Polydisperse Brush with the Linear Density Profile
Macromolecules densely end-grafted to a planar solid surface form a polymer monolayer (brush). It is known that, in a good solvent, the density profile of monodisperse brushes parabolically decays on moving away from the plane. Using the analytical theory and computer simulation methods, we studied...
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| Published in | Polymer science. Series C Vol. 60; no. Suppl 1; pp. 84 - 94 |
|---|---|
| Main Authors | , , , |
| Format | Journal Article |
| Language | English |
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Moscow
Pleiades Publishing
01.12.2018
Springer Nature B.V |
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| Abstract | Macromolecules densely end-grafted to a planar solid surface form a polymer monolayer (brush). It is known that, in a good solvent, the density profile of monodisperse brushes parabolically decays on moving away from the plane. Using the analytical theory and computer simulation methods, we studied the structure of a polydisperse brush from homopolymers, for which molecular-mass distribution is set by the Schulz–Zimm distribution. It is found that, at a polydispersity index of 1.143, the polymer brush in a good solvent has a linear density profile. In this brush, the average distance of chain ends to the grafting plane is proportional to the square of their contour length. If any chain of the brush is chemically modified so that it will be able to adsorb on the grafting surface, then the adsorption of this chain inside the brush will proceed via a discontinuous first-order phase transition with the bimodal distribution of the order parameter (free end height). This transition has unusual features: the energy of adsorption corresponding to the midpoint of the transition is proportional to the contour length of the adsorbing chain
N
, the sharpness of the transition is proportional to
N
2
, and the height of the barrier separating adsorbed and desorbed states is proportional to
N
3
. The predicted dependences are verified by computer simulation. |
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| AbstractList | Macromolecules densely end-grafted to a planar solid surface form a polymer monolayer (brush). It is known that, in a good solvent, the density profile of monodisperse brushes parabolically decays on moving away from the plane. Using the analytical theory and computer simulation methods, we studied the structure of a polydisperse brush from homopolymers, for which molecular-mass distribution is set by the Schulz–Zimm distribution. It is found that, at a polydispersity index of 1.143, the polymer brush in a good solvent has a linear density profile. In this brush, the average distance of chain ends to the grafting plane is proportional to the square of their contour length. If any chain of the brush is chemically modified so that it will be able to adsorb on the grafting surface, then the adsorption of this chain inside the brush will proceed via a discontinuous first-order phase transition with the bimodal distribution of the order parameter (free end height). This transition has unusual features: the energy of adsorption corresponding to the midpoint of the transition is proportional to the contour length of the adsorbing chain N, the sharpness of the transition is proportional to N2, and the height of the barrier separating adsorbed and desorbed states is proportional to N3. The predicted dependences are verified by computer simulation. Macromolecules densely end-grafted to a planar solid surface form a polymer monolayer (brush). It is known that, in a good solvent, the density profile of monodisperse brushes parabolically decays on moving away from the plane. Using the analytical theory and computer simulation methods, we studied the structure of a polydisperse brush from homopolymers, for which molecular-mass distribution is set by the Schulz–Zimm distribution. It is found that, at a polydispersity index of 1.143, the polymer brush in a good solvent has a linear density profile. In this brush, the average distance of chain ends to the grafting plane is proportional to the square of their contour length. If any chain of the brush is chemically modified so that it will be able to adsorb on the grafting surface, then the adsorption of this chain inside the brush will proceed via a discontinuous first-order phase transition with the bimodal distribution of the order parameter (free end height). This transition has unusual features: the energy of adsorption corresponding to the midpoint of the transition is proportional to the contour length of the adsorbing chain N , the sharpness of the transition is proportional to N 2 , and the height of the barrier separating adsorbed and desorbed states is proportional to N 3 . The predicted dependences are verified by computer simulation. |
| Author | Klushin, L. I. Skvortsov, A. M. Qi, S. Schmid, F. |
| Author_xml | – sequence: 1 givenname: L. I. surname: Klushin fullname: Klushin, L. I. organization: Institute of Macromolecular Compounds, Russian Academy of Sciences, Department of Physics, American University of Beirut – sequence: 2 givenname: A. M. surname: Skvortsov fullname: Skvortsov, A. M. email: astarling@yandex.ru organization: St. Petersburg State Chemical and Pharmaceutical Academy – sequence: 3 givenname: S. surname: Qi fullname: Qi, S. organization: Institut für Physik, Johannes Gutenberg-Universität – sequence: 4 givenname: F. surname: Schmid fullname: Schmid, F. organization: Institut für Physik, Johannes Gutenberg-Universität |
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| SubjectTerms | Adsorption Brushes Chemistry Chemistry and Materials Science Computer simulation Contours Density Grafting Macromolecules Mass distribution Order parameters Organic chemistry Phase transitions Polydispersity Polymer Sciences Polymers Shape Sharpness Solid surfaces Solvents Surface chemistry |
| Title | Polydisperse Brush with the Linear Density Profile |
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