We study the changes in the conformations of brushes upon the addition of crosslinks between the chains using the bond fluctuation model. The Flory-Rehner model applied to uniaxially swollen networks predicts a collapse for large degrees of crosslinking q proportional to q−1/3 in disagreement with our simulation data. We show that the height reduction of the brushes is driven by monomer fluctuations in a direction perpendicular to the grafting plane and not due to network elasticity. We observe that the impact of crosslinking is different for reactions between monomers of the same or on different chains. If the length reduction of the effective chain length due to both types of reactions is accounted for in a function β(q), the height of the brush can be derived from a Flory approach for the equilibrium brush height leading to H(q) ≈ Hbβ(q)1/3, whereby Hb denotes the height of the non-crosslinked brush.
Skip Nav Destination
Article navigation
28 October 2013
Research Article|
October 23 2013
Fluctuation driven height reduction of crosslinked polymer brushes: A Monte Carlo study
M. Lang;
M. Lang
a)
1
Leibniz-Institute of Polymer Research Dresden
, Hohe Straße 6, 01069 Dresden, Germany
Search for other works by this author on:
M. Hoffmann;
M. Hoffmann
b)
1
Leibniz-Institute of Polymer Research Dresden
, Hohe Straße 6, 01069 Dresden, Germany
2Institute of Theoretical Physics,
Technische Universität Dresden
, Zellescher Weg 17, 01062 Dresden, Germany
Search for other works by this author on:
R. Dockhorn;
R. Dockhorn
1
Leibniz-Institute of Polymer Research Dresden
, Hohe Straße 6, 01069 Dresden, Germany
2Institute of Theoretical Physics,
Technische Universität Dresden
, Zellescher Weg 17, 01062 Dresden, Germany
Search for other works by this author on:
M. Werner;
M. Werner
1
Leibniz-Institute of Polymer Research Dresden
, Hohe Straße 6, 01069 Dresden, Germany
2Institute of Theoretical Physics,
Technische Universität Dresden
, Zellescher Weg 17, 01062 Dresden, Germany
Search for other works by this author on:
J.-U. Sommer
J.-U. Sommer
1
Leibniz-Institute of Polymer Research Dresden
, Hohe Straße 6, 01069 Dresden, Germany
2Institute of Theoretical Physics,
Technische Universität Dresden
, Zellescher Weg 17, 01062 Dresden, Germany
Search for other works by this author on:
a)
Author to whom correspondence should be addressed. Electronic mail: [email protected]
b)
Current address: BioQuant & Institute for Theoretical Physics, Heidelberg University, 69120 Heidelberg, Germany.
J. Chem. Phys. 139, 164903 (2013)
Article history
Received:
August 30 2013
Accepted:
October 02 2013
Connected Content
Citation
M. Lang, M. Hoffmann, R. Dockhorn, M. Werner, J.-U. Sommer; Fluctuation driven height reduction of crosslinked polymer brushes: A Monte Carlo study. J. Chem. Phys. 28 October 2013; 139 (16): 164903. https://doi.org/10.1063/1.4825207
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
Evaluation of the MACE force field architecture: From medicinal chemistry to materials science
Dávid Péter Kovács, Ilyes Batatia, et al.
Related Content
A correspondence between the Flory–Rehner theory for microgels and the Daoud–Cotton model for polymer-grafted nanoparticles
J. Appl. Phys. (December 2020)
Excluded volume effects in polymer brushes at moderate chain stretching
J. Chem. Phys. (September 2014)
Insertion of nanoparticles into polymer brush under variable solvent conditions
J. Chem. Phys. (October 2012)
Spherical brushes within spherical cavities: A self-consistent field and Monte Carlo study
J. Chem. Phys. (October 2009)
Synthesis and Characterization of PEG Polymer Brushes via Cyclopolymerization of 1,2,3-Triazole Tethered Diacrylates
Chin. J. Chem. Phys. (December 2015)