained cemented prosthesis is a device...

21 CFR 888.3640 - Shoulder joint metal/metal or metal/polymer constrained cemented prosthesis.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Shoulder joint metal/metal or metal/polymer... § 888.3640 Shoulder joint metal/metal or metal/polymer constrained cemented prosthesis. (a) Identification. A shoulder joint metal/metal or metal/polymer constrained cemented prosthesis is a device...

21 CFR 888.3640 - Shoulder joint metal/metal or metal/polymer constrained cemented prosthesis.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Shoulder joint metal/metal or metal/polymer... § 888.3640 Shoulder joint metal/metal or metal/polymer constrained cemented prosthesis. (a) Identification. A shoulder joint metal/metal or metal/polymer constrained cemented prosthesis is a device...

Ionic electroactive polymer artificial muscles in space applications.

PubMed

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.

Task-specific ionic liquid-assisted extraction and separation of astaxanthin from shrimp waste.

PubMed

Bi, Wentao; Tian, Minglei; Zhou, Jun; Row, Kyung Ho

2010-08-15

Astaxanthin, as an outstanding antioxidant reagent, was successfully extracted from shrimp waste by the ionic liquids based ultrasonic-assisted extraction. Seven kinds of imidazolium ionic liquids with different cations and anions were investigated in this work and one task-specific ionic liquid in ethanol with 0.50molL(-1) was selected as the solvent. At the optimized ultrasonic extraction conditions, the extraction amount of astaxanthin increased 98% (92.7microg g(-1)) compared to the conventional method (46.7microg g(-1)). Furthermore, the extracted solution was isolated through the solid-phase extraction with a molecularly imprinted polymer sorbent. After loading the samples on molecularly imprinted polymer cartridge, the different washing and elution solvents, such as water, methanol, n-hexane, acetone and dichloromethane, were evaluated, and finally, astaxanthin was separated from the shrimp waste extract. Copyright 2010 Elsevier B.V. All rights reserved.

[Advances of poly (ionic liquid) materials in separation science].

PubMed

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

2015-11-01

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

Electrostatic interactions between ions near Thomas-Fermi substrates and the surface energy of ionic crystal at imperfect metals

PubMed Central

Kaiser, V.; Comtet, J.; Niguès, A.; Siria, A.; Coasne, B.; Bocquet, L.

2017-01-01

The electrostatic interaction between two charged particles is strongly modified in the vicinity of a metal. This situation is usually accounted for by the celebrated image charges approach, which was further extended to account for the electronic screening properties of the metal at the level of the Thomas-Fermi description. In this paper we build upon the approach by [Kornyshev et al. Zh. Eksp. Teor. Fiz., 78(3):1008–1019, 1980] and successive works to calculate the 1-body and 2-body electrostatic energy of ions near a metal in terms of the Thomas-Fermi screening length. We propose workable approximations suitable for molecular simulations of ionic systems close to metallic walls. Furthermore, we use this framework to calculate analytically the electrostatic contribution to the surface energy of a one dimensional crystal at a metallic wall and its dependence on the Thomas-Fermi screening length. These calculations provide a simple interpretation for the surface energy in terms of image charges, which allow for an estimate of interfacial properties in more complex situations of a disordered ionic liquid close to a metal surface. A counterintuitive outcome is that electronic screening, as characterized by a molecular Thomas-Fermi length ℓTF, profoundly affects the wetting of ionic systems close to a metal, in line with the recent experimental observation of capillary freezing of ionic liquids in metallic confinement. PMID:28436506

21 CFR 888.3410 - Hip joint metal/polymer or ceramic/polymer semiconstrained resurfacing cemented prosthesis.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Hip joint metal/polymer or ceramic/polymer... Devices § 888.3410 Hip joint metal/polymer or ceramic/polymer semiconstrained resurfacing cemented prosthesis. (a) Identification. A hip joint metal/polymer or ceramic/polymer semi-constrained resurfacing...

21 CFR 888.3410 - Hip joint metal/polymer or ceramic/polymer semiconstrained resurfacing cemented prosthesis.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Hip joint metal/polymer or ceramic/polymer... Devices § 888.3410 Hip joint metal/polymer or ceramic/polymer semiconstrained resurfacing cemented prosthesis. (a) Identification. A hip joint metal/polymer or ceramic/polymer semi-constrained resurfacing...

21 CFR 888.3410 - Hip joint metal/polymer or ceramic/polymer semiconstrained resurfacing cemented prosthesis.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Hip joint metal/polymer or ceramic/polymer... Devices § 888.3410 Hip joint metal/polymer or ceramic/polymer semiconstrained resurfacing cemented prosthesis. (a) Identification. A hip joint metal/polymer or ceramic/polymer semi-constrained resurfacing...

21 CFR 888.3410 - Hip joint metal/polymer or ceramic/polymer semiconstrained resurfacing cemented prosthesis.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Hip joint metal/polymer or ceramic/polymer... Devices § 888.3410 Hip joint metal/polymer or ceramic/polymer semiconstrained resurfacing cemented prosthesis. (a) Identification. A hip joint metal/polymer or ceramic/polymer semi-constrained resurfacing...

21 CFR 888.3410 - Hip joint metal/polymer or ceramic/polymer semiconstrained resurfacing cemented prosthesis.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Hip joint metal/polymer or ceramic/polymer... Devices § 888.3410 Hip joint metal/polymer or ceramic/polymer semiconstrained resurfacing cemented prosthesis. (a) Identification. A hip joint metal/polymer or ceramic/polymer semi-constrained resurfacing...

Thermodynamics of aggregate formation between a non-ionic polymer and ionic surfactants: An isothermal titration calorimetric study.

PubMed

Patel, Salin Gupta; Bummer, Paul M

2017-01-10

This report examines the energetics of aggregate formation between hydroxypropyl methylcellulose (HPMC) and model ionic surfactants including sodium dodecyl sulfate (SDS) at pharmaceutically relevant concentrations using the isothermal titration calorimetry (ITC) technique and a novel treatment of calorimetric data that accounts for the various species formed. The influence of molecular weight of HPMC, temperature and ionic strength of solution on the aggregate formation process was explored. The interaction between SDS and HPMC was determined to be an endothermic process and initiated at a critical aggregation concentration (CAC). The SDS-HPMC interactions were observed to be cooperative in nature and dependent on temperature and ionic strength of the solution. Molecular weight of HPMC significantly shifted the interaction parameters between HPMC and SDS such that at the highest molecular weight (HPMC K-100M;>240kDa), although the general shape of the titration curve (enthalpogram) was observed to remain similar, the critical concentration parameters (CAC, polymer saturation concentration (C sat ) and critical micelle concentration (CMC)) were significantly altered and shifted to lower concentrations of SDS. Ionic strength was also observed to influence the critical concentration parameters for the SDS-HPMC aggregation and decreased to lower SDS concentrations with increasing ionic strength for both anionic and cationic surfactant-HPMC systems. From these data, other thermodynamic parameters of aggregation such as ΔH agg ° , ΔG agg ° , H agg ° , ΔS agg ° , and ΔC p were calculated and utilized to postulate the hydrophobic nature of SDS-HPMC aggregate formation. The type of ionic surfactant head group (anionic vs. cationic i.e., dodecyltrimethylammonium bromide (DTAB)) was found to influence the strength of HPMC-surfactant interactions wherein a distinct CAC signifying the strength of HPMC-DTAB interactions was not observed. The interpretation of the microcalorimetric data at different temperatures and ionic strengths while varying properties of polymer and surfactant was a very effective tool in investigating the nature and energetics of HPMC and ionic surfactant interactions. Copyright © 2016 Elsevier B.V. All rights reserved.

Structural, microstructural and electrochemical properties of dispersed-type polymer nanocomposite films

NASA Astrophysics Data System (ADS)

Arya, Anil; Sharma, A. L.

2018-01-01

Free-standing solid polymer nanocomposite (PEO-PVC)  +  LiPF6-TiO2 films have been prepared through a standard solution-cast technique. The improvement in structural, microstructural and electrochemical properties has been observed on the dispersion of nanofiller in polymer salt complex. X-ray diffraction studies clearly reflect the formation of complex formation, as no corresponding salt peak appeared in the diffractograms. The Fourier transform infrared analysis suggested clear and convincing evidence of polymer-ion, ion-ion and polymer-ion-nanofiller interaction. The highest ionic conductivity of the prepared solid polymer electrolyte (SPE) films is ~5  ×  10-5 S cm-1 for 7 wt.% TiO2. The linear sweep voltammetry provides the electrochemical stability window of the prepared SPE films, about ~3.5 V. The ion transference number has been estimated, t ion  =  0.99 through the DC polarization technique. Dielectric spectroscopic studies were performed to understand the ion transport process in polymer electrolytes. All solid polymer electrolytes possess good thermal stability up to 300 °C. Differential scanning calorimetry analysis confirms the decrease of the melting temperature and signal of glass transition temperature with the addition of nanofiller, which indicates the decrease of crystallinity of the polymer matrix. An absolute correlation between diffusion coefficient (D), ion mobility (µ), number density (n), double-layer capacitance (C dl), glass transition temperature, melting temperature (T m), free ion area (%) and conductivity (σ) has been observed. A convincing model to study the role of nanofiller in a polymer salt complex has been proposed, which supports the experimental findings. The prepared polymer electrolyte system with significant ionic conductivity, high ionic transference number, and good thermal and voltage stability could be suggested as a potential candidate as electrolyte cum separator for the fabrication of a rechargeable lithium-ion battery system.

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

NASA Astrophysics Data System (ADS)

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

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

Investigation of Cross-Linked and Additive Containing Polymer Materials for Membranes with Improved Performance in Pervaporation and Gas Separation

PubMed Central

Hunger, Katharina; Schmeling, Nadine; Jeazet, Harold B. Tanh; Janiak, Christoph; Staudt, Claudia; Kleinermanns, Karl

2012-01-01

Pervaporation and gas separation performances of polymer membranes can be improved by crosslinking or addition of metal-organic frameworks (MOFs). Crosslinked copolyimide membranes show higher plasticization resistance and no significant loss in selectivity compared to non-crosslinked membranes when exposed to mixtures of CO2/CH4 or toluene/cyclohexane. Covalently crosslinked membranes reveal better separation performances than ionically crosslinked systems. Covalent interlacing with 3-hydroxypropyldimethylmaleimide as photocrosslinker can be investigated in situ in solution as well as in films, using transient UV/Vis and FTIR spectroscopy. The photocrosslinking yield can be determined from the FTIR-spectra. It is restricted by the stiffness of the copolyimide backbone, which inhibits the photoreaction due to spatial separation of the crosslinker side chains. Mixed-matrix membranes (MMMs) with MOFs as additives (fillers) have increased permeabilities and often also selectivities compared to the pure polymer. Incorporation of MOFs into polysulfone and Matrimid® polymers for MMMs gives defect-free membranes with performances similar to the best polymer membranes for gas mixtures, such as O2/N2 H2/CH4, CO2/CH4, H2/CO2, CH4/N2 and CO2/N2 (preferentially permeating gas is named first). The MOF porosity, its particle size and content in the MMM are factors to influence the permeability and the separation performance of the membranes. PMID:24958427

Electrospinning biopolymers from ionic liquids requires control of different solution properties than volatile organic solvents

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

Zavgorodnya, Oleksandra; Shamshina, Julia L.; Bonner, Jonathan R.

Here, we report the correlation between key solution properties and spinability of chitin from the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([C 2mim][OAc]), and the similarities and differences to electrospinning solutions of non-ionic polymers in volatile organic compounds (VOCs). We found that when electrospinning is conducted from ILs, conductivity and surface tension are not the key parameters regulating spinability, while solution viscosity and polymer concentration are. Contrarily, for electrospinning of polymers from VOCs, solution conductivity and viscosity have been reported to be among some of the most important factors controlling fiber formation. For chitin electrospun from [C 2mim][OAc], we found bothmore » a critical chitin concentration required for continuous fiber formation (> 0.20 wt%) and a required viscosity for the spinning solution (between ca. 450 – 1500 cP). The high viscosities of the biopolymer-IL solutions made it possible to electrospin solutions with low, less than 1 wt% of polymer concentration and produce thin fibers without the need to adjust the electrospinning parameters. These results suggest new prospects for the control of fiber architecture in non-woven mats, which is crucial for materials performance.« less

Electrospinning biopolymers from ionic liquids requires control of different solution properties than volatile organic solvents

DOE PAGES

Zavgorodnya, Oleksandra; Shamshina, Julia L.; Bonner, Jonathan R.; ...

