Molecular Weight Dependence of Ion-Mode Relaxation and DC Conduction in Polypropylene Oxide Complexed with LiClO4
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概要
- 論文の詳細を見る
Broadband dielectric spectroscopy has been employed to investigate the ion dynamics in polypropylene oxide (PPO) complexed with 0.1% LiClO4 over a molecular weight range of $M=425\text{--}3500$. It is found that ions undergo two types of motions: local fluctuation (ion-mode relaxation) and long-range diffusion (dc conduction). The dc conductivity $\sigma_{\text{dc}}$ decreases markedly with increasing molecular weight ($\propto M^{-2}$) whereas the ion-mode relaxation time $\tau_{\text{ion}}$ and its strength $\Delta \varepsilon_{\text{ion}}$ are nearly independent of $M$. The ion-mode relaxation is an indication of some structural inhomogeneity that confines ions temporarily in a certain domain. Analyses of these experimental results based on a dynamic percolation model lead us to propose the following ionic processes in PPO/LiClO4 systems. The ionic motion originates in the elementary jumps for a distance equivalent to a monomer length at a frequency of segmental mode molecular motion. Due to structural inhomogeneity, such an elementary motion is confined in a domain of approximately 1.2 nm in diameter to result in a relaxational nature specified by the time constant $\tau_{\text{f}}$. Structural renewal occurring at a rate of 1$/\tau_{\text{r}}$ allows ions to jump into adjacent domains and to undergo long-range diffusion. Below $M=400$, $\tau_{\text{r}}$ equals $\tau_{\text{f}}$. In a high $M$ range, $\tau_{\text{r}}$ becomes much larger than $\tau_{\text{f}}$ to control $\sigma_{\text{dc}}$ according to $\sigma_{\text{dc}}=\Delta \varepsilon_{\text{ion}}/\tau_{\text{r}}$. Structural renewal is suggested to occur in association with a large-scale molecular motion.
- Published by the Japan Society of Applied Physics through the Institute of Pure and Applied Physicsの論文
- 2001-05-15
著者
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Furukawa Takeo
Department Of Chemistry Faculty Of Science Science University Of Tokyo
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Kano Kenji
Department Of Agricultural Chemistry Faculty Of Agriculture Kyoto University
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Takahashi Yoshiyuki
Department Of Anesthesiology Dokkyo Medical University
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Takahashi Yoshiyuki
Department of Chemistry, Faculty of Science, Science University of Tokyo, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan
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Furukawa Takeo
Department of Chemistry, Faculty of Science, Science University of Tokyo, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan
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Kano Kenji
Department of Chemistry, Faculty of Science, Science University of Tokyo, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan
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Takahashi Yoshiyuki
Department Of Anesthesia And Pain Medicine, Dokkyo Medical University School Of Medicine
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