Effect of the finite extensibility of polymer chains and of the finite size of added electrolyte ions on polyelectrolyte brushes
Effect of the finite extensibility of polymer chains and of the finite size of added electrolyte ions on polyelectrolyte brushes
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聚合物链的有限延伸性和添加的电解质离子的有限尺寸对聚电解质刷的影响
DOI：
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发表时间：
1991
期刊：
影响因子：
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通讯作者：
S. Varanasi
中科院分区：
文献类型：
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作者：
S. Misra;S. Varanasi
我们早期的聚电解质刷理论 [Macromolecules 22, 4173 (1989)] 是通过将聚合物链段的非静电和静电电势之和等同于 Milner、Witten 和 Cates (MWC) [Macromolecules 21, 2610 (1988)] 所示刷中存在的整体抛物线电势而得出的。在这里，我们通过采用 Shim 和 Cates 的非高斯拉伸（或熵）项来修正理论，以考虑链的有限可扩展性 [J.物理。法国 50, 3535 (1989)]。这种修正导致刷子高度永远不会超过链条长度； MWC 早期工作中没有考虑到这一点。此外，添加的对称电解质的离子被认为是硬球，阳离子和阴离子的尺寸通常取不同的值。因此，离子的总电化学势也包括体积排除项。假设离子将溶剂“视为”连续体（仅以其介电常数为特征......
Our earlier polyelectrolyte brush theory [Macromolecules 22, 4173 (1989)] was derived by equating the sum of the nonelectrostatic and electrostatic potentials of the polymer segment to an overall parabolic potential shown to exist in the brush by Milner, Witten, and Cates (MWC) [Macromolecules 21, 2610 (1988)]. Here we correct the theory to take into account the finite extensibility of the chains by adopting the non‐Gaussian stretch (or entropy) term of Shim and Cates [J. Phys. France 50, 3535 (1989)]. This correction leads to brush heights which will never exceed the chain length; an aspect that was not accounted for in the earlier work of MWC. In addition, the ions of the added symmetric electrolyte are considered to be hard spheres, the size of the cation and anion assuming different values in general. The total electrochemical potential of the ions, therefore, includes a volume exclusion term as well. The ions are assumed to ‘‘view’’ the solvent as a continuum (characterized only by its dielectric con...