2017-04-27

Here, we report the correlation between key solution properties and spinability of chitin from the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([C 2mim][OAc]), and the similarities and differences to electrospinning solutions of non-ionic polymers in volatile organic compounds (VOCs). We found that when electrospinning is conducted from ILs, conductivity and surface tension are not the key parameters regulating spinability, while solution viscosity and polymer concentration are. Contrarily, for electrospinning of polymers from VOCs, solution conductivity and viscosity have been reported to be among some of the most important factors controlling fiber formation. For chitin electrospun from [C 2mim][OAc], we found bothmore » a critical chitin concentration required for continuous fiber formation (> 0.20 wt%) and a required viscosity for the spinning solution (between ca. 450 – 1500 cP). The high viscosities of the biopolymer-IL solutions made it possible to electrospin solutions with low, less than 1 wt% of polymer concentration and produce thin fibers without the need to adjust the electrospinning parameters. These results suggest new prospects for the control of fiber architecture in non-woven mats, which is crucial for materials performance.« less

Effect of Chain Rigidity on the Decoupling of Ion Motion from Segmental Relaxation in Polymerized Ionic Liquids: Ambient and Elevated Pressure Studies

DOE PAGES

Wojnarowska, Zaneta; Feng, Hongbo; Fu, Yao; ...

2017-08-21

Conductivity in polymer electrolytes has been generally discussed with the assumption that the segmental motions control charge transport. However, much less attention has been paid to the mechanism of ion conductivity where the motions of ions are less dependent (decoupled) on segmental dynamics. We present that this phenomenon is observed in ionic materials as they approach their glass transition temperature and becomes essential for design and development of highly conducting solid polymer electrolytes. In this paper, we study the effect of chain rigidity on the decoupling of ion transport from segmental motion in three polymerized ionic liquids (polyILs) containing themore » same cation–anion pair but differing in flexibility of the polymer backbones and side groups. Analysis of dielectric and rheology data reveals that decoupling is strong in vinyl-based rigid polymers while almost negligible in novel siloxane-based flexible polyILs. To explain this behavior, we investigated ion and chain dynamics at ambient and elevated pressure. Our results suggest that decoupling has a direct relationship to the frustration in chain packing and free volume. Finally, these conclusions are also supported by coarse-grained molecular dynamics simulations.« less

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

PubMed

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

2014-01-15

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

Effect of Chain Rigidity on the Decoupling of Ion Motion from Segmental Relaxation in Polymerized Ionic Liquids: Ambient and Elevated Pressure Studies

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

Wojnarowska, Zaneta; Feng, Hongbo; Fu, Yao

Conductivity in polymer electrolytes has been generally discussed with the assumption that the segmental motions control charge transport. However, much less attention has been paid to the mechanism of ion conductivity where the motions of ions are less dependent (decoupled) on segmental dynamics. We present that this phenomenon is observed in ionic materials as they approach their glass transition temperature and becomes essential for design and development of highly conducting solid polymer electrolytes. In this paper, we study the effect of chain rigidity on the decoupling of ion transport from segmental motion in three polymerized ionic liquids (polyILs) containing themore » same cation–anion pair but differing in flexibility of the polymer backbones and side groups. Analysis of dielectric and rheology data reveals that decoupling is strong in vinyl-based rigid polymers while almost negligible in novel siloxane-based flexible polyILs. To explain this behavior, we investigated ion and chain dynamics at ambient and elevated pressure. Our results suggest that decoupling has a direct relationship to the frustration in chain packing and free volume. Finally, these conclusions are also supported by coarse-grained molecular dynamics simulations.« less

Composite Polymer-Garnet Solid State Electrolytes

NASA Astrophysics Data System (ADS)

Villa, Andres; Oduncu, Muhammed R.; Scofield, Gregory D.; Marinero, Ernesto E.; Forbey, Scott

Solid-state electrolytes provide a potential solution to the safety and reliability issues of Li-ion batteries. We have synthesized cubic-phase Li7-xLa3Zr2-xBixO12 compounds utilizing inexpensive, scalable Sol-gel synthesis and obtained ionic conductivities 1.2 x 10-4 S/cm at RT in not-fully densified pellets. In this work we report on the fabrication of composite polymer-garnet ceramic particle electrolytes to produce flexible membranes that can be integrated with standard battery electrodes without the need for a separator. As a first step we incorporated the ceramic particles into polyethylene oxide polymers (PEO) to form flexible membranes. Early results are encouraging yielding ionic conductivity values 1.0 x 10-5 S/cm at RT. To increment the conductivity in the membranes, we are optimizing amongst other: the ceramic particle size distribution and weight load, the polymer molecular weight and chemical composition and the solvated Li-salt composition and content. Unhindered ion transport across interfaces between the composites and the battery electrode materials is paramount for battery performance. To this end, we are investigating the effect of interface morphology, its atomic composition and exploring novel electrode structures that facilitate ionic transport.

Microwave-assisted synthesis of gold, silver, platinum and palladium nanostructures and their use in electrocatalytic applications.

PubMed

Safavi, Afsaneh; Tohidi, Maryam

2014-09-01

Microwave-assisted ionic liquid method was used for synthesis of various noble metals, such as gold, silver, platinum and palladium nanomaterials. This route does not employ any template agent, surface capping agents or reducing agents. The process is fast, simple and of high yield. Different metal precursors in various ionic liquids media (1-butyl-3-methylimidazolium tetrafluoroborate, octyl pyridinium hexaflurophosphate and 1-octyl-3-methylimidazolium hexaflurophosphate) were applied to produce metal nanomaterials. Silver, platinium and palladium nanoparticles exhibit spherical morphology while nanosheets with high aspect ratio were obtained for gold. These metal nanostructures were incorporated into a carbon ionic liquid electrode to investigate their electrocatalytic properties. It was found that synthesis in different ionic liquids result in different activity. Excellent electrocatalytic effects toward adenine, hydrazine, formaldehyde and ethanol were observed for the modified electrodes with different nanoparticles synthesized in 1-butyl-3-methylimidazolium tetrafluoroborate. The high conductivity, large surface-to-volume ratio and active sites of nanosized metal particles are responsible for their electrocatalytic activity. In contrast, the carbon ionic liquid electrode modified with synthesized metal nanoparticles in octyl pyridinium hexaflurophosphate and 1-octyl-3-methylimidazolium hexaflurophosphate showed negligible activity for detection of these probes.

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

PubMed

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

2016-05-25

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

A Water Dissolvable Electrolyte with an Ionic Liquid for Eco-Friendly Electronics.

PubMed

Yamada, Shunsuke; Toshiyoshi, Hiroshi

2018-06-21

A water-dissolvable electrolyte is developed by combining an ionic liquid (IL) with poly(vinyl alcohol) (PVA), which decays over time by contact with water. An IL generally consists of two species of ions (anion and cation), and forms an electrical double layer (EDL) of a large electrostatic capacitance due to the ions accumulated in the vicinity of a conductive electrode when voltage is applied. In a similar manner, the ionic gel developed in this work forms an EDL due to the ions suspended in the conjugated polymer network while maintaining the gel form. Test measurements show a large capacitance of 13 µF cm -2 within the potential window of the IL. The ionic gel shows an electrical conductance of 20 µS cm -1 due to the ionic conduction, which depends on the weight ratio of the IL with respect to the polymer. The developed ionic gel dissolves into water in 16 h. Potential application includes the electrolyte in disposable electronics such as distributed sensors and energy harvesters that are supposed to be harmless to environment. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoporous adsorption effect on altering Li+ diffusion pathway by a highly ordered porous electrolyte additive for high rate all-solid-state lithium metal batteries.

PubMed

Li, Wenwen; Zhang, Sanpei; Wang, Bangrun; Gu, Sui; Xu, Dong; Wang, Jianing; Chen, Chunhua; Wen, Zhaoyin

2018-06-19

Solid polymer electrolytes (SPEs) have shown extraordinary promise for all-solid-state lithium metal batteries with high energy density and flexibility but are mainly limited by the low ionic conductivity and their poor stability with lithium metal anode. In this work, we propose a highly ordered porous electrolyte additive derived from SSZ-13 for high-rate all-solid-state lithium metal batteries. The nanoporous adsorption effect provided by the highly ordered porous nanoparticles in the poly (ethylene oxide) (PEO) electrolyte are found to significantly improve the Li + conductivity (1.91×10 -3 S cm -1 at 60°C, 4.43×10 -5 S cm -1 at 20°C) and widen the electrochemical stability window to 4.7 V vs Li + /Li. Meanwhile, the designed PEO-based electrolyte demonstrates enhanced stability with the lithium metal anode. Through systematically increasing Li + diffusion, widening the electrochemical stability window and enhancing the stability of the SSZ-CPE electrolyte, the LiFePO4/SSZ-CPE/Li cell is optimized to deliver high-rate capability and stable cycling performance, which demonstrates great potential for all-solid-state energy storage application.

Creating Lithium-Ion Electrolytes with Biomimetic Ionic Channels in Metal-Organic Frameworks.

PubMed

Shen, Li; Wu, Hao Bin; Liu, Fang; Brosmer, Jonathan L; Shen, Gurong; Wang, Xiaofeng; Zink, Jeffrey I; Xiao, Qiangfeng; Cai, Mei; Wang, Ge; Lu, Yunfeng; Dunn, Bruce

2018-06-01

Solid-state electrolytes are the key to the development of lithium-based batteries with dramatically improved energy density and safety. Inspired by ionic channels in biological systems, a novel class of pseudo solid-state electrolytes with biomimetic ionic channels is reported herein. This is achieved by complexing the anions of an electrolyte to the open metal sites of metal-organic frameworks (MOFs), which transforms the MOF scaffolds into ionic-channel analogs with lithium-ion conduction and low activation energy. This work suggests the emergence of a new class of pseudo solid-state lithium-ion conducting electrolytes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed Central

Tan, Ming; Lu, Jingting; Zhang, Yang; Jiang, Heqing

2017-01-01

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. PMID:28961187

Developing a polymeric sensor to monitor intracellular conditions

NASA Astrophysics Data System (ADS)

Mudarri, Timothy C.; Leo, Donald J.; Wood, Brett C.; Shires, Peter K.

2004-07-01

Ionic electroactive polymers have been developed as mechanical sensors or actuators, taking advantage of the electromechanical coupling of the materials. This research attempts to take advantage of the chemomechanical and chemoelectrical coupling by characterizing the transient response as the polymer undergoes an ion exchange, thus using the polymer for ionic sensing. Nafion is a biocompatible material, and an implantable polymeric ion sensor which has applications in the biomedical field for bone healing research. An ion sensor and a strain gauge could determine the effects of motion allowed at the fracture site, thus improving rehabilitation procedures for bone fractures. The charge sensitivity of the material and the capacitance of the material were analyzed to determine the transient response. Both measures indicate a change when immersed in ionic salt solutions. It is demonstrated that measuring the capacitance is the best indicator of an ion exchange. Relative to a flat response in deionized water (+/-2%), the capacitance of the polymer exhibits an exponential decay of ~25% of its peak when placed in a salt solution. A linear correlation between the time constant of the decay and the ionic size of the exchanging ion was developed that could reasonably predict a diffusing ion. Tests using an energy dispersive spectrometer (EDS) indicate that 90% of the exchange occurs in the first 20 minutes, shown by both capacitance decay and an atomic level scan. The diffusion rate time constant was found to within 0.3% of the capacitance time constant, confirming the ability of capacitance to measure ion exchange.

Acidic Ionic Liquids.

PubMed

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.

Room temperature electrodeposition of actinides from ionic solutions

DOEpatents

Hatchett, David W.; Czerwinski, Kenneth R.; Droessler, Janelle; Kinyanjui, John

2017-04-25

Uranic and transuranic metals and metal oxides are first dissolved in ozone compositions. The resulting solution in ozone can be further dissolved in ionic liquids to form a second solution. The metals in the second solution are then electrochemically deposited from the second solutions as room temperature ionic liquid (RTIL), tri-methyl-n-butyl ammonium n-bis(trifluoromethansulfonylimide) [Me.sub.3N.sup.nBu][TFSI] providing an alternative non-aqueous system for the extraction and reclamation of actinides from reprocessed fuel materials. Deposition of U metal is achieved using TFSI complexes of U(III) and U(IV) containing the anion common to the RTIL. TFSI complexes of uranium were produced to ensure solubility of the species in the ionic liquid. The methods provide a first measure of the thermodynamic properties of U metal deposition using Uranium complexes with different oxidation states from RTIL solution at room temperature.

21 CFR 888.3550 - Knee joint patellofemorotibial polymer/metal/metal constrained cemented prosthesis.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Knee joint patellofemorotibial polymer/metal/metal... § 888.3550 Knee joint patellofemorotibial polymer/metal/metal constrained cemented prosthesis. (a) Identification. A knee joint patellofemorotibial polymer/metal/metal constrained cemented prosthesis is a device...

21 CFR 888.3550 - Knee joint patellofemorotibial polymer/metal/metal constrained cemented prosthesis.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Knee joint patellofemorotibial polymer/metal/metal... § 888.3550 Knee joint patellofemorotibial polymer/metal/metal constrained cemented prosthesis. (a) Identification. A knee joint patellofemorotibial polymer/metal/metal constrained cemented prosthesis is a device...

21 CFR 888.3550 - Knee joint patellofemorotibial polymer/metal/metal constrained cemented prosthesis.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Knee joint patellofemorotibial polymer/metal/metal... § 888.3550 Knee joint patellofemorotibial polymer/metal/metal constrained cemented prosthesis. (a) Identification. A knee joint patellofemorotibial polymer/metal/metal constrained cemented prosthesis is a device...

