Random-Walk Model of Chain-Polymer Adsorption at a Surface

被引:284
作者
Rubin, Robert J. [1 ]
机构
[1] Natl Bur Stand, Washington, DC USA
关键词
D O I
10.1063/1.1697138
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A random-walk lattice model of adsorption of an isolated polymer chain at a solution surface is investigated. One-dimensional characteristics of the monomer-unit distribution are determined analytically in the limit of long polymer chains, neglecting the self-excluded volume. The mean number of monomer units adsorbed in the surface layer v(theta, N) is determined, assuming that one end of the polymer chain lies in the surface layer. The parameter N is the number of monomer units in the chain, and theta is the adsorption energy of each monomer unit in the surface layer measured in units of kT. In addition, the mean distance of the free end of the chain from the surface z(theta, N) is determined. The lattice models considered include the simple-cubic, hexagonal-closepacked, face-centered-cubic, and body-centered-cubic lattices. In the limit in which N -> infinity, both v(theta, N) and z(theta, N) exhibit a very interesting discontinuity at a lattice-dependent adsorption energy theta(c). For example for theta>theta(c), v(theta, N) (which is also proportional to the average adsorption energy of a polymer chain) is proportional to N. For theta<theta(c), v(theta, N) is proportional to a constant of order unity; and for theta=theta(c), v(theta, N) is proportional to N-1/2. It is shown that the probability distribution of the end of the chain decreases exponentially with increasing distance from the surface layer for theta>theta(c). In addition, the mean number of monomer units in the kth layer from the surface is determined for N >> 1 and theta>theta(c) and is found to decrease exponentially with increasing k. In effect, for theta>theta(c), the polymer chain exists in an adsorbed state. An improvement in the model, which includes short-range correlation between successive steps in the random-walk description, is also considered.
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页码:2392 / 2407
页数:16
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