Investigating the Effect of Miscibility on the Ionic Conductivity of LiClO<sub>4</sub>/PEO/PCL Ternary Blends

Chiu, Chun-Yi; Chen, Hsien‐Wei; Kuo, Shiao‐Wei; Huang, Chih‐Feng; Chang, Feng-Chin

doi:10.1021/ma0488156

Cited by 89 publications

(58 citation statements)

References 19 publications

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“…In a related phenomenon, the alloy Cu-Au-Ni mixture shows a closed loop miscibility gap of their solid solutions (25)(26)(27). Similar phase behavior has been found in a polymer blend for which there is spectroscopic evidence for a pairwise binding of two components (28).…”

Section: Discussionsupporting

confidence: 57%

Condensed complexes in vesicles containing cholesterol and phospholipids

Radhakrishnan

McConnell

2005

Proc. Natl. Acad. Sci. U.S.A.

148

147

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Animal cell membranes pose conceptual problems related to the physical chemistry of liquids. An avenue to the solution of some of these problems has been opened by the discovery of liquid-liquid immiscibility in synthetic membranes composed of cholesterol and phospholipids. This discovery has led to the development of a thermodynamic model involving condensed complexes. In this model, the phospholipids with longer fatty-acid chains react reversibly with cholesterol to form complexes. The complexes themselves can have a repulsive interaction with other phospholipids, leading to immiscibility. A striking example of this effect is revealed in the phase diagrams of ternary mixtures of cholesterol, a saturated phosphatidylcholine (or sphingomyelin), and an unsaturated phosphatidylcholine. As found by a number of investigators, all binary pairs are miscible in bilayers, whereas the ternary mixture can form two liquid phases. The model of condensed complexes accounts for this effect. Condensed complexes also have a major effect on the chemical activity of cholesterol and on the ordering of phospholipid acyl chains both in the presence and absence of phase separations. Model calculations of phospholipid order parameters account for several features of the deuterium NMR spectra of labeled phospholipid molecules in bilayer mixtures with cholesterol.chemical activity ͉ deuterium NMR ͉ membrane ͉ phase diagrams A number of early investigators have interpreted various physical chemical effects of cholesterol on phospholipids in membranes in terms of the formation of cholesterolphospholipid complexes (1-5). The use of complexes to account for the properties of nonideal liquids has a long history (6, 7). Even so, this chemical picture of cholesterolphospholipid interactions has been criticized in later work, because such complexes have never been isolated, and molecular dynamics calculations have not suggested specific molecular structures (8 -11). Nonetheless, more recent studies have demonstrated the utility of a quantitative thermodynamic model for the formation of complexes between cholesterol and the more saturated phospholipids. In this model, the complexes were referred to as ''condensed complexes'' in recognition of the well-known effect of cholesterol in ordering the fatty-acid chains of phospholipids (12, 13). This thermodynamic model implies short-range order, but there is no requirement that the complexes have highly specific, static molecular structures. That is, the complexes may have structures that f luctuate rapidly over a range of conformations.A striking example of the utility of the condensed complex model is provided by recent determinations of the ternary phase diagrams of lipid mixtures (14, 15). These diagrams describe mixtures of cholesterol and two phospholipids, one phospholipid with a relatively high melting temperature and the other with a low melting temperature. For these lipids, no binary pair shows liquid-liquid immiscibility, whereas some ternary mixtures form two liquid phases (14-17). That i...

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Section: Discussionsupporting

confidence: 57%

Condensed complexes in vesicles containing cholesterol and phospholipids

Radhakrishnan

McConnell

2005

Proc. Natl. Acad. Sci. U.S.A.

148

147

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“…Polymer electrolytes which are complexes of solvent-free polar polymers and inorganic metal salts are prepared by dissolving salts in high-molecular-weight polymer hosts. Polymer electrolytes have been studied extensively by researchers because of their potential applications, namely, in high-energy density batteries and fuel cells [2]. The key advantages of solid polymeric electrolytes over liquid electrolytes are good mechanical properties, ease of fabrication to thin films, desirable sizes, and their capability to form proper electrode-electrolyte contact [3,4].…”

Section: Introductionmentioning

confidence: 99%

“…Biodegradable polymers have attracted much attention in biomedical application [9]. Previous studies [2] have shown that PCL can be used as a polymer matrix for the preparation of polymer electrolytes due to the existence of carbonyl functional groups in its backbone structure. Thus, the ability of PCL as a host polymer is due to the presence of carbonyl groups in its structure that can dissolve inorganic salt as a result of electrostatic interaction.…”