21 CFR 888.3550 - Knee joint patellofemorotibial polymer/metal/metal constrained cemented prosthesis.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Knee joint patellofemorotibial polymer/metal/metal... § 888.3550 Knee joint patellofemorotibial polymer/metal/metal constrained cemented prosthesis. (a) Identification. A knee joint patellofemorotibial polymer/metal/metal constrained cemented prosthesis is a device...

21 CFR 888.3550 - Knee joint patellofemorotibial polymer/metal/metal constrained cemented prosthesis.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Knee joint patellofemorotibial polymer/metal/metal... § 888.3550 Knee joint patellofemorotibial polymer/metal/metal constrained cemented prosthesis. (a) Identification. A knee joint patellofemorotibial polymer/metal/metal constrained cemented prosthesis is a device...

21 CFR 888.3220 - Finger joint metal/polymer constrained cemented prosthesis.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Finger joint metal/polymer constrained cemented... metal/polymer constrained cemented prosthesis. (a) Identification. A finger joint metal/polymer..., 1996 for any finger joint metal/polymer constrained cemented prosthesis that was in commercial...

21 CFR 888.3220 - Finger joint metal/polymer constrained cemented prosthesis.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Finger joint metal/polymer constrained cemented... metal/polymer constrained cemented prosthesis. (a) Identification. A finger joint metal/polymer..., 1996 for any finger joint metal/polymer constrained cemented prosthesis that was in commercial...

21 CFR 888.3220 - Finger joint metal/polymer constrained cemented prosthesis.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Finger joint metal/polymer constrained cemented... metal/polymer constrained cemented prosthesis. (a) Identification. A finger joint metal/polymer..., 1996 for any finger joint metal/polymer constrained cemented prosthesis that was in commercial...

21 CFR 888.3220 - Finger joint metal/polymer constrained cemented prosthesis.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Finger joint metal/polymer constrained cemented... metal/polymer constrained cemented prosthesis. (a) Identification. A finger joint metal/polymer..., 1996 for any finger joint metal/polymer constrained cemented prosthesis that was in commercial...

21 CFR 888.3220 - Finger joint metal/polymer constrained cemented prosthesis.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Finger joint metal/polymer constrained cemented... metal/polymer constrained cemented prosthesis. (a) Identification. A finger joint metal/polymer..., 1996 for any finger joint metal/polymer constrained cemented prosthesis that was in commercial...

Ionic Liquids as a Basis Context for Developing High school Chemistry Teaching Materials

NASA Astrophysics Data System (ADS)

Hernani; Mudzakir, A.; Sumarna, O.

2017-02-01

This research aims to produce a map of connectedness highschool chemical content with the context of the modern chemical materials applications based on ionic liquids. The research method is content analysis of journal articles related to the ionic liquid materials and the textbooks of high school chemistry and textbooks of general chemistry at the university. The instrument used is the development format of basic text that connect and combine content and context. The results showed the connectedness between: (1) the context lubricants ionic liquid with the content of ionic bonding, covalent bonding, metal bonding, interaction between the particles of matter, the elements of main group, the elements of transition group, and the classification of macromolecules; (2) the context of fuel cell electrolite with the content of ionic bonding, covalent bonding, metal bonding, interaction between the particles of matter, Volta cell, and electrolysis cell; (3) the contect of nanocellulose with the content of ionic bonding, covalent bonding, metal bonding, interaction between the particles of matter, colloid, carbon compound, and the classification of macromolecules; and (4) the context of artificial muscle system with the content of ionic bond, covalent bond, metal bonding, interaction between the particles of matter, hydrocarbons, electrolytes and non-electrolytes, and the classification of macromolecules. Based on the result of this content analysis, the context of ionic liquid is predicted can be utilized for the enrichment of high school chemistry and has the potential to become teaching material’s context of high school chemistry in the future.

The use of ionic liquids based on choline chloride for metal deposition: A green alternative?

PubMed

Haerens, Kurt; Matthijs, Edward; Chmielarz, Andrzej; Van der Bruggen, Bart

2009-08-01

Ionic liquids are studied intensively for different applications. They tend to be denoted as "green solvents", largely because of their low vapour pressure. In recent years toxicity and biotoxicity of ionic liquids have also been investigated, which proved that not all of these are "green". In this paper the use of ionic liquids based on choline chloride and ethylene glycol in electrochemistry is discussed in the context of their use as green solvents. Due to their low toxicity and ready biodegradability, these deep eutectic solvents are promising for the electrodeposition of metals. The influence of the use of these liquids as metal deposition baths on the waste water is investigated. Drag-out was found to be the most influencing parameter on the environmental impact of the process, as it is three times higher compared to classical solutions due to the higher viscosity of the ionic liquid. There are no major changes needed in the rinsing configuration of classic electroplating plants, and ion exchange to remove the metal out of the waste water was not hindered by the presence of the ionic liquid. The formation of by-products during the deposition of metals has to be further investigated and evaluated in consideration of the environmental impact.

Mass and charge transport in IPMC actuators with fractal interfaces

NASA Astrophysics Data System (ADS)

Chang, Longfei; Wu, Yucheng; Zhu, Zicai; Li, Heng

2016-04-01

Ionic Polymer-Metal Composite (IPMC) actuators have been attracting a growing interest in extensive applications, which consequently raises the demands on the accuracy of its theoretical modeling. For the last few years, rough landscape of the interface between the electrode and the ionic membrane of IPMC has been well-documented as one of the key elements to ensure a satisfied performance. However, in most of the available work, the interface morphology of IPMC was simplified with structural idealization, which lead to perplexity in the physical interpretation on its interface mechanism. In this paper, the quasi-random rough interface of IPMC was described with fractal dimension and scaling parameters. And the electro-chemical field was modeled by Poisson equation and a properly simplified Nernst-Planck equation set. Then, by simulation with Finite Element Method, a comprehensive analysis on he inner mass and charge transportation in IPMC actuators with different fractal interfaces was provided, which may be further adopted to instruct the performance-oriented interface design for ionic electro-active actuators. The results also verified that rough interface can impact the electrical and mechanical response of IPMC, not only from the respect of the real surface increase, but also from mass distribution difference caused by the complexity of the micro profile.

Covalent Incorporation of Ionic Liquid into Ion-Conductive Networks via Thiol-Ene Photopolymerization.

PubMed

Tibbits, Andrew C; Yan, Yushan S; Kloxin, Christopher J

2017-07-01

Ene-functionalized ionic liquids with a range of different cationic groups and counteranions react stoichiometrically within a tetrathiol-divinyl ether formulation within 20 minutes to form thiol-ene polymers with measurable ionic conductivities via a photoinitiated polymerization and crosslinking reaction. Dynamic mechanical analysis indicates that these networks are more spatially heterogeneous and possess higher glass transition temperatures (T g ) compared with thiol-ene formulations without charge. While tuning the molar content of ionic liquid monomer is one method for adjusting the crosslink and charge densities of the thiol-ene polymeric ionic liquid networks, the presence of cation-anion interactions also plays a critical role in dictating the thermomechanical and conductive properties. Particularly, while cationic structure effects are not significant on the polymer properties, the use of a weakly coordinating hydrophobic anion (bistriflimide) instead of bromide-based networks results in an apparent decrease in hydrated ion conductivity (7.4 to 1.5 mS cm -1 ) and T g (-9.6 to -17.8 °C). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed Central

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

21 CFR 888.3670 - Shoulder joint metal/polymer/metal nonconstrained or semi-constrained porous-coated uncemented...

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Shoulder joint metal/polymer/metal nonconstrained... ORTHOPEDIC DEVICES Prosthetic Devices § 888.3670 Shoulder joint metal/polymer/metal nonconstrained or semi-constrained porous-coated uncemented prosthesis. (a) Identification. A shoulder joint metal/polymer/metal...

The Effect of Hydrogen Bonding in Enhancing the Ionic Affinities of Immobilized Monoprotic Phosphate Ligands

DOE PAGES

Alexandratos, Spiro D.; Zhu, Xiaoping

2017-08-18

Environmental remediation requires ion-selective polymers that operate under a wide range of solution conditions. In one example, removal of trivalent and divalent metal ions from waste streams resulting from mining operations before they enter the environment requires treatment at acidic pH. The monoethyl ester phosphate ligands developed in this report operate from acidic solutions. They have been prepared on polystyrene-bound ethylene glycol, glycerol, and pentaerythritol, and it is found that intra-ligand hydrogen bonding affects their metal ion affinities. The affinity for a set of trivalent (Fe(III), Al(III), La(III), and Lu(III)) and divalent (Pb(II), Cd(II), Cu(II), and Zn(II)) ions is greatermore » than that of corresponding neutral diethyl esters and phosphonic acid. In an earlier study, hydrogen bonding was found important in determining the metal ion affinities of immobilized phosphorylated polyol diethyl ester coordinating ligands; their Fourier transform infrared (FTIR) band shifts indicated that the basicity of the phosphoryl oxygen increased by hydrogen bonding to auxiliary –OH groups on the neighboring polyol. The same mechanism is operative with the monoprotic resins along with hydrogen bonding to the P–OH acid site. This is reflected in the FTIR spectra: the neutral phosphate diethyl ester resins have the P=O band at 1265 cm -1 while the monoethyl ester resins have the band shifted to 1230 cm -1; hydrogen bonding is further indicated by the broadness of this region down to 900 cm -1. Of the polymers studied, monoprotic pentaerythritol has the highest metal ion affinities.« less

The Effect of Hydrogen Bonding in Enhancing the Ionic Affinities of Immobilized Monoprotic Phosphate Ligands

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

Alexandratos, Spiro D.; Zhu, Xiaoping

Environmental remediation requires ion-selective polymers that operate under a wide range of solution conditions. In one example, removal of trivalent and divalent metal ions from waste streams resulting from mining operations before they enter the environment requires treatment at acidic pH. The monoethyl ester phosphate ligands developed in this report operate from acidic solutions. They have been prepared on polystyrene-bound ethylene glycol, glycerol, and pentaerythritol, and it is found that intra-ligand hydrogen bonding affects their metal ion affinities. The affinity for a set of trivalent (Fe(III), Al(III), La(III), and Lu(III)) and divalent (Pb(II), Cd(II), Cu(II), and Zn(II)) ions is greatermore » than that of corresponding neutral diethyl esters and phosphonic acid. In an earlier study, hydrogen bonding was found important in determining the metal ion affinities of immobilized phosphorylated polyol diethyl ester coordinating ligands; their Fourier transform infrared (FTIR) band shifts indicated that the basicity of the phosphoryl oxygen increased by hydrogen bonding to auxiliary –OH groups on the neighboring polyol. The same mechanism is operative with the monoprotic resins along with hydrogen bonding to the P–OH acid site. This is reflected in the FTIR spectra: the neutral phosphate diethyl ester resins have the P=O band at 1265 cm -1 while the monoethyl ester resins have the band shifted to 1230 cm -1; hydrogen bonding is further indicated by the broadness of this region down to 900 cm -1. Of the polymers studied, monoprotic pentaerythritol has the highest metal ion affinities.« less

Electrostatic interactions between ions near Thomas-Fermi substrates and the surface energy of ionic crystals at imperfect metals.

PubMed

Kaiser, V; Comtet, J; Niguès, A; Siria, A; Coasne, B; Bocquet, L

2017-07-01

The electrostatic interaction between two charged particles is strongly modified in the vicinity of a metal. This situation is usually accounted for by the celebrated image charges approach, which was further extended to account for the electronic screening properties of the metal at the level of the Thomas-Fermi description. In this paper we build upon a previous approach [M. A. Vorotyntsev and A. A. Kornyshev, Zh. Eksp. Teor. Fiz., 1980, 78(3), 1008-1019] and successive works to calculate the 1-body and 2-body electrostatic energy of ions near a metal in terms of the Thomas-Fermi screening length. We propose workable approximations suitable for molecular simulations of ionic systems close to metallic walls. Furthermore, we use this framework to calculate analytically the electrostatic contribution to the surface energy of a one dimensional crystal at a metallic wall and its dependence on the Thomas-Fermi screening length. These calculations provide a simple interpretation for the surface energy in terms of image charges, which allows for an estimation of the interfacial properties in more complex situations of a disordered ionic liquid close to a metal surface. The counter-intuitive outcome is that electronic screening, as characterized by a molecular Thomas-Fermi length l TF , profoundly affects the wetting of ionic systems close to a metal, in line with the recent experimental observation of capillary freezing of ionic liquids in metallic confinement.

Novel polymer electrolytes based on cationic polyurethane with different alkyl chain length

NASA Astrophysics Data System (ADS)

Liu, Libin; Wu, Xiwen; Li, Tianduo

2014-03-01

A series of comb-like cationic polyurethanes (PUs) were synthesized by quaternizing different bromoalkane (C2H5Br, C8H17Br, and C14H29Br) with polyurethane. Solid polymer electrolytes were prepared by complexes cationic PUs with different content of LiClO4. All the solid polymer electrolytes had sufficient thermal stability as confirmed by TGA and exhibited a single-phase behavior evidenced by DSC results. For these electrolytes, FT-IR spectra indicated the formation of polymer-ion complexes. The ac impedance spectra show that the conductivity of the electrolytes follow the Arrhenius behavior, and ionic conductivity is associated with both the charge migration of ions between coordination sites and transmission between aggregates, as confirmed by FT-IR and SEM. Alkyl quaternary ammonium salts in the polymer backbone are recognized as inherent plasticizers, which make the electrolytes exhibit liquid-like behavior. The plasticizing effect of PU-C8 and PU-C14 electrolytes are more effective than that of PU-C2 electrolyte. Maximum ionic conductivity at room temperature for PU-C8 electrolytes containing 50 wt% LiClO4 reached 1.1 × 10-4 S cm-1. This work provides a new research clue that alkyl quaternary ammonium salts could be used as inherent plasticizers and hence make the system behave like a liquid with high ionic conductivity, while preserving the dimensional stability of the solids.

