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An adsorption blob is a subchain of size comparable to the adsorbed layer thickness $\xi$. If the free-chain size law is $R\sim b{g}^{\nu }$, it contains $g\sim (\xi /b{)}^{1/\nu }$ monomers. Confinement costs of order $k_{B}T$ per blob produce $F_{\mathrm{conf}}\sim N{k}_{B}T/g$. A simple contact fraction $b/\xi$ gives $F/(N{k}_{B}T)\sim (b/\xi {)}^{1/\nu }-ϵb/\xi$. This model predicts $\xi /b\sim {ϵ}^{-\nu /(1-\nu )}$ and binding gain per monomer of order $k_{B}T{ϵ}^{1/(1-\nu )}$. It assumes a many-blob layer and a monomer-scale attraction range; it does not replace the full surface-critical theory of polymer adsorption.

For an ideal chain, independent Kuhn length steps give the random walk relationwhere $R_{\mathrm{sub}}$ denotes the end-to-end displacement of a subchain. Equivalently the mass-size fractal exponent is $2$. Numerical factors depend on the chosen definition of blob diameter.

A subchain smaller than the adsorption height explores three dimensions much as a free ideal chain does. At scales exceeding $\xi$, adsorption restricts its perpendicular extent to order $\xi$, so the coil is anisotropic. Its in-plane projection may still have a random walk law for an ideal chain, but the isotropic three-dimensional blob construction cannot be extrapolated to $\sigma >\xi$. This is the reason to use adsorption blobs of size $\xi$.

Here $T$ is the absolute temperature and $k_B$ the Boltzmann constant. An adsorption blob contains $g\sim (\xi /b{)}^2$ monomers, so there are $N/g\sim N(b/\xi {)}^2$ such blobs. Confining a blob removes an amount of conformational entropy of order $k_B$; thus the positive confinement contribution to the Helmholtz free energy isThe statement about one blob's entropy is used as an entropy loss relative to the free chain, rather than as an absolute entropy.

In the assumed slab model, contacts occur within a monomer-scale distance $b$ of the substrate. The contact fraction is approximately $b/\xi$, giving $N_c\simeq Nb/\xi$. Multiplying this by the negative contact energy yieldsThe two contributions express the competition between loss of conformational entropy and gain of adsorption energy. The numerical coefficients are the ones stipulated by this blob approximation.