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• W2143010300 endingPage "230" @default.
• W2143010300 startingPage "213" @default.
• W2143010300 abstract "We study irreversible polymer adsorption from dilute solutions theoretically. Universal features of the resultant non-equilibrium layers are predicted. Two broad cases are considered, distinguished by the magnitude of the local monomer-surface sticking rate Q: chemisorption (very small Q) and physisorption (large Q). Early stages of layer formation entail single-chain adsorption. While single-chain physisorption times tau ads are typically micro- to milli-seconds, for chemisorbing chains of N units we find experimentally accessible times tau ads=Q(-1)N(3/5), ranging from seconds to hours. We establish 3 chemisorption universality classes, determined by a critical contact exponent: zipping, accelerated zipping and homogeneous collapse. For dilute solutions, the mechanism is accelerated zipping: zipping propagates outwards from the first attachment, accelerated by occasional formation of large loops which nucleate further zipping. This leads to a transient distribution omega(s) approximately s(-7/5) of loop lengths s up to a maximum size smax approximately (Qt)(5/3) after time t. By times of order tau ads the entire chain is adsorbed. The outcome of the single-chain adsorption episode is a monolayer of fully collapsed chains. Having only a few vacant sites to adsorb onto, late-arriving chains form a diffuse outer layer. In a simple picture we find for both chemisorption and physisorption a final loop distribution Omega(s) approximately s(-11/5) and density profile c(z) approximately z(-4/3) whose forms are the same as for equilibrium layers. In contrast to equilibrium layers, however, the statistical properties of a given chain depend on its adsorption time; the outer layer contains many classes of chain, each characterized by a different fraction of adsorbed monomers f. Consistent with strong physisorption experiments, we find the f values follow a distribution P(f) approximately f(-4/5)." @default.
• W2143010300 created "2016-06-24" @default.
• W2143010300 creator A5036890832 @default.
• W2143010300 creator A5062845468 @default.
• W2143010300 date "2003-07-01" @default.
• W2143010300 modified "2023-10-16" @default.
• W2143010300 title "Irreversible adsorption from dilute polymer solutions" @default.
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• W2143010300 doi "https://doi.org/10.1140/epje/i2003-10015-9" @default.
• W2143010300 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/15011043" @default.
• W2143010300 hasPublicationYear "2003" @default.
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