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

PubMed

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.

Electrical conductivity studies on Ammonium bromide incorporated with Zwitterionic polymer blend electrolyte for battery application

NASA Astrophysics Data System (ADS)

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

2017-06-01

Solid polymer blend electrolytes are widely studied due to their extensive applications particularly in electrochemical devices. Blending polymer makes the thermal stability, higher mechanical strength and inorganic salt provide ionic charge carrier to enhance the conductivity. In these studies, 50% polyvinyl alcohol (PVA), 50% poly (N-vinyl pyrrolidone) (PVP) and 2.5% L-Asparagine mixed with different ratio of the Ammonium bromide (NH4Br), have been synthesized using solution casting technique. The prepared PVA/PVP/L-Asparagine/doped-NH4Br polymer blend electrolyte films have been characterized by various analytical methods such as FT-IR, XRD, impedance spectroscopy, TG-DSC and scanning electron microscopy. FT-IR, XRD and TG/DSC analysis revealed the structural and thermal behavior of the complex formation between PVA/PVP/L-Asparagine/doped-NH4Br. The ionic conductivity and the dielectric properties of PVA/PVP/L-Asparagine/doped-NH4Br polymer blend electrolyte films were examined using impedance analysis. The highest ionic conductivity was found to be 2.34×10-4 S cm-1 for the m.wt. composition of 50%PVA:50%PVP:2.5%L-Asparagine:doped 0.15 g NH4Br at ambient temperature. Solid state proton battery is fabricated and the observed open circuit voltage is 1.1 V and its performance has been studied.

Heterogeneous catalyst for the production of ethylidene diacetate from acetic anhydride

DOEpatents

Ramprasad, D.; Waller, F.J.

1998-06-16

This invention relates to a process for producing ethylidene diacetate by the reaction of acetic anhydride, acetic acid, hydrogen and carbon monoxide at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that is stable to hydrogenation and comprises an insoluble polymer having pendant quaternized heteroatoms, some of which heteroatoms are ionically bonded to anionic Group VIII metal complexes, the remainder of the heteroatoms being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled without loss in activity.

Heterogeneous catalyst for the production of ethylidene diacetate from acetic anhydride

DOEpatents

Ramprasad, Dorai; Waller, Francis Joseph

1998-01-01

This invention relates to a process for producing ethylidene diacetate by the reaction of acetic anhydride, acetic acid, hydrogen and carbon monoxide at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that is stable to hydrogenation and comprises an insoluble polymer having pendant quaternized heteroatoms, some of which heteroatoms are ionically bonded to anionic Group VIII metal complexes, the remainder of the heteroatoms being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled without loss in activity.

21 CFR 888.3358 - Hip joint metal/polymer/metal semi-constrained porous-coated uncemented prosthesis.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Hip joint metal/polymer/metal semi-constrained... Devices § 888.3358 Hip joint metal/polymer/metal semi-constrained porous-coated uncemented prosthesis. (a) Identification. A hip joint metal/polymer/metal semi-constrained porous-coated uncemented prosthesis is a device...

Metal-containing and related polymers for biomedical applications.

PubMed

Yan, Yi; Zhang, Jiuyang; Ren, Lixia; Tang, Chuanbing

2016-10-07

A survey of the most recent progress in the biomedical applications of metal-containing polymers is given. Due to the unique optical, electrochemical, and magnetic properties, at least 30 different metal elements, most of them transition metals, are introduced into polymeric frameworks for interactions with biology-relevant substrates via various means. Inspired by the advance of metal-containing small molecular drugs and promoted by the great progress in polymer chemistry, metal-containing polymers have gained momentum during recent decades. According to their different applications, this review summarizes the following biomedical applications: (1) metal-containing polymers as drug delivery vehicles; (2) metal-containing polymeric drugs and biocides, including antimicrobial and antiviral agents, anticancer drugs, photodynamic therapy agents, radiotherapy agents and biocides; (3) metal-containing polymers as biosensors, and (4) metal-containing polymers in bioimaging.

Ionic electroactive polymer artificial muscles in space applications

PubMed Central

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

2014-01-01

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. PMID:25372857

21 CFR 888.3120 - Ankle joint metal/polymer non-constrained cemented prosthesis.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Ankle joint metal/polymer non-constrained cemented... metal/polymer non-constrained cemented prosthesis. (a) Identification. An ankle joint metal/polymer non... December 26, 1996 for any ankle joint metal/polymer non-constrained cemented prosthesis that was in...

21 CFR 888.3120 - Ankle joint metal/polymer non-constrained cemented prosthesis.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Ankle joint metal/polymer non-constrained cemented... metal/polymer non-constrained cemented prosthesis. (a) Identification. An ankle joint metal/polymer non... December 26, 1996 for any ankle joint metal/polymer non-constrained cemented prosthesis that was in...

21 CFR 888.3120 - Ankle joint metal/polymer non-constrained cemented prosthesis.

Code of Federal Regulations, 2011 CFR

2011-04-01

... substantially equivalent to an ankle joint metal/polymer non-constrained cemented prosthesis that was in... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Ankle joint metal/polymer non-constrained cemented... metal/polymer non-constrained cemented prosthesis. (a) Identification. An ankle joint metal/polymer non...

21 CFR 888.3120 - Ankle joint metal/polymer non-constrained cemented prosthesis.

Code of Federal Regulations, 2012 CFR

2012-04-01

... substantially equivalent to an ankle joint metal/polymer non-constrained cemented prosthesis that was in... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Ankle joint metal/polymer non-constrained cemented... metal/polymer non-constrained cemented prosthesis. (a) Identification. An ankle joint metal/polymer non...

21 CFR 888.3120 - Ankle joint metal/polymer non-constrained cemented prosthesis.

Code of Federal Regulations, 2014 CFR

2014-04-01

... substantially equivalent to an ankle joint metal/polymer non-constrained cemented prosthesis that was in... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Ankle joint metal/polymer non-constrained cemented... metal/polymer non-constrained cemented prosthesis. (a) Identification. An ankle joint metal/polymer non...

New Class of Flow Batteries for Terrestrial and Aerospace Energy Storage Applications

NASA Technical Reports Server (NTRS)

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

2013-01-01

Future sustainable energy generation technologies such as photovoltaic and wind farms require advanced energy storage systems on a massive scale to make the alternate (green) energy options practical. The daunting requirements of such large-scale energy systems such as long operating and cycle life, safety, and low cost are not adequately met by state-of-the-art energy storage technologies such as vanadium flow cells, lead-acid, and zinc-bromine batteries. Much attention is being paid to redox batteries specifically to the vanadium redox battery (VRB) due to their simplicity, low cost, and good life characteristics compared to other related battery technologies. NASA is currently seeking high-specific- energy and long-cycle-life rechargeable batteries in the 10-to-100-kW range to support future human exploration missions, such as planetary habitats, human rovers, etc. The flow batteries described above are excellent candidates for these applications, as well as other applications that propose to use regenerative fuel cells. A new flow cell technology is proposed based on coupling two novel electrodes in the form of solvated electron systems (SES) between an alkali (or alkaline earth) metal and poly aromatic hydrocarbons (PAH), separated by an ionically conducting separator. The cell reaction involves the formation of such SES with a PAH of high voltage in the cathode, while the alkali (or alkaline earth metal) is reduced from such an MPAH complex in the anode half-cell. During recharge, the reactions are reversed in both electrodes. In other words, the alkali (alkaline earth) metal ion simply shuttles from one M-PAH complex (SES) to another, which are separated by a metal-ion conducting solid or polymer electrolyte separator. As an example, the concept was demonstrated with Li-naphthalene//Li DDQ (DDQ is 2,3-Dichloro-5,6-dicyano- 1,4-benzoquinone) separated by lithium super ion conductor, either ceramic or polymer (solid polymer or gel polymer) electrolytes. The reactants are Li-naphthalene dissolved in tetrahydrofuran (THF) with a lithium salt of 1M LiBF4 (lithium tetra fluoroborate) in the anode compartment, and DDQ again dissolved in THF and also containing 1M LiBF4 salt in the cathode half-cell. The solid electrolyte separator used in the first set of experiments is a ceramic solid electrolyte, available from a commercial source. The open circuit voltage of the cells is close to 3.0 V, as expected from the individual half-cell voltages of Li-naphthalene and Li-DDQ. Upon discharge, the cell shows steady discharge voltage of 2.7 V, which confirms that the electrochemical processes do involve lithium ion shuttling from the anodic compartment to the cathode half-cell. The reversibility or rechargeability is demonstrated by charging the partially discharged cells (i.e., with lithium present in the DDQ half). Once again, a steady voltage close to 3.0 V was observed during charge, indicating that the system is quite reversible. In the subsequent concept-demonstration studies, the ceramic electrolyte has been replaced with a gel polymer electrolyte, e.g., PVDF-HFP (poly vinylene difluoride hexafluoropropene) gel, which has several advantages such as high ionic conductivity (almost comparable to liquid electrolyte and about 2 orders of magnitude better than the ceramic equivalent), lower cost, and possibly higher chemical stability at the anode. In addition, it can be bonded to the electrode by thermal fusion to form membrane electrode assemblies (MEAs), as is done in fuel cells.

Comparative activity of silver based antimicrobial composites for urinary catheters.

PubMed

Thokala, Nikhil; Kealey, Carmel; Kennedy, James; Brady, Damien B; Farrell, Joseph

2018-04-04

Biomedical polymers are an integral component in a wide range of medical device designs due to their range of desirable properties. However, extensive use of polymer materials in medical devices have also been associated with an increasing incidence of patient infections. Efforts to address this issue have included the incorporation of antimicrobial additives for developing novel antimicrobial polymeric materials. Silver with its high toxicity towards bacteria, oligodynamic effect and good thermal stability has been employed as an additive for polymeric medical devices. In the present study, commercially available elemental (Biogate) and ionic (Ultrafresh 16) silver additives were incorporated into a Polyamide 11 (PA 11) matrix using a compression press. These polymer composites were evaluated for their antimicrobial and ion release properties. Elemental silver composites were determined to retain their antimicrobial properties for extended periods and actively release silver ions for 84 days; whereas the ionic silver composites lost their ion release activity and therefore antibacterial activity after 56 days. Bacterial log reduction units of 3.87 for ionic silver and 2.41 for elemental silver was identified within 24 hr, when tested in accordance with ISO 22196 test standard; indicating that ionic silver is more efficient for short-term applications compared to elemental silver. Copyright © 2018 Elsevier Ltd. All rights reserved.

Innovative Poly(Ionic Liquid)s by the Polymerization of Deep Eutectic Monomers.

