TY - JOUR

T1 - Continuum formulation of the Scheutjens-Fleer lattice statistical theory for homopolymer adsorption from solution

AU - Mavrantzas, V.G.

AU - Beris, A.N.

AU - Leermakers, F.A.M.

AU - Fleer, G.J.

PY - 2005

Y1 - 2005

N2 - Homopolymer adsorption from a dilute solution on an interacting (attractive) surface under static equilibrium conditions is studied in the framework of a Hamiltonian model. The model makes use of the density of chain ends n1,e and utilizes the concept of the propagator G describing conformational probabilities to locally define the polymer segment density or volume fraction ¿; both n1,e and ¿ enter into the expression for the system free energy. The propagator G obeys the Edwards diffusion equation for walks in a self-consistent potential field. The equilibrium distribution of chain ends and, consequently, of chain conformational probabilities is found by minimizing the system free energy. This results in a set of model equations that constitute the exact continuum-space analog of the Scheutjens-Fleer (SF) lattice statistical theory for the adsorption of interacting chains. Since for distances too close to the surface the continuum formulation breaks down, the continuum model is here employed to describe the probability of chain configurations only for distances z greater than 2l, where l denotes the segment length, from the surface; instead, for distances z¿2l, the SF lattice model is utilized. Through this novel formulation, the lattice solution at z=2l provides the boundary condition for the continuum model. The resulting hybrid (lattice for distances z¿2l, continuum for distances z>2l) model is solved numerically through an efficient implementation of the pseudospectral collocation method. Representative results obtained with the new model and a direct application of the SF lattice model are extensively compared with each other and, in all cases studied, are found to be practically identical.

AB - Homopolymer adsorption from a dilute solution on an interacting (attractive) surface under static equilibrium conditions is studied in the framework of a Hamiltonian model. The model makes use of the density of chain ends n1,e and utilizes the concept of the propagator G describing conformational probabilities to locally define the polymer segment density or volume fraction ¿; both n1,e and ¿ enter into the expression for the system free energy. The propagator G obeys the Edwards diffusion equation for walks in a self-consistent potential field. The equilibrium distribution of chain ends and, consequently, of chain conformational probabilities is found by minimizing the system free energy. This results in a set of model equations that constitute the exact continuum-space analog of the Scheutjens-Fleer (SF) lattice statistical theory for the adsorption of interacting chains. Since for distances too close to the surface the continuum formulation breaks down, the continuum model is here employed to describe the probability of chain configurations only for distances z greater than 2l, where l denotes the segment length, from the surface; instead, for distances z¿2l, the SF lattice model is utilized. Through this novel formulation, the lattice solution at z=2l provides the boundary condition for the continuum model. The resulting hybrid (lattice for distances z¿2l, continuum for distances z>2l) model is solved numerically through an efficient implementation of the pseudospectral collocation method. Representative results obtained with the new model and a direct application of the SF lattice model are extensively compared with each other and, in all cases studied, are found to be practically identical.

U2 - 10.1063/1.2075027

DO - 10.1063/1.2075027

M3 - Article

VL - 123

SP - 1

EP - 11

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 17

ER -