Computer Simulations of Bottle Brushes: From Melts to Soft Networks

Cao, Zhen; Carrillo, Jan-Michael Y.; Sheiko, Sergei S.; Dobrynin, Andrey V.

doi:10.1021/acs.macromol.5b00682

Title: Computer Simulations of Bottle Brushes: From Melts to Soft Networks

Journal Article · Mon Jul 13 04:00:00 UTC 2015 · Macromolecules

DOI: https://doi.org/10.1021/acs.macromol.5b00682 · OSTI ID:1261458

Cao, Zhen ^[1]; Carrillo, Jan-Michael Y. ^[2]; Sheiko, Sergei S. ^[3]; Dobrynin, Andrey V. ^[1]

Univ. of Connecticut, Storrs, CT (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of North Carolina, Chapel Hill, NC (United States)

We use a combination of Molecular dynamics simulations and analytical calculations, and study dens bottle-brush systems in a melt and network State. Analysis of our simulation results shows that bottle-brush macromolecules in melt behave as ideal chains with effective Kuhn length b_K. Simulations show that the bottle-brush-induced bending rigidity is due to an entropy decrease caused by redistribution of the side chains upon backbone bending. The Kuhn length of the bottle:brushes increases with increasing the side-chain degree of polymerization n_sc as b_K proportional to n_sc^0.46. Moreover, this model of bottle brush macromolecules is extended to describe mechanical properties of bottle brush networks in linear and nonlinear deformation regimes. In the linear deformation regime, the network shear modulus scales with the degree of polymerization of the side chains as G₀ proportional to (n_sc + 1)^-1 as long as the ratio of the Kuhn length, b_K, to the size of the fully extended bottle-brush backbone between cross-links, R-max, is smaller than unity, b_K/R_max << 1. Bottle-brush networks With b_K/R_max proportional to 1 demonstrate behavior similar to that of networks Of semiflexible chains with G₀ proportional to n_sc^-0.5. Finally, in the nonlinear network deformation regime, the deformation-dependent shear modulus is a universal function of the first strain invariant I₁ and bottle-brush backbone deformation ratio beta describing stretching ability of the bottle-brush backbone between cross-links.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)

Sponsoring Organization:: DOE Office of Science; USDOE; National Science Foundation (NSF)

Grant/Contract Number:: AC05-00OR22725; AC52-06NA25396; AC04-94AL85000; AC05-00OR22725

OSTI ID:: 1261458

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 14 Vol. 48; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Comb and Bottlebrush Polymers with Superior Rheological and Mechanical Properties Abbasi, Mahdi; Faust, Lorenz; Wilhelm, Manfred Advanced Materials, Vol. 31, Issue 26 https://doi.org/10.1002/adma.201806484	journal	February 2019
Solvent-free, supersoft and superelastic bottlebrush melts and networks Daniel, William F. M.; Burdyńska, Joanna; Vatankhah-Varnoosfaderani, Mohammad Nature Materials, Vol. 15, Issue 2 https://doi.org/10.1038/nmat4508	journal	November 2015
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Dilute solution structure of bottlebrush polymers Dutta, Sarit; Wade, Matthew A.; Walsh, Dylan J. Soft Matter, Vol. 15, Issue 14 https://doi.org/10.1039/c9sm00033j	journal	January 2019
Field-theoretic simulations of bottlebrush copolymers Spencer, Russell K. W.; Matsen, Mark W. The Journal of Chemical Physics, Vol. 149, Issue 18 https://doi.org/10.1063/1.5051744	journal	November 2018
Chameleon-like elastomers with molecularly encoded strain-adaptive stiffening and coloration Vatankhah-Varnosfaderani, Mohammad; Keith, Andrew N.; Cong, Yidan Science, Vol. 359, Issue 6383 https://doi.org/10.1126/science.aar5308	journal	March 2018
Dilute Solution Structure of Bottlebrush Polymers Dutta, Sarit; Wade, Matthew A.; Walsh, Dylan J. https://doi.org/10.26434/chemrxiv.7556690.v1	posted_content	January 2019
Comb and Bottlebrush Polymers with Superior Rheological and Mechanical Properties Abbasi, Mahdi; Faust, Lorenz; Wilhelm, Manfred Karlsruhe https://doi.org/10.5445/ir/1000096375	text	January 2019

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