PubMed

Isik, Mehmet; Ruiperez, Fernando; Sardon, Haritz; Gonzalez, Alba; Zulfiqar, Sonia; Mecerreyes, David

2016-07-01

The incorporation of ionic liquid (IL) chemistry into functional polymers has extended the properties and applications of polyelectrolytes. However, ILs are expensive due to the presence of fluorinated anions or complicated synthetic steps which limit their technological viability. Here, we show a new family of poly(ionic liquid)s (PILs) which are based in cheap and renewable chemicals and involves facile synthetic approaches. Thus, deep eutectic monomers (DEMs) are prepared for the first time by using quaternary ammonium compounds and various hydrogen bond donors such as citric acid, terephthalic acid or an amidoxime. The deep eutectic formation is made through a simple mixing of the ingredients. Differential scanning calorimetry, nuclear magnetic resonance (NMR) and computational studies reveal the formation of the DEMs due to the ionic interactions. The resulting DEMs are liquid which facilitates their polymerization using mild photopolymerization or polycondensation strategies. Spectroscopic characterizations reveal the successful formation of the polymers. By this way, a new family of PILs can be synthesized which can be used for different applications. As an example, the polymers show promising performance as solid CO2 sorbents. Altogether the deep eutectic monomer route can lead to non-toxic, cheap and easy-to-prepare alternatives to current PILs for different applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural Effects of Gating Poly(3-hexylthiophene) through an Ionic Liquid

DOE PAGES

Guardado, Jesus O.; Salleo, Alberto

2017-07-17

Ionic liquids are increasingly employed as dielectrics to generate high charge densities and enable low-voltage operation with organic semiconductors. But, effects on structure and morphology of the active material are not fully known, particularly for permeable semiconductors such as conjugated polymers, in which ions from the ionic liquid can enter and electrochemically dope the semicrystalline film. In order to understand when ions enter, where they go, and how they affect the film, thin films of the archetypal semiconducting polymer, poly(3-hexylthiophene), are electrochemically doped with 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, the archetypal ionic liquid. High-resolution, ex situ X-ray diffraction measurements and complete pole figuresmore » reveal changes with applied voltage, cycling, and frequency in lattice spacing, crystallite orientation, and crystallinity in the bulk and at the buried interface. Dopant ions penetrate the film and enter the crystallites at sufficiently high voltages and low frequencies. Upon infiltrating crystallites, ions permanently expand lamellar stacking and contract pi-stacking. Cycling amplifies these effects, but higher frequencies mitigate the expansion of bulk crystallites as ions are hindered from entering crystallites. Furthermore, this mechanistic understanding of the structural effects of ion penetration will help develop models of the frequency and voltage impedance response of electrochemically doped conjugated polymers and advance electronic applications.« less

On the structural and impedance characteristics of Li- doped PEO, using n-butyl lithium in hexane as dopant

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

Anand, P. B., E-mail: anandputhirath@gmail.com, E-mail: jayalekshmi@cusat.ac.in; Jayalekshmi, S., E-mail: anandputhirath@gmail.com, E-mail: jayalekshmi@cusat.ac.in

2014-01-28

Nowadays polymer based solid state electrolytes for applications in rechargeable battery systems are highly sought after materials, pursued extensively by various research groups worldwide. Numerous methods are discussed in literature to improve the fundamental properties like electrical conductivity, mechanical stability and interfacial stability of polymer based electrolytes. The application of these electrolytes in Li-ion cells is still in the amateur state, due to low ionic conductivity, low lithium transport number and the processing difficulties. The present work is an attempt to study the effects of Li doping on the structural and transport properties of the polymer electrolyte, poly-ethelene oxide (PEO)more » (Molecular weight: 200,000). Li doped PEO was obtained by treating PEO with n-Butyllithium in hexane for different doping concentrations. Structural characterization of the samples was done by XRD and FTIR techniques. Impedance measurements were carried out to estimate the ionic conductivity of Li doped PEO samples. It is seen that, the crystallinity of the doped PEO decreases on increasing the doping concentration. XRD and FTIR studies support this observation. It is inferred that, ionic conductivity of the sample is increasing on increasing the doping concentration since less crystallinity permits more ionic transport. Impedance measurements confirm the results quantitatively.« less

Structural Effects of Gating Poly(3-hexylthiophene) through an Ionic Liquid

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

Guardado, Jesus O.; Salleo, Alberto

Ionic liquids are increasingly employed as dielectrics to generate high charge densities and enable low-voltage operation with organic semiconductors. But, effects on structure and morphology of the active material are not fully known, particularly for permeable semiconductors such as conjugated polymers, in which ions from the ionic liquid can enter and electrochemically dope the semicrystalline film. In order to understand when ions enter, where they go, and how they affect the film, thin films of the archetypal semiconducting polymer, poly(3-hexylthiophene), are electrochemically doped with 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, the archetypal ionic liquid. High-resolution, ex situ X-ray diffraction measurements and complete pole figuresmore » reveal changes with applied voltage, cycling, and frequency in lattice spacing, crystallite orientation, and crystallinity in the bulk and at the buried interface. Dopant ions penetrate the film and enter the crystallites at sufficiently high voltages and low frequencies. Upon infiltrating crystallites, ions permanently expand lamellar stacking and contract pi-stacking. Cycling amplifies these effects, but higher frequencies mitigate the expansion of bulk crystallites as ions are hindered from entering crystallites. Furthermore, this mechanistic understanding of the structural effects of ion penetration will help develop models of the frequency and voltage impedance response of electrochemically doped conjugated polymers and advance electronic applications.« less

Swelling and erosion properties of hydroxypropylmethylcellulose (Hypromellose) matrices--influence of agitation rate and dissolution medium composition.

PubMed

Kavanagh, Nicole; Corrigan, Owen I

2004-07-26

The effect of dissolution medium variables, such as medium composition, ionic strength and agitation rate, on the swelling and erosion of Hypromellose (hydroxypropylmethylcellulose, HPMC) matrices of different molecular weights was examined. Swelling and erosion of HPMC polymers was determined by measuring the wet and subsequent dry weights of matrices. It was possible to describe the rate of dissolution medium uptake in terms of a square root relationship and the erosion of the polymer in terms of the cube root law. The extent of swelling increased with increasing molecular weight, and decreased with increasing agitation rate. The erosion rate was seen to increase with decrease in polymer molecular weight, with a decrease in ionic strength and with increasing agitation rate. The sensitivity of polymer erosion to the degree of agitation may influence the ability of these polymers to give reproducible, agitation-independent release, compared to more rigid non-eroding matrix materials, in the complex hydrodynamic environment of the gastrointestinal tract.

``Smart'' Surfaces of Polymer Brushes

NASA Astrophysics Data System (ADS)

Wang, Qiang; Meng, Dong

2009-03-01

``Smart'' surfaces, also known as stimuli-responsive surfaces, can change their properties (e.g., wettability, adhesion, friction, elasticity, and biocompatibility) in response to external stimuli (e.g., temperature, pressure, light, solvent selectivity, ionic strength, type of salt, pH, applied electric field, etc.). In this work, we use numerical self-consistent field calculations to study in detail the structure and stimuli- responses of various polymer brushes, including (1) the thermo- response of PNIPAM brushes in water, (2) solvent-response of uncharged diblock copolymer brushes, and (3) the stimuli- response of charged two-component polymer brushes (including both the binary A/B brushes and diblock copolymer A-B brushes) to ionic strength, pH, and applied electric field. Among the many design parameters (e.g., chain lengths, grafting densities, A-B incompatibility, degree of ionization of charged polymers, etc.) we identify those that strongly affect the surface switchability. Such knowledge is useful to the experimental design of these smart polymer brushes for their applications.

Combinatorial synthesis and screening of non-biological polymers

DOEpatents

Schultz, Peter G.; Xiang, Xiao-Dong; Goldwasser, Isy; Briceno, Gabriel; Sun, Xiao-Dong; Wang, Kai-An

2006-04-25

Methods and apparatus for the preparation and use of a substrate having an array of diverse materials in predefined regions thereon. A substrate having an array of diverse materials thereon is generally prepared by delivering components of materials to predefined regions on a substrate, and simultaneously reacting the components to form at least two materials. Materials which can be prepared using the methods and apparatus of the present invention include, for example, covalent network solids, ionic solids and molecular solids. More particularly, materials which can be prepared using the methods and apparatus of the present invention include, for example, inorganic materials, intermetallic materials, metal alloys, ceramic materials, organic materials, organometallic materials, non-biological organic polymers, composite materials (e.g., inorganic composites, organic composites, or combinations thereof), etc. Once prepared, these materials can be screened for useful properties including, for example, electrical, thermal, mechanical, morphological, optical, magnetic, chemical, or other properties. Thus, the present invention provides methods for the parallel synthesis and analysis of novel materials having useful properties.

Polymer arrays from the combinatorial synthesis of novel materials

DOEpatents

Schultz, Peter G.; Xiang, Xiao-Dong; Goldwasser, Isy; Briceno, Gabriel; Sun, Xiao-Dong

2004-09-21

Methods and apparatus for the preparation and use of a substrate having an array of diverse materials in predefined regions thereon. A substrate having an array of diverse materials thereon is generally prepared by delivering components of materials to predefined regions on a substrate, and simultaneously reacting the components to form at least two materials. Materials which can be prepared using the methods and apparatus of the present invention include, for example, covalent network solids, ionic solids and molecular solids. More particularly, materials which can be prepared using the methods and apparatus of the present invention include, for example, inorganic materials, intermetallic materials, metal alloys, ceramic materials, organic materials, organometallic materials, non-biological organic polymers, composite materials (e.g., inorganic composites, organic composites, or combinations thereof), etc. Once prepared, these materials can be screened for useful properties including, for example, electrical, thermal, mechanical, morphological, optical, magnetic, chemical, or other properties. Thus, the present invention provides methods for the parallel synthesis and analysis of novel materials having useful properties.

The electrode/ionic liquid interface: electric double layer and metal electrodeposition.

PubMed

Su, Yu-Zhuan; Fu, Yong-Chun; Wei, Yi-Min; Yan, Jia-Wei; Mao, Bing-Wei

2010-09-10

The last decade has witnessed remarkable advances in interfacial electrochemistry in room-temperature ionic liquids. Although the wide electrochemical window of ionic liquids is of primary concern in this new type of solvent for electrochemistry, the unusual bulk and interfacial properties brought about by the intrinsic strong interactions in the ionic liquid system also substantially influence the structure and processes at electrode/ionic liquid interfaces. Theoretical modeling and experimental characterizations have been indispensable in reaching a microscopic understanding of electrode/ionic liquid interfaces and in elucidating the physics behind new phenomena in ionic liquids. This Minireview describes the status of some aspects of interfacial electrochemistry in ionic liquids. Emphasis is placed on high-resolution and molecular-level characterization by scanning tunneling microscopy and vibrational spectroscopies of interfacial structures, and the initial stage of metal electrodeposition with application in surface nanostructuring.

Electrical conductivity studies on (1-x)[PVA/PVP]: x[MgCl2{6H2O}] blend polymer electrolytes

NASA Astrophysics Data System (ADS)

Basha, S. K. Shahenoor; Reddy, K. Veera Bhadra; Rao, M. C.

2018-05-01

Blend polymer electrolytes of polyvinyl alcohol and polyvinyl pyrrolidone were prepared with different molecular wt% ratios of MgCl2.6H2O by solution cast technique. Electrical conductivity measurements for the prepared films were performed using Keithley electrometer model 6514 and the maximum ionic conductivity was found to be 1.01x10-3 S/cm at 373 K for the prepared composition of 35PVA/35PVP:30MgCl2.6H2O. The maximum ionic conductivity of polymer electrolyte has been used in fabrication of electrochemical cell with the configuration of Mg+/(PVA/PVP+MgCl2.6H2O)/(I2+C+electrolyte).

Training and shape retention in conducting polymer artificial muscles

NASA Astrophysics Data System (ADS)

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

2011-12-01

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

Novel proton conducting polymer electrolytes based on polyparabanic acid doped with H 3PO 4 for high temperature fuel cell

NASA Astrophysics Data System (ADS)

Aihara, Yuichi; Sonai, Atsuo

Three novel proton conducting polymer electrolytes based on polyparabanic acid doped with H 3PO 4 were synthesized and their use in high temperature fuel cells characterized. The precursor polymers, PMD-Im, POD-Im and PDMDP-Im, were synthesized by cyclization polymerization of diisocynanates. After doping with H 3PO 4, the ionic conductivity and the thermal degradation were studied by using the AC impedance method and thermal gravimetric analysis, respectively. These membranes showed high ionic conductivity of the order of 10 -2 S cm -1 at 423 K with good thermal stability. Their application to fuel cells was demonstrated and polarization curves were obtained at 423 K were obtained without humidification.

Simulation of Ionic Aggregation and Ion Dynamics in Model Ionomers

NASA Astrophysics Data System (ADS)

Frischknecht, Amalie L.

2012-02-01

Ionomers, polymers containing a small fraction of covalently bound ionic groups, are of interest as possible electrolytes in batteries. A single-ion conducting polymer electrolyte would be safer and have higher efficiency than the currently-used liquid electrolytes. However, to date ionomeric materials do not have sufficiently high conductivities for practical application. This is most likely because the ions tend to form aggregates, leading to slow ion transport. A key question is therefore how molecular structure affects the ionic aggregation and ion dynamics. To probe these structure-property relationships, we have performed molecular simulations of a set of recently synthesized poly(ethylene-co-acrylic acid) copolymers and ionomers, with a focus on the morphology of the ionic aggregates. The ionomers have a precise, constant spacing of charged groups, making them ideal for direct comparisons with simulations. Ab initio calculations give insight into the expected coordination of cations with fragments of the ionomers. All-atom molecular dynamics (MD) simulations of the ionomer melt show aggregation of the ionic groups into extended string-like clusters. An extensive set of coarse-grained molecular dynamics simulations extend the results to longer times and larger length scales. The structure factors calculated from the MD simulations compare favorably with x-ray scattering data. Furthermore, the simulations give a detailed picture of the sizes, shapes, and composition of the ionic aggregates, and how they depend on polymer architecture. Implications for ion transport will be discussed. [Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Method of making metal-polymer composite catalysts

DOEpatents

Zelena, Piotr [Los Alamos, NM; Bashyam, Rajesh [Los Alamos, NM

2009-06-23

A metal-polymer-carbon composite catalyst for use as a cathode electrocatalyst in fuel cells. The catalyst includes a heteroatomic polymer; a transition metal linked to the heteroatomic polymer by one of nitrogen, sulfur, and phosphorus, and a recast ionomer dispersed throughout the heteroatomic polymer-carbon composite. The method includes forming a heteroatomic polymer-carbon composite and loading the transition metal onto the composite. The invention also provides a method of making a membrane electrode assembly for a fuel cell that includes the metal-polymer-carbon composite catalyst.