Section: Introductionmentioning

confidence: 99%

Li+ ion conduction mechanism in poly (ε-caprolactone)-based polymer electrolyte

Aziz

2013

Iran Polym J

150

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In this work, solid polymer electrolytes based on poly(e-caprolactone) (PCL) with lithium bis(oxalato)borate as a doping salt were prepared by solution cast technique using DMF as a solvent. The electrical DC conductivity and dielectric constant of the solid polymer electrolyte samples were investigated by electrochemical impedance spectroscopy over a frequency range from 50 Hz to 1 MHz. It was found that the DC conductivity increased with increase in the salt concentration to up to 4 wt% and thereafter decreased. Dielectric constant versus salt concentration was used to interpret the decrease in DC conductivity with increase in salt concentration. The DC conductivity as a function of temperature follows Arrhenius behavior in low temperature region, which reveals that ion conduction occurs through successful hopping. The curvature of DC conductivity at high temperatures indicates the contribution of segmental motion to ion conduction. High values for dielectric constant and dielectric loss were observed at low frequencies. The plateau of dielectric constant and dielectric loss at high frequencies can be observed as a result of rapid oscillation of the AC electric field. The HN dielectric function was utilized to study the dielectric relaxation. The experimental and theoretical data of dielectric constant are very close to each other at low temperatures. At high temperatures, the simulated data are more deviated from the experimental curve of dielectric constant due to the dominance of electrode polarization. The non-unity of relaxation parameters (a and b) reveals that the relaxation processes in PCL-based solid electrolyte is a non-Debye type of relaxation.

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“…The ionic conductivities increased with the increase of salt concentration up to 5 wt.%, after which they gradually decreased with increasing salt concentration. The increase of ionic conductivity in polymer electrolytes is attributable to the increased number of charge carriers, but the decrease at higher salt concentrations is considered to be because of the formation of ion pairs in the polymer electrolytes [23][24][25]. As a result, the maximum ionic conductivity at room temperature was achieved as 3.7×10 −5 S/cm at 5 wt.% of salt concentration.…”

Section: Characterization Of Polymer Electrolytesmentioning

confidence: 99%

Graft polymerization of poly(epichlorohydrin-g-poly((oxyethylene) methacrylate)) using ATRP and its polymer electrolyte with KI

Lee

Park

Koh

et al. 2008

Ionics

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This contribution demonstrates a synthesis of comb polymer consisting of a poly(epichlorohydrin) (PECH) backbone and poly(oxyethylene methacrylate) side chains. Atom transfer radical polymerization (ATRP) was used to directly initiate the chlorine atoms of PECH macroinitiator. The structure of comb polymer was characterized by nuclear magnetic resonance ( 1 H nuclear magnetic resonance) and Fourier transform infrared (FT-IR) spectroscopy, presenting the successful "grafting from" method using ATRP. The comb polymer was used as a polymer matrix for dissolving potassium iodide (KI) to prepare solid polymer electrolyte. FT-IR spectroscopy indicates that the potassium salts are dissolved in the polymeric matrix due to coordination interaction with the ether oxygens of graft copolymer. Differential scanning calorimetry showed that glass transition temperature (T g ) of polymer electrolytes continuously increased with increasing salt concentration up to 15 wt.%, mostly due to coordinative interactions between the potassium ions and the ether oxygens of polymer matrix. Ionic conductivity at room temperature increased with increasing salt concentrations up to 5 wt.% (maximum ionic conductivity~3.7×10 −5 S/cm), after which it gradually decreased.

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Investigating the Effect of Miscibility on the Ionic Conductivity of LiClO₄/PEO/PCL Ternary Blends

Cited by 89 publications

References 19 publications

Condensed complexes in vesicles containing cholesterol and phospholipids

Condensed complexes in vesicles containing cholesterol and phospholipids

Li+ ion conduction mechanism in poly (ε-caprolactone)-based polymer electrolyte

Graft polymerization of poly(epichlorohydrin-g-poly((oxyethylene) methacrylate)) using ATRP and its polymer electrolyte with KI

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Investigating the Effect of Miscibility on the Ionic Conductivity of LiClO4/PEO/PCL Ternary Blends

Cited by 89 publications

References 19 publications

Condensed complexes in vesicles containing cholesterol and phospholipids

Condensed complexes in vesicles containing cholesterol and phospholipids

Li+ ion conduction mechanism in poly (ε-caprolactone)-based polymer electrolyte

Graft polymerization of poly(epichlorohydrin-g-poly((oxyethylene) methacrylate)) using ATRP and its polymer electrolyte with KI

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Investigating the Effect of Miscibility on the Ionic Conductivity of LiClO₄/PEO/PCL Ternary Blends