Tension Amplification in Tethered Layers of Bottle-Brush Polymers.
Molecular dynamics simulations of a coarse-grained bead-spring model have been used to study the effects of molecular crowding on the accumulation of tension in the backbone of bottle-brush polymers tethered to a flat substrate. The number of bottle-brushes per unit surface area, Σ, as well as the lengths of the bottle-brush backbonesNbb(50 ≤Nbb≤ 200) and side chainsNsc(50 ≤Nsc≤ 200) were varied to determine how the dimensions and degree of crowding of bottle-brushes give rise to bond tension amplification along the backbone, especially near the substrate. From these simulations, we have identified three separate regimes of tension. For low Σ, the tension is due solely to intramolecular interactions and is dominated by the side chain repulsion that governs the lateral brush dimensions. With increasing Σ, the interactions between bottle-brush polymers induce compression of the side chains, transmitting increasing tension to the backbone. For large Σ, intermolecular side chain repulsion increases, forcing side chain extension and reorientation in the direction normal to the surface and transmitting considerable tension to the backbone.
Department of Polymer Science, The University of Akron, Akron, Ohio 44325, United States.
Gary M
GM
Leuty
Department of Polymer Science, The University of Akron, Akron, Ohio 44325, United States.
Mesfin
M
Tsige
Sandia National Laboratories, Albuquerque, New Mexico 87185, United States.
Gary S
GS
Grest
Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States.
Michael
M
Rubinstein
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