Adaptive observer-based control for an IPMC actuator under varying humidity conditions

NASA Astrophysics Data System (ADS)

Bernat, Jakub; Kolota, Jakub

2018-05-01

As ionic polymer metal composites (IPMC) are increasingly applied to mechatronic systems, many new IPMC modeling efforts have been reported in the literature. The demands of rapidly growing technology has generated interest in advancing the intrinsic actuation and sensing capabilities of IPMC. Classical IPMC applications need constant hydration to operate. On the other hand, for IPMCs operating in air, the water content of the polymer varies with the humidity level of the ambient environment, which leads to its strong humidity-dependent behavior. Furthermore, decreasing water content over time plays a crucial role in the effectiveness of IPMC. Therefore, the primary challenge of this work is to accurately model this phenomenon. The principal contribution of the paper is a new IPMC model, which considers the change of moisture content. A novel nonlinear adaptive observer is designed to determine the unknown electric potential and humidity level in the polymer membrane. This approach effectively determines the moisture content of the IPMC during long-term continuous operation in air. This subsequently allows us to develop an effective back-stepping control algorithm that considers varying moisture content. Data from experiments are presented to support the effectiveness of the observation process, which is shown in illustrative examples.

Dynamic evolution of the oscillatory Belousov--Zhabotinsky reaction upon addition of a non-ionic polymer

NASA Astrophysics Data System (ADS)

Sciascia, Luciana; Lombardo, Renato; Turco Liveri, Maria Liria

2006-10-01

The dynamic evolution of the oscillatory Belousov-Zhabotinsky reaction upon addition of increasing amount of the non-ionic polymer polypropylene glycol with molecular weight 425 g mol -1 (PPG-425) was investigated in a stirred-batch reactor by monitoring the Ce(IV) absorbance changes. The oscillatory parameters are significantly altered by the presence of the polymer. The findings obtained in the present work revealed that the PPG-425 is not only more effective, than other polymer previously [R. Lombardo, C. Sbriziolo, M.L. Turco Liveri, K. Pelle, M. Wittmann, Z. Noszticzius, in: J.A. Pojman, Q. Tran-Cong-Miyata (Eds.), Nonlinear Dynamics in Polymeric Systems, American Chemical Society, Washington, DC, 869 (2004) 292] studied, in perturbing the BZ systems but also more capable of producing key radical species, which in turn can be exploited for the preparation of new polymeric materials.

Recent progress of task-specific ionic liquids in chiral resolution and extraction of biological samples and metal ions.

PubMed

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

2018-01-01

Ionic liquids have been functionalized for modern applications. The functional ionic liquids are also called task-specific ionic liquids. Various task-specific ionic liquids with certain groups have been constructed and exploited widely in the field of separation. To take advantage of their properties in separation science, task-specific ionic liquids are generally used in techniques such as liquid-liquid extraction, solid-phase extraction, gas chromatography, high-performance liquid chromatography, and capillary electrophoresis. This review mainly covers original research papers published in the last five years, and we will focus on task-specific ionic liquids as the chiral selectors in chiral resolution and as extractant or sensor for biological samples and metal ion purification. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

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

2006-06-01

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

Canopy Dynamics in Nanoscale Ionic Materials Probed by NMR

NASA Astrophysics Data System (ADS)

Mirau, Peter

2013-03-01

Nanoscale ionic materials (NIMs) are hybrids prepared from ionically functionalized nanoparticles (NP) neutralized by oligomeric polymer counter-ions. NIMs are designed to behave as liquids under ambient conditions in the absence of solvent and have no volatile organic content, making them useful for a number of applications. We have used NMR relaxation and pulse-field gradient NMR to probe local and collective canopy dynamics in NIMs based on silica nanoparticles (NP), fullerols and proteins in order to understand the relationship between the core and canopy structure and the bulk properties. The NMR studies show that the canopy dynamics depend on the degree of neutralization, the canopy radius of gyration and molecular crowding at the ionically modified NP surface. The viscosity in NIMs can be directly controlled with the addition of ions that enhance the exchange rate for polymers at the NP surface. These results show that NIMs for many applications can be prepared by controlling the dynamics of the NP interface.

Cluster Morphology-Polymer Dynamics Correlations in Sulfonated Polystyrene Melts: Computational Study

DOE PAGES

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

2016-04-11

Reaching exceptionally long times up to 500 ns in equilibrium and nonequilibrium molecular dynamics simulations studies, we have attained a fundamental molecular understanding of the correlation of ionomer clusters structure and multiscale dynamics, providing new insight into one critical, long-standing challenge in ionic polymer physics. The cluster structure in melts of sulfonated polystyrene with Na + and Mg 2+ counterions are resolved and correlated with the dynamics on multiple length and time scales extracted from measurements of the dynamic structure factor and shear rheology. We find that as the morphology of the ionic clusters changes from ladderlike for Na +more » to disordered structures for Mg 2+, the dynamic structure factor is affected on the length scale corresponding to the ionic clusters. Lastly, rheology studies show that the viscosity for Mg 2+ melts is higher than for Na + ones for all shear rates, which is well correlated with the larger ionic clusters’ size for the Mg 2+ melts.« less

Dependence of Ion Dynamics on the Polymer Chain Length in Poly(ethylene oxide)-Based Polymer Electrolytes.

PubMed

Chattoraj, Joyjit; Knappe, Marisa; Heuer, Andreas

2015-06-04

It is known from experiments that in the polymer electrolyte system, which contains poly(ethylene oxide) chains (PEO), lithium-cations (Li(+)), and bis(trifluoromethanesulfonyl)imide-anions (TFSI(-)), the cation and the anion diffusion and the ionic conductivity exhibit a similar chain-length dependence: with increasing chain length, they start dropping steadily, and later, they saturate to constant values. These results are surprising because Li-cations are strongly correlated with the polymer chains, whereas TFSI-anions do not have such bonding. To understand this phenomenon, we perform molecular dynamics simulations of this system for four different polymer chain lengths. The diffusion results obtained from our simulations display excellent agreement with the experimental data. The cation transport model based on the Rouse dynamics can successfully quantify the Li-diffusion results, which correlates Li diffusion with the polymer center-of-mass motion and the polymer segmental motion. The ionic conductivity as a function of the chain length is then estimated based on the chain-length-dependent ion diffusion, which shows a temperature-dependent deviation for short chain lengths. We argue that in the first regime, counterion correlations modify the conductivity, whereas for the long chains, the system behaves as a strong electrolyte.

Dual phase polymer gel electrolyte based on non-woven poly(vinylidenefluoride-co-hexafluoropropylene)–layered clay nanocomposite fibrous membranes for lithium ion batteries

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

Shubha, Nageswaran; Prasanth, Raghavan; Energy Research Institute - NTU

2013-02-15

Graphical abstract: Display Omitted Highlights: ► P(VdF-co-HFP)–clay nanocomposite based electrospun membranes are prepared. ► The membranes are used as polymer gel electrolyte (PGE) in lithium ion batteries. ► The composite PGE shows ionic conductivity of 5.5 mS cm{sup −1} at room temperature. ► Li/PGE/LiFePO{sub 4} cell delivers initial discharge capacity of 160 mAh g{sup −1}. ► The use of prepared electrolyte significantly improved the cell performance. -- Abstract: A new approach for fabricating polymer gel electrolytes (PGEs) based on electrospun poly(vinylidenefluoride-co-hexafluoropropylene) (P(VdF-co-HFP)) incorporated with layered nanoclay has been employed to enhance the ionic conductivity and electrochemical properties of P(VdF-co-HFP) withoutmore » compromising its mechanical strength. The effect of layered nanoclay on properties of membranes has been evaluated by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). Surface morphology of the membranes has been studied using field-emission scanning electron microscopy (FE-SEM). Polymer gel electrolytes are prepared by soaking the fibrous membrane into 1 M LiPF{sub 6} in EC/DEC. The electrochemical studies show that incorporation of layered nanoclay into the polymer matrix greatly enhanced the ionic conductivity and compatibility with lithium electrodes. The charge–discharge properties and cycling performance of Li/LiFePO{sub 4} cells comprising nanocomposite polymer gel electrolytes have been evaluated at room temperature.« less

Comparison between polymerized ionic liquids synthesized using chain-growth and step-growth mechanisms used as stationary phase in gas chromatography.

PubMed

Roeleveld, Kevin; David, Frank; Lynen, Frédéric

2016-06-17

In this study the merits of polymerized imidazolium based ionic liquid (PIL) stationary phases obtained via condensation and free radical polymerizations are compared as stationary phases in gas chromatography (GC). Poly(1-vinyl-3-butyl-imidazolium - bis(trifluoromethane)sulfonamide) (poly(ViC4Im(+) NTf2(-))) was obtained via a chain-growth mechanism while poly(propylimidazolium-NTf2) (poly(C3Im(+) NTf2(-))) was synthesized via a step-growth polymerization. The thermal stability of both polymers was assessed using thermal gravimetric analysis and compared with bleeding profiles obtained from the statically coated GC columns (30m×0.25mm×0.25μm). The performance was compared to what could be obtained on commercially available 1,5-di(2,3-dimethylimidazolium)pentane(2+) 2NTf2(-) (SLB-IL111) ionic liquid based columns. It was observed that the step-growth polymer was more thermally stable, up to 325°C, while the chain-growth polymer showed initial degradation at 250°C. Both polymers allowed reaching minimal plate heights of 0.400-0.500mm for retained solutes such as benzaldehyde, acetophenone, 1-methylnaphthalene and aniline. Assessment of the McReynolds constants illustrated that the polarity of the step-growth polymer was similar to the SLB-IL111 column, while displaying improved column stability. The PIL phases and particularly the so far little studied condensation based polymer shows particular retention and satisfactory column performance for polar moieties such as esters, amine and carbonyl functionalities. Copyright © 2016 Elsevier B.V. All rights reserved.

Selective extraction and recovery of rare earth metals from phosphor powders in waste fluorescent lamps using an ionic liquid system.

PubMed

Yang, Fan; Kubota, Fukiko; Baba, Yuzo; Kamiya, Noriho; Goto, Masahiro

2013-06-15

The recycling of rare earth metals from phosphor powders in waste fluorescent lamps by solvent extraction using ionic liquids was studied. Acid leaching of rare earth metals from the waste phosphor powder was examined first. Yttrium (Y) and europium (Eu) dissolved readily in the acid solution; however, the leaching of other rare earth metals required substantial energy input. Ionization of target rare earth metals from the waste phosphor powders into the leach solution was critical for their successful recovery. As a high temperature was required for the complete leaching of all rare earth metals, ionic liquids, for which vapor pressure is negligible, were used as an alternative extracting phase to the conventional organic diluent. An extractant, N, N-dioctyldiglycol amic acid (DODGAA), which was recently developed, showed a high affinity for rare earth metal ions in liquid-liquid extraction although a conventional commercial phosphonic extractant did not. An effective recovery of the rare earth metals, Y, Eu, La and Ce, from the metal impurities, Fe, Al and Zn, was achieved from the acidic leach solution of phosphor powders using an ionic liquid containing DODGAA as novel extractant system. Copyright © 2013 Elsevier B.V. All rights reserved.

Bridging the gap between ionic liquids and molten salts: group 1 metal salts of the bistriflamide anion in the gas phase.

PubMed

Leal, João P; da Piedade, Manuel E Minas; Canongia Lopes, José N; Tomaszowska, Alina A; Esperança, José M S S; Rebelo, Luís Paulo N; Seddon, Kenneth R

2009-03-19

Fourier transform ion cyclotron resonance mass spectrometry experiments showed that liquid Group 1 metal salts of the bistriflamide anion undergoing reduced-pressure distillation exhibit a remarkable behavior that is in transition between that of the vapor-liquid equilibrium characteristics of aprotic ionic liquids and that of the Group 1 metal halides: the unperturbed vapors resemble those of aprotic ionic liquids, in the sense that they are essentially composed of discrete ion pairs. However, the formation of large aggregates through a succession of ion-molecule reactions is closer to what might be expected for Group 1 metal halides. Similar experiments were also carried out with bis{(trifluoromethyl)sulfonyl}amine to investigate the effect of H(+), which despite being the smallest Group 1 cation, is generally regarded as a nonmetal species. In this case, instead of the complex ion-molecule reaction pattern found for the vapors of Group 1 metal salts, an equilibrium similar to those observed for aprotic ionic liquids was observed.

Novel Nanocomposite Structures as Active and Passive Barrier Materials

DTIC Science & Technology

2010-06-01

during the course of this ARO-funded project. The development of a novel polymer material based on a diol-functionalized room-temperature ionic liquid ...material based on a diol-functionalized room- temperature ionic liquid (RTIL) monomer led to fabrication of membranes, which were tested for their...stimulant vapor. Technical Report A polymerizable room-temperature ionic liquid (4, Figure 1) was chosen as the starting material for making poly(RTIL

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

PubMed

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.

Ductile thermoset polymers via controlling network flexibility.

PubMed

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.

