Abstract
Thermodynamics of polymer chains in the Θ condition confined to a space between two parallel walls was studied by using lattice Monte Carlo simulations. The Θ state was realized by allocating positive interaction to nearest-neighbor pairs of a polymer segment and a solvent molecule that is now explicitly included, rather than giving attractive interaction between polymer segments with no explicit solvent molecules present. The two models can be equivalent when used to specify the Θ state in unconfined solutions, but missing segment-solvent contacts at the wall make the two models different for confined solutions. The effectively attractive wall facilitates entry of polymer chains into narrow slits in the corrected model and lifts the segment density at sites adjacent to the walls. The dependence of the segment density near the wall on the distance from the wall follows a power law different from the one that holds for the conventional model of the Θ state. In particular, when the wall has explicit interaction with the polymer segments, our model makes the profile highly sensitive to the solvent quality. The corrected model explains enhanced adsorption in a poorer solvent reported in experiments.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 9638-9646 |
| Number of pages | 9 |
| Journal | Macromolecules |
| Volume | 36 |
| Issue number | 25 |
| DOIs | |
| State | Published - Dec 16 2003 |
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ASJC Scopus subject areas
- Materials Chemistry
Cite this
Confined polymer chains in a Θ solvent : A model with polymer-solvent interactions. / Cifra, Peter; Teraoka, Iwao.
In: Macromolecules, Vol. 36, No. 25, 16.12.2003, p. 9638-9646.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Confined polymer chains in a Θ solvent
T2 - A model with polymer-solvent interactions
AU - Cifra, Peter
AU - Teraoka, Iwao
PY - 2003/12/16
Y1 - 2003/12/16
N2 - Thermodynamics of polymer chains in the Θ condition confined to a space between two parallel walls was studied by using lattice Monte Carlo simulations. The Θ state was realized by allocating positive interaction to nearest-neighbor pairs of a polymer segment and a solvent molecule that is now explicitly included, rather than giving attractive interaction between polymer segments with no explicit solvent molecules present. The two models can be equivalent when used to specify the Θ state in unconfined solutions, but missing segment-solvent contacts at the wall make the two models different for confined solutions. The effectively attractive wall facilitates entry of polymer chains into narrow slits in the corrected model and lifts the segment density at sites adjacent to the walls. The dependence of the segment density near the wall on the distance from the wall follows a power law different from the one that holds for the conventional model of the Θ state. In particular, when the wall has explicit interaction with the polymer segments, our model makes the profile highly sensitive to the solvent quality. The corrected model explains enhanced adsorption in a poorer solvent reported in experiments.
AB - Thermodynamics of polymer chains in the Θ condition confined to a space between two parallel walls was studied by using lattice Monte Carlo simulations. The Θ state was realized by allocating positive interaction to nearest-neighbor pairs of a polymer segment and a solvent molecule that is now explicitly included, rather than giving attractive interaction between polymer segments with no explicit solvent molecules present. The two models can be equivalent when used to specify the Θ state in unconfined solutions, but missing segment-solvent contacts at the wall make the two models different for confined solutions. The effectively attractive wall facilitates entry of polymer chains into narrow slits in the corrected model and lifts the segment density at sites adjacent to the walls. The dependence of the segment density near the wall on the distance from the wall follows a power law different from the one that holds for the conventional model of the Θ state. In particular, when the wall has explicit interaction with the polymer segments, our model makes the profile highly sensitive to the solvent quality. The corrected model explains enhanced adsorption in a poorer solvent reported in experiments.
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U2 - 10.1021/ma034656z
DO - 10.1021/ma034656z
M3 - Article
VL - 36
SP - 9638
EP - 9646
JO - Macromolecules
JF - Macromolecules
SN - 0024-9297
IS - 25
ER -