### Abstract

Original language | English |
---|---|

Pages (from-to) | 3026-3036 |

Journal | Macromolecules |

Volume | 37 |

Issue number | 8 |

DOIs | |

Publication status | Published - 2004 |

### Fingerprint

### Keywords

- interacting chain molecules
- living polymers
- supramolecular polymers
- polydisperse polymers
- surface segregation
- reversible polymers
- statistical-theory
- adsorption
- lattice
- dilute

### Cite this

*Macromolecules*,

*37*(8), 3026-3036. https://doi.org/10.1021/ma0351773

}

*Macromolecules*, vol. 37, no. 8, pp. 3026-3036. https://doi.org/10.1021/ma0351773

**Equilibrium polymers at interfaces : analytical self-consistent-field theory.** / van der Gucht, J.; Besseling, N.A.M.; Fleer, G.J.

Research output: Contribution to journal › Article › Academic › peer-review

TY - JOUR

T1 - Equilibrium polymers at interfaces : analytical self-consistent-field theory

AU - van der Gucht, J.

AU - Besseling, N.A.M.

AU - Fleer, G.J.

PY - 2004

Y1 - 2004

N2 - An analytical mean-field theory is constructed for equilibrium (or "living") polymers with excluded volume at a surface. Within a mean-field approximation, exact analytical expressions are obtained for the monomer concentration profile at the surface and for the excess amount, both for adsorbing and nonadsorbing surfaces, and for the whole concentration range from the dilute to the marginal regime. A ground-state approximation is not needed. For nonadsorbing polymers there is a depletion layer next to the surface with a thickness that passes through a maximum as a function of the monomer concentration. If the equilibrium polymers adsorb on the surface, their behavior is qualitatively different from that of monodisperse chains. For weak adsorption, the excess amount increases gradually as the adsorption energy increases. At a certain finite value of the adsorption energy (which depends on the average length of the chains in the bulk), the excess amount starts to increases very rapidly by orders of magnitude. For chains without excluded volume the excess amount diverges at this point, whereas for real chains it remains finite. Adsorption isotherms of equilibrium polymers show a similar behavior: a gradual increase at low concentrations, then a very steep increase at some finite concentration, and a plateau at higher concentrations.

AB - An analytical mean-field theory is constructed for equilibrium (or "living") polymers with excluded volume at a surface. Within a mean-field approximation, exact analytical expressions are obtained for the monomer concentration profile at the surface and for the excess amount, both for adsorbing and nonadsorbing surfaces, and for the whole concentration range from the dilute to the marginal regime. A ground-state approximation is not needed. For nonadsorbing polymers there is a depletion layer next to the surface with a thickness that passes through a maximum as a function of the monomer concentration. If the equilibrium polymers adsorb on the surface, their behavior is qualitatively different from that of monodisperse chains. For weak adsorption, the excess amount increases gradually as the adsorption energy increases. At a certain finite value of the adsorption energy (which depends on the average length of the chains in the bulk), the excess amount starts to increases very rapidly by orders of magnitude. For chains without excluded volume the excess amount diverges at this point, whereas for real chains it remains finite. Adsorption isotherms of equilibrium polymers show a similar behavior: a gradual increase at low concentrations, then a very steep increase at some finite concentration, and a plateau at higher concentrations.

KW - interacting chain molecules

KW - living polymers

KW - supramolecular polymers

KW - polydisperse polymers

KW - surface segregation

KW - reversible polymers

KW - statistical-theory

KW - adsorption

KW - lattice

KW - dilute

U2 - 10.1021/ma0351773

DO - 10.1021/ma0351773

M3 - Article

VL - 37

SP - 3026

EP - 3036

JO - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 8

ER -