Development of multilayer conducting polymer actuator for power application

NASA Astrophysics Data System (ADS)

Ikushima, Kimiya; Kudoh, Yuji; Hiraoka, Maki; Yokoyama, Kazuo; Nagamitsu, Sachio

2009-03-01

In late years many kinds of home-use robot have been developed to assist elderly care and housework. Most of these robots are designed with conventional electromagnetic motors. For safety it is desirable to replace these electromagnetic motors with artificial muscle. However, an actuator for such a robot is required to have simple structure, low driving voltage, high stress generation, high durability, and operability in the air. No polymer actuator satisfying all these requirements has been realized yet. To meet these we took following two approaches focusing on conducting polymer actuators which can output high power in the air. (Approach 1) We have newly developed an actuator by multiply laminating ionic liquid infiltrated separators and polypyrrole films. Compared with conventional actuator that is driven in a bath of ionic liquid, the new actuator can greatly increase generated stress since the total sectional area is tremendously small. In our experiment, the new actuator consists of minimum unit with thickness of 128um and has work/weight ratio of 0.92J/kg by laminating 9 units in 0.5Hz driving condition. In addition, the driving experiment has shown a stable driving characteristic even for 10,000 cycles durability test. Furthermore, from our design consideration, it has been found that the work/weight ratio can be improved up to 8J/kg (1/8 of mammalian muscle of 64J/kg) in 0.1Hz by reducing the thickness of each unit to 30um. (Approach 2) In order to realize a simplified actuator structure in the air without sealing, we propose the use of ionic liquid gel. The actuation characteristic of suggested multilayered actuator using ionic liquid gel is simulated by computer. The result shows that performance degradation due to the use of ionic liquid gel is negligible small when ionic liquid gel with the elasticity of 3kPa or less is used. From above two results it is concluded that the proposed multilayerd actuator is promising for the future robotic applications because it has advantages of high work/weight ratio and in-the-air operation, in addition to advantages of conventional polymer actuators.

Feasibility study of custom manufacturing methods of ionic polymer-metal composite sensors

NASA Astrophysics Data System (ADS)

Nelson, Shelby E.

The ability to create an ion exchange membrane with any shape or thickness through custom manufacturing techniques is highly desirable in ionic polymer-metal composite (IPMC) research. This is caused by the poor selection and limited availability of certain thicknesses of commercial ion exchange membranes. The objective of this study is to determine the feasibility of manufacturing custom ion exchange membranes for IPMC sensors. The manufacturing methods used in this study are extrusion, injection molding, and hot pressing. A commercial membrane from Golden Energy Fuel Cells (GEFC) is used as a comparison. After the membranes are fabricated, certain properties of the membranes are tested throughout each processing stage to determine if they are suitable to be developed into IPMCs. The three processing stages are pre-activation, activation (hydrated and dehydrated), and IPMC. It was observed that the stiffness of the membranes increased from pre-activation to activation and decreased from activation to IPMC. A more flexible membrane in an IPMC allows for larger cation displacement within the membrane. The extruded and injection molded membranes showed the most potential with having the lowest stiffness of all the samples; however, they were not able to be made into IPMCs due to repeated membrane failures in the primary plating process. Gas accumulated between the layers that formed in the membranes due to the extrusion and injection molding cooling process during manufacturing. The hot pressed membrane was the only custom manufactured membrane to be fully processed into an IPMC. The hot pressed and GEFC IPMC sensors were operated at 1 Hz, 5 Hz, and 10 Hz frequencies with the GEFC IPMC producing the strongest output voltage signal. While the extruded and injection molded membranes showed potential to become IPMCs with their high water uptake percentage, high ion exchange capacity, and low stiffness, more development is needed within the manufacturing process to make a uniform sample that does not fail during chemical processing.

Micro-mechanics of ionic electroactive polymer actuators

NASA Astrophysics Data System (ADS)

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.

Structure and Dynamics of Ionic Block Copolymer Melts: Computational Study

DOE PAGES

Aryal, Dipak; Agrawal, Anupriya; Perahia, Dvora; ...

2017-09-06

Structure and dynamics of melts of copolymers with an ABCBA topology, where C is an ionizable block, have been studied by fully atomistic molecular dynamics (MD) simulations. Introducing an ionizable block for functionality adds a significant element to the coupled set of interactions that determine the structure and dynamics of the macromolecule. The polymer consists of a randomly sulfonated polystyrene C block tethered to a flexible poly(ethylene-r-propylene) bridge B and end-capped with poly(tert-butylstyrene) A. The chemical structure and topology of these polymers constitute a model for incorporation of ionic blocks within a framework that provides tactility and mechanical stability. Heremore » in this paper we resolve the structure and dynamics of a structured polymer on the nanoscale constrained by ionic clusters. We find that the melts form intertwined networks of the A and C blocks independent of the degree of sulfonation of the C block with no long-range order. The cluster cohesiveness and morphology affect both macroscopic translational motion and segmental dynamics of all the blocks.« less

Structure and Dynamics of Ionic Block Copolymer Melts: Computational Study

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

Aryal, Dipak; Agrawal, Anupriya; Perahia, Dvora

Structure and dynamics of melts of copolymers with an ABCBA topology, where C is an ionizable block, have been studied by fully atomistic molecular dynamics (MD) simulations. Introducing an ionizable block for functionality adds a significant element to the coupled set of interactions that determine the structure and dynamics of the macromolecule. The polymer consists of a randomly sulfonated polystyrene C block tethered to a flexible poly(ethylene-r-propylene) bridge B and end-capped with poly(tert-butylstyrene) A. The chemical structure and topology of these polymers constitute a model for incorporation of ionic blocks within a framework that provides tactility and mechanical stability. Heremore » in this paper we resolve the structure and dynamics of a structured polymer on the nanoscale constrained by ionic clusters. We find that the melts form intertwined networks of the A and C blocks independent of the degree of sulfonation of the C block with no long-range order. The cluster cohesiveness and morphology affect both macroscopic translational motion and segmental dynamics of all the blocks.« less

Beneficial effect of added water on sodium metal cycling in super concentrated ionic liquid sodium electrolytes

NASA Astrophysics Data System (ADS)

Basile, Andrew; Ferdousi, Shammi A.; Makhlooghiazad, Faezeh; Yunis, Ruhamah; Hilder, Matthias; Forsyth, Maria; Howlett, Patrick C.

2018-03-01

The plating and stripping performance of sodium metal in an ionic liquid electrolyte is improved when including water as an additive. Herein we report for the first time the trend of improved cycling behavior of Na0/+ in N-methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide with 500 ppm H2O. The addition of water to this ionic liquid electrolyte promotes the breakdown of the [FSI]- anion towards beneficial SEI formation. The benefits during plating and stripping of sodium is observed as lower total polarization during symmetrical cell cycling and decreased electrode/electrolyte interface impedance. Sodium metal surfaces after cycling with 500 ppm H2O are shown to be smooth in morphology in comparison to lower additive concentrations. The outcome of adventitious moisture benefiting Na0/+ cycling in an ionic liquid, contrary to conventional electrolytes, allows flexibility in ionic liquid electrolyte design to the benefit of battery manufacturers.

Ionic liquid-based extraction followed by graphite-furnace atomic absorption spectrometry for the determination of trace heavy metals in high-purity iron metal.

PubMed

Matsumiya, Hiroaki; Kato, Tatsuya; Hiraide, Masataka

2014-02-01

The analysis of high-purity materials for trace impurities is an important and challenging task. The present paper describes a facile and sensitive method for the determination of trace heavy metals in high-purity iron metal. Trace heavy metals in an iron sample solution were rapidly and selectively preconcentrated by the extraction into a tiny volume of an ionic liquid [1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide] for the determination by graphite-furnace atomic absorption spectrometry (GFAAS). A nitrogen-donating neutral ligand, 2,4,6-tris(2-pyridyl)-1,3,5-triazine (TPTZ), was found to be effective in the ionic liquid-based selective extraction, allowing the nearly complete (~99.8%) elimination of the iron matrix. The combination with the optimized GFAAS was successful. The detectability reached sub-μg g(-1) levels in iron metal. The novel use of TPTZ in ionic liquid-based extraction followed by GFAAS was successfully applied to the determination of traces of Co, Ni, Cu, Cd, and Pb in certified reference materials for high-purity iron metal. © 2013 Published by Elsevier B.V.

Electrochemical Impedance Spectrometer with an Environmental Chamber for Rapid Screening of New Precise Copolymers

DTIC Science & Technology

2017-10-07

polymerization to make linear polyethylenes with carboxylic acid groups at precise intervals along the polymer . Precise acid- containing polymers provide...acid polyethylene and the a polymerized ionic liquids based on cyclopropenium. The instrument is also be used to study polymer segmental dynamics...Advances in batteries, fuel cells, and permselective membranes are materials limited. New acid- and ion-containing polymers must be designed and

Influence of nanoparticle-ion and nanoparticle-polymer interactions on ion transport and viscoelastic properties of polymer electrolytes

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

Mogurampelly, Santosh; Sethuraman, Vaidyanathan; Pryamitsyn, Victor

We use atomistic simulations to probe the ion conductivities and mechanical properties of polyethylene oxide electrolytes containing Al{sub 2}O{sub 3} nanoparticles. We specifically study the influence of repulsive polymer-nanoparticle and ion-nanoparticle interactions and compare the results with those reported for electrolytes containing the polymorph β-Al{sub 2}O{sub 3} nanoparticles. We observe that incorporating repulsive nanoparticle interactions generally results in increased ionic mobilities and decreased elastic moduli for the electrolyte. Our results indicate that both ion transport and mechanical properties are influenced by the polymer segmental dynamics in the interfacial zones of the nanoparticle in the ion-doped systems. Such effects were seenmore » to be determined by an interplay between the nanoparticle-polymer, nanoparticle-ion, and ion-polymer interactions. In addition, such interactions were also observed to influence the number of dissociated ions and the resulting conductivities. Within the perspective of the influence of nanoparticles on the polymer relaxation times in ion-doped systems, our results in the context of viscoelastic properties were consistent with the ionic mobilities. Overall, our results serve to highlight some issues that confront the efforts to use nanoparticle dispersions to simultaneously enhance the conductivity and the mechanical strength of polymer electrolyte.« less

Towards flexible solid-state supercapacitors for smart and wearable electronics.

PubMed

Dubal, Deepak P; Chodankar, Nilesh R; Kim, Do-Heyoung; Gomez-Romero, Pedro

2018-03-21

Flexible solid-state supercapacitors (FSSCs) are frontrunners in energy storage device technology and have attracted extensive attention owing to recent significant breakthroughs in modern wearable electronics. In this study, we review the state-of-the-art advancements in FSSCs to provide new insights on mechanisms, emerging electrode materials, flexible gel electrolytes and novel cell designs. The review begins with a brief introduction on the fundamental understanding of charge storage mechanisms based on the structural properties of electrode materials. The next sections briefly summarise the latest progress in flexible electrodes (i.e., freestanding and substrate-supported, including textile, paper, metal foil/wire and polymer-based substrates) and flexible gel electrolytes (i.e., aqueous, organic, ionic liquids and redox-active gels). Subsequently, a comprehensive summary of FSSC cell designs introduces some emerging electrode materials, including MXenes, metal nitrides, metal-organic frameworks (MOFs), polyoxometalates (POMs) and black phosphorus. Some potential practical applications, such as the development of piezoelectric, photo-, shape-memory, self-healing, electrochromic and integrated sensor-supercapacitors are also discussed. The final section highlights current challenges and future perspectives on research in this thriving field.

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

PubMed Central

2013-01-01

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

Charge carrier dynamics and relaxation in (polyethylene oxide-lithium-salt)-based polymer electrolyte containing 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide as ionic liquid

NASA Astrophysics Data System (ADS)

Karmakar, A.; Ghosh, A.

2011-11-01

In this paper we report the dynamics of charge carriers and relaxation in polymer electrolytes based on polyethylene oxide (PEO), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMPTFSI) ionic liquid prepared by solution cast technique. It has been observed that the incorporation of BMPTFSI into PEO-LiTFSI electrolyte is an effective way for increasing the amorphous phase to a large extent. It has also been observed that both the glass transition and melting temperatures decrease with the increase of BMPTFSI concentration. The ionic conductivity of these polymer electrolytes increases with the increase of BMPTFSI concentration. The highest ionic conductivity obtained at 25 °C is ˜3×10-4 S cm-1 for the electrolyte containing 60 wt % BMPTFSI and ethylene oxide (EO)/Li ratio of 20. The temperature dependence of the dc conductivity and the hopping frequency show Vogel-Tamman-Fulcher type behavior indicating a strong coupling between the ionic and the polymer chain segmental motions. The frequency dependence of the ac conductivity exhibits a power law with an exponent n which decreases with the increase of temperature. The scaling of the ac conductivity indicates that relaxation dynamics of charge carriers follows a common mechanism for all temperatures and BMPTFSI concentrations. We have also presented the electric modulus data which have been analyzed in the framework of a Havriliak-Negami equation and the shape parameters obtained by the analysis show slight temperature dependence, but change sharply with BMPTFSI concentration. The stretched exponent β obtained from Kohlrausch-Williams-Watts fit to the modulus data is much lower than unity signifying that the relaxation is highly nonexponential. The decay function obtained from analysis of experimental modulus data is highly asymmetric with time.

Molecular Simulation of Ionic Polyimides and Composites with Ionic Liquids as Gas-Separation Membranes.

PubMed

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.

New Insights into the Compositional Dependence of Li-Ion Transport in Polymer-Ceramic Composite Electrolytes.

