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  • 1
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 655-662 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: In the present study of ion conducting polymers we demonstrate how light scattering can be used to obtain information about the elastic properties and the local intrachain mobility, which are essential characteristics of a high performance polymeric solid electrolyte. Brillouin scattering has been applied in studies of sodium triflate (NaCF3SO3)–poly(propylene glycol) (PPG) complexes of concentrations O:M=5:1, 8:1, and 16:1, where O:M is the backbone oxygen to sodium ratio. From the spectra sound velocity and absorption data were obtained. The acoustic data reveal structural relaxation processes associated with local translational (and orientational) intrachain motions of the polymer segments. The characteristic relaxations times τ were determined and found to be strongly dependent on the concentration of the dopant salt. This is because the dissociated ions act both as crosslinks betwen polymer chain segments and as "free'' ions available for conduction. Therefore, as the concentration of dissociated ions increases the intrachain mobility is slowed down (τ increases) due to increased crosslinking. The effect is demonstrated in the hypersonic velocity dispersion curve and in the absorption peak which both shift to higher temperatures with increasing salt concentration. The shift correlates with the increase in the glass transition temperature as salt is added to the polymer. It also correlates, at least at low salt concentrations, with the concentration of dissocated ions and with the conductivity. It can be concluded that the motions of free ions responsible for charge transport are strongly coupled to the intrachain motions of the polymer.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 6862-6867 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The symmetric stretch modes for the anions in poly(propylene glycol) (PPG) complexed with NaCF3SO3 and LiClO4 at an ether oxygen of alkali metal cation ratio of 16:1 have been studied as a function of the molecular weight of PPG and temperature using Raman spectroscopy. The splitting of these modes has been analyzed in terms of "free'' anions and ion pairs. We have observed that the number of ion pairs increases with increasing molecular weight and increasing temperature. The effect is greater in the PPG–NaCF3SO3 complex than in the PPG–LiClO4 complex. We have found a simple exponential relationship for the number of free anions in a master-plot representation using a shift factor T* which increases with increasing molecular weight. These results are discussed in terms of the entropy and energetics of polymer–salt systems.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 6271-6277 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Raman scattering measurements have been carried out on poly(propylene oxide) complexed with NaCF3SO3 salt of concentration O:M=30:1 (where O:M is the PO:Na ratio) over a temperature range of 186–360 K in order to study ion–ion associations of the dopant salt and their temperature dependence. Splitting of the symmetric stretching mode of the CF3SO−3 anion into a double band was observed and attributed to the existence of different environments of the anions. A two-component band analysis led to the identification of coexisting dissociated free ions and ion pairs, suggested to be in contact. Below the glass transition temperature, Tg, the intensity of the mode corresponding to the free ions was more or less constant with temperature; the amount of free ions in the glassy state was found to be about 84% of the total salt concentration. Above Tg the amount of dissociated free ions decreased rapidly with temperature in an Arrhenius-type behavior. The resulting reduction of the number of charge carriers has little influence on the conductivity, which is reported to dramatically increase with increasing temperature. It is concluded that the major factor determining the temperature dependence of the conductivity is the mobility rather than the number of charge carriers.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 101 (1994), S. 4621-4627 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The luminescence of Eu3+ in a salt–polymer complex, poly(propylene oxide) containing Eu(CF3SO3)3 salt, was studied using broad band and site-selective excitation. Two distinctly different types of local structure around Eu3+ were detected. To investigate and compare the local structure around the SO3CF−3 anions with that around the Eu3+ cations, a Raman scattering study of the SO3 symmetric stretch vibration was performed in the same system. The vibrational data clearly reveal that also the anions are subject to two types of local environment. It is found that neither of the two states can be attributed to "free'' (completely solvated) ions, which implies the existence of two different anion–cation configurations. Temperature and concentration dependent studies of the site-selective Eu3+ luminescence and the SO3 vibrational spectrum show that the relative amount of ions in the two states is, within the experimental accuracy, constant. However at elevated temperatures there is a rapid exchange between the two states not found at lower temperatures. The characteristic time scale for the ionic exchange is found to be closely related to the structural relaxation time of the polymer segmental mobility. The findings support the idea that ionic diffusion in salt–polymer complexes is assisted by the local polymer chain mobility which is used in models to explain polymer electrolyte performance.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 64 (1988), S. 2038-2043 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Raman spectra of LiClO4 complexed in poly(propylene-glycol) (PPG) have been obtained for concentrations of the monomer to salt ratio (ether oxygen):Li in the range 30:1–5:1. Splitting of the symmetric stretching mode of the ClO4− anion was observed with an intensity profile that varied with salt concentration. This phenomenon indicates a changing environment about the anion. A two-component band analysis leads to the identification of dissociated ions on one hand and solvent-separated ion pairs on the other. The concentration of ion pairs is relatively low compared to that of the dissociated ions, which are predominant for all concentrations. Despite the observed increase in the absolute number of dissociated ions at higher salt concentration, the electrical conductivity is reported to decrease in the same range. This indicates that the number of "free'' charge carriers is of less importance for the conductivity than the mobility, which is damped in this concentration range. Frequency shifts of the disordered longitudinal-acoustic mode and increased hypersonic velocities, measured with Raman and Brillouin scattering techniques, respectively, indicate increased stiffness of the polymer matrix for increasing salt concentration, which probably results in decreased ion mobility.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Oxford, UK : Blackwell Publishing Ltd
    Annals of the New York Academy of Sciences 335 (1980), S. 0 
    ISSN: 1749-6632
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Natural Sciences in General
    Type of Medium: Electronic Resource
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