PubMed

Zheng, Jin; Hu, Yan-Yan

2018-01-31

Composite electrolytes are widely studied for their potential in realizing improved ionic conductivity and electrochemical stability. Understanding the complex mechanisms of ion transport within composites is critical for effectively designing high-performance solid electrolytes. This study examines the compositional dependence of the three determining factors for ionic conductivity, including ion mobility, ion transport pathways, and active ion concentration. The results show that with increase in the fraction of ceramic Li 7 La 3 Zr 2 O 12 (LLZO) phase in the LLZO-poly(ethylene oxide) composites, ion mobility decreases, ion transport pathways transit from polymer to ceramic routes, and the active ion concentration increases. These changes in ion mobility, transport pathways, and concentration collectively explain the observed trend of ionic conductivity in composite electrolytes. Liquid additives alter ion transport pathways and increase ion mobility, thus enhancing ionic conductivity significantly. It is also found that a higher content of LLZO leads to improved electrochemical stability of composite electrolytes. This study provides insight into the recurring observations of compositional dependence of ionic conductivity in current composite electrolytes and pinpoints the intrinsic limitations of composite electrolytes in achieving fast ion conduction.

Studies on the effect of dispersoid(ZrO2) in PVdF-co-HFP based gel polymer electrolytes

NASA Astrophysics Data System (ADS)

Sivakumar, M.; Subadevi, R.; Muthupradeepa, R.

2013-06-01

Gel polymer electrolytes containing poly(vinylidenefluoride-co-hexafluoropropylene) (P(VdF-co-HFP)) / Lithium bis(trifluoromethane sulfon)imide (LiTFSI) / mixture of ethylene carbonate and propylene carbonate (EC+PC) with different concendration of ZrO2 has been prepared using the solution casting technique. The conductivity of the prepared electrolyte sample has been determined by AC impedance technique in the range 303-353K. The temperature dependent ionic conductivity plot seems to obey VTF relation. The maximum ionic conductivity value of 4.46 × 10-3S/cm has been obtained for PVdF-co-HFP(32%) - LiTFSI(8%) - EC+PC (60%) + ZrO2(6wt%) based polymer electrolyte. The surface morphology of the prepared electrolyte sample has been studied using SEM.

Command Surface of Self-Organizing Structures by Radical Polymers with Cooperative Redox Reactivity.

PubMed

Sato, Kan; Mizuma, Takahiro; Nishide, Hiroyuki; Oyaizu, Kenichi

2017-10-04

Robust radical-substituted polymers with ideal redox capability were used as "command surfaces" for liquid crystal orientation. The alignment of the smectic liquid crystal electrolytes with low-dimensional ion conduction pathways was reversible and readily switched in response to the redox states of the polymers. In one example, a charge storage device with a cooperative redox effect was fabricated. The bulk ionic conductivity of the cell was significantly decreased only after the electrode was fully charged, due to the anisotropic ionic conductivity of the electrolytes (ratio >10 3 ). The switching enabled both a rapid cell response and long charge retention. Such a cooperative command surface of self-assembled structures will give rise to new highly energy efficient supramolecular-based devices including batteries, charge carriers, and actuators.

Novel Proton Conducting Solid Bio-polymer Electrolytes Based on Carboxymethyl Cellulose Doped with Oleic Acid and Plasticized with Glycerol

NASA Astrophysics Data System (ADS)

Chai, M. N.; Isa, M. I. N.

2016-06-01

The plasticized solid bio-polymer electrolytes (SBEs) system has been formed by introducing glycerol (Gly) as the plasticizer into the carboxymethyl cellulose (CMC) doped with oleic acid (OA) via solution casting techniques. The ionic conductivity of the plasticized SBEs has been studied using Electrical Impedance Spectroscopy. The highest conductivity achieved is 1.64 × 10-4 S cm-1 for system containing 40 wt. % of glycerol. FTIR deconvolution technique had shown that the conductivity of CMC-OA-Gly SBEs is primarily influenced by the number density of mobile ions. Transference number measurement has shown that the cation diffusion coefficient and ionic mobility is higher than anion which proved the plasticized polymer system is a proton conductor.

Composite Solid Electrolyte For Lithium Cells

NASA Technical Reports Server (NTRS)

Peled, Emmanuel; Nagasubramanian, Ganesan; Halpert, Gerald; Attia, Alan I.

1994-01-01

Composite solid electrolyte material consists of very small particles, each coated with thin layer of Lil, bonded together with polymer electrolyte or other organic binder. Material offers significant advantages over other solid electrolytes in lithium cells and batteries. Features include high ionic conductivity and strength. Composite solid electrolyte expected to exhibit flexibility of polymeric electrolytes. Polymer in composite solid electrolyte serves two purposes: used as binder alone, conduction taking place only in AI2O3 particles coated with solid Lil; or used as both binder and polymeric electrolyte, providing ionic conductivity between solid particles that it binds together.

Interfacial behavior of polymer electrolytes

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

Kerr, John; Kerr, John B.; Han, Yong Bong

2003-06-03

Evidence is presented concerning the effect of surfaces on the segmental motion of PEO-based polymer electrolytes in lithium batteries. For dry systems with no moisture the effect of surfaces of nano-particle fillers is to inhibit the segmental motion and to reduce the lithium ion transport. These effects also occur at the surfaces in composite electrodes that contain considerable quantities of carbon black nano-particles for electronic connection. The problem of reduced polymer mobility is compounded by the generation of salt concentration gradients within the composite electrode. Highly concentrated polymer electrolytes have reduced transport properties due to the increased ionic cross-linking. Combinedmore » with the interfacial interactions this leads to the generation of low mobility electrolyte layers within the electrode and to loss of capacity and power capability. It is shown that even with planar lithium metal electrodes the concentration gradients can significantly impact the interfacial impedance. The interfacial impedance of lithium/PEO-LiTFSI cells varies depending upon the time elapsed since current was turned off after polarization. The behavior is consistent with relaxation of the salt concentration gradients and indicates that a portion of the interfacial impedance usually attributed to the SEI layer is due to concentrated salt solutions next to the electrode surfaces that are very resistive. These resistive layers may undergo actual phase changes in a non-uniform manner and the possible role of the reduced mobility polymer layers in dendrite initiation and growth is also explored. It is concluded that PEO and ethylene oxide-based polymers are less than ideal with respect to this interfacial behavior.« less

High-throughput approach for the identification of anilinium-based ionic liquids that are suitable for electropolymerisation.

PubMed

Abdelhamid, Muhammad E; Murdoch, Timothy; Greaves, Tamar L; O'Mullane, Anthony P; Snook, Graeme A

2015-07-21

We report the synthesis of new protic ionic liquids (PILs) based on aniline derivatives and the use of high-throughput (HT) techniques to screen possible candidates. In this work, a simple HT method was applied to rapidly screen different aniline derivatives against different acids in order to identify possible combinations that produce PILs. This was followed by repeating the HT process with a Chemspeed robotic synthesis platform for more accurate results. One of the successful combinations were then chosen to be synthesised on a larger scale for further analysis. The new PILs are of interest to the fields of ionic liquids, energy storage and especially, conducting polymers as they serve as solvents, electrolytes and monomers at the same time for possible electropolymerisation (i.e. a self-contained polymer precursor).

New Polymer Electrolyte Cell Systems

NASA Technical Reports Server (NTRS)

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.

A classical density functional theory of ionic liquids.

PubMed

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.

A PEGylated Fibrin-Based Wound Dressing with Antimicrobial and Angiogenic Activity

DTIC Science & Technology

2011-04-13

naturally available, cost-effective, biocompatible, and biodegradable. Among these natural polymers chitosan ( poly (b-(1,4)-2-amino-2-deoxy-D...drying, ionic gela- tion, and sieving. Among these, ionic gelation is preferred for drugs that require an initial short burst release while maintaining...form ionic interactions with anionic mole- cules, and have been previously used for the controlled release of drugs [18]. Since SSD is a weak anionic

Continuous process to produce lithium-polymer batteries

DOEpatents

Chern, Terry Song-Hsing; Keller, David Gerard; MacFadden, Kenneth Orville

1998-01-01

Solid polymer electrolytes are extruded with active electrode material in a continuous, one-step process to form composite electrolyte-electrodes ready for assembly into battery cells. The composite electrolyte-electrode sheets are extruded onto current collectors to form electrodes. The composite electrodes, as extruded, are electronically and ionically conductive. The composite electrodes can be overcoated with a solid polymer electrolyte, which acts as a separator upon battery assembly. The interface between the solid polymer electrolyte composite electrodes and the solid polymer electrolyte separator has low resistance.

Polymer-induced phase separation and crystallization in immunoglobulin G solutions.

PubMed

Li, Jianguo; Rajagopalan, Raj; Jiang, Jianwen

2008-05-28

We study the effects of the size of polymer additives and ionic strength on the phase behavior of a nonglobular protein-immunoglobulin G (IgG)-by using a simple four-site model to mimic the shape of IgG. The interaction potential between the protein molecules consists of a Derjaguin-Landau-Verwey-Overbeek-type colloidal potential and an Asakura-Oosawa depletion potential arising from the addition of polymer. Liquid-liquid equilibria and fluid-solid equilibria are calculated by using the Gibbs ensemble Monte Carlo technique and the Gibbs-Duhem integration (GDI) method, respectively. Absolute Helmholtz energy is also calculated to get an initial coexisting point as required by GDI. The results reveal a nonmonotonic dependence of the critical polymer concentration rho(PEG) (*) (i.e., the minimum polymer concentration needed to induce liquid-liquid phase separation) on the polymer-to-protein size ratio q (equivalently, the range of the polymer-induced depletion interaction potential). We have developed a simple equation for estimating the minimum amount of polymer needed to induce the liquid-liquid phase separation and show that rho(PEG) (*) approximately [q(1+q)(3)]. The results also show that the liquid-liquid phase separation is metastable for low-molecular weight polymers (q=0.2) but stable at large molecular weights (q=1.0), thereby indicating that small sizes of polymer are required for protein crystallization. The simulation results provide practical guidelines for the selection of polymer size and ionic strength for protein phase separation and crystallization.

Photoinitiated Bottom-Up Click Synthesis of Ion-Containing Networks as Hydroxide Exchange Membranes

NASA Astrophysics Data System (ADS)

Tibbits, Andrew Charles

Fuel cells are energy conversion devices which directly convert chemical energy into electrical energy and environmentally friendly byproducts (i.e., water) with potential versatility for transportation and portable applications. Hydroxide exchange membrane fuel cells (HEMFCs) have the potential to decrease the overall fuel cell cost through the utilization of non-precious metal catalysts such as nickel and silver as opposed to platinum which is used by the current standard technology, proton exchange membrane fuel cells (PEMFCs). However, substantial improvements in thermal and alkaline stability, hydroxide conductivity, mechanical flexibility, and processing are needed to create a competitive membrane for HEMFC applications. Regardless of the type of membrane, the high water uptake that is typically associated with increased ionic conductivity is problematic and can result in the dissolution of the membrane during fuel cell operation. Covalent crosslinking of the membrane is an approach which has been effectively applied to reduce water uptake without a significant compromise of the hydroxide conductivity. The synthesis and processing of membrane materials is vastly simplified by using click polymerization schemes. Click chemistry is a collection of organic chemical reactions that are rapid, selective, and high yielding. One of the most versatile and facile click reactions is the thiol-ene reaction, which is the radical-mediated addition reaction between a thiol (an -SH group) and an 'ene' (an electron rich vinyl group, C=C) in the presence of a photoinitiator and light. The click attributes of the thiol-ene reaction enables potential of "bottom-up" design of ion-containing polymers via a single step photoinitiated crosslinking reaction with precise control over structure and physicochemical properties not only for fuel cell membranes but also for a range of other applications including separations, sensors, flexible electronics, and coatings. However, a fundamental understanding of the formation and properties of ion-containing thiol-ene materials and their implementation as hydroxide exchange membranes is largely absent from the current literature. The work described herein will highlight the versatility of click reactions, primarily the thiol-ene reaction, for fabrication of ion-containing networks with tunable properties based on the rational design and synthesis of photopolymerizable ionic liquid comonomers with an emphasis on applicability for HEMFC applications. The role of ionic liquid monomer structure on the kinetics and mechanism of thiol-ene ionic network formation and the subsequent properties (i.e., ion conductive, thermomechanical, and structural) will be elucidated to establish a guided framework for click ionic material development. This framework will be directed onto the development of alkaline stable hydroxide-conductive membranes for fuel cell applications as well as the incorporation of catalytic nanoparticles into a photocrosslinkable formulation as a self-standing catalyst layer. Finally, novel approaches to membrane fabrication will be implemented to build on the foundational studies that will simultaneously enhance the ionic conductivity and mechanical properties of the ion-containing polymer materials: these approaches include the synthesis and crosslinking of photopolymerizable cationic surfactants for microphase separated membranes as well as the first "bottom-up" ion-containing polymer synthesized from the photoinitiated copper-catalyzed azide-alkyne cycloaddition (photo-CuAAC) reaction which exhibits enhanced processability and hydroxide conductivity (>50 mS/cm).

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

PubMed

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

2013-11-01

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