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Effect of sequence dispersity on morphology of tapered diblock copolymers from molecular dynamics simulations

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4972141· OSTI ID:1465369
 [1];  [2];  [2];  [2]
  1. The Ohio State Univ., Columbus, OH (United States). William G. Lowrie Dept. of Chemical and Biomolecular Engineering; California Inst. of Technology (CalTech), Pasadena, CA (United States). Division of Physics, Mathematics and Astronomy; William G. Lowrie Department of Chemical and Biomolecular Engineering, The Ohio State University, 151 W. Woodruff Ave., Columbus, Ohio 43210, USA
  2. The Ohio State Univ., Columbus, OH (United States). William G. Lowrie Dept. of Chemical and Biomolecular Engineering
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Tapered diblock copolymers are similar to typical AB diblock copolymers but have an added transition region between the two blocks which changes gradually in composition from pure A to pure B. This tapered region can be varied from 0% (true diblock) to 100% (gradient copolymer) of the polymer length, and this allows some control over the microphase separated domain spacing and other material properties. We perform molecular dynamics simulations of linearly tapered block copolymers with tapers of various lengths, initialized from fluids density functional theory predictions. To investigate the effect of sequence dispersity, we compare systems composed of identical polymers, whose taper has a fixed sequence that most closely approximates a linear gradient, with sequentially disperse polymers, whose sequences are created statistically to yield the appropriate ensemble average linear gradient. Especially at high segregation strength, we find clear differences in polymer conformations and microstructures between these systems. Importantly, the statistical polymers are able to find more favorable conformations given their sequence, for instance, a statistical polymer with a larger fraction of A than the median will tend towards the A lamellae. The conformations of the statistically different polymers can thus be less stretched, and these systems have higher overall density. Consequently, the lamellae formed by statistical polymers have smaller domain spacing with sharper interfaces
Research Organization:
The Ohio State Univ., Columbus, OH (United States). William G. Lowrie Dept. of Chemical and Biomolecular Engineering
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0014209; SC0014458
OSTI ID:
1465369
Alternate ID(s):
OSTI ID: 1336839
OSTI ID: 1468591
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 23 Vol. 145; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

References (47)

Diblock copolymers as emulsifying agents in polymer blends: Influence of molecular weight, architecture, and chemical composition journal July 1996
Some effects of monomer sequence on the viscoelastic behavior of random copolymers of butadiene and styrene journal April 1971
Properties of random and block copolymers of butadiene and styrene. I. Dynamic properties and glassy transition temperatures journal August 1967
Copolymers with controlled distribution of comonomers along the chain, 1. Structure, thermodynamics and dynamic properties of gradient copolymers. Computer simulation journal September 1996
Effects of Blockiness and Polydispersity on the Phase Behavior of Random Block Copolymers journal August 2016
Molecular design of multicomponent polymer systems. III. Comparative behavior of pure and tapered block copolymers in emulsification of blends of low-density polyethylene and polystyrene journal December 1982
Stabilization of a cocontinuous phase morphology by a tapered diblock or triblock copolymer in polystyrene-rich low-density polyethylene/polystyrene blends: Cocontinuous Phase Morphology journal December 2002
Molecular design of multicomponent polymer systems. XIV. Control of the mechanical properties of polyethylene–polystyrene blends by block copolymers journal March 1989
Effect of diblock copolymers on dynamic mechanical properties of polyethylene/polystyrene blends journal July 1991
Fast Parallel Algorithms for Short-Range Molecular Dynamics journal March 1995
Effect of block copolymers of various molecular architecture on the phase morphology and tensile properties of LDPE rich (LDPE/PS) blends journal February 2002
Influence of interfacial structure on morphology and deformation behavior of SBS block copolymers journal February 2003
Computer simulation study of polydispersity effect on the phase behavior of short diblock copolymers journal July 2016
Impact of Conformational and Chemical Correlations on Microphase Segregation in Random Copolymers journal May 2016
Determination of Interfacial Mixing in Tapered Block Polymer Thin Films: Experimental and Theoretical Investigations journal July 2016
Ionic Aggregate Structure in Ionomer Melts: Effect of Molecular Architecture on Aggregates and the Ionomer Peak journal December 2011
Interfacial Manipulations: Controlling Nanoscale Assembly in Bulk, Thin Film, and Solution Block Copolymer Systems journal February 2013
Thermodynamic considerations of triblock copolymers with a random middle block journal October 1992
Microphase Separation in Normal and Inverse Tapered Block Copolymers of Polystyrene and Polyisoprene. 1. Phase State journal January 2001
Shape of unperturbed linear polymers: polypropylene journal November 1985
Structure and properties of tapered block polymers. 4. "Domain-boundary mixing" and "mixing-in-domain" effects on microdomain morphology and linear dynamic mechanical response journal July 1983
Controlling Micellar Properties of Styrene/Isoprene Copolymers by Altering the Monomer Arrangement along the Chain journal January 2002
Interfacial Activity of Gradient Copolymers journal October 2002
Double-Gyroid Network Morphology in Tapered Diblock Copolymers journal May 2011
Blockiness and Sequence Polydispersity Effects on the Phase Behavior and Interfacial Properties of Gradient Copolymers journal July 2012
Collective and Single-Chain Correlations in Disordered Melts of Symmetric Diblock Copolymers: Quantitative Comparison of Simulations and Theory journal January 2014
Effect of Tapering on Morphology and Interfacial Behavior of Diblock Copolymers from Molecular Dynamics Simulations journal July 2015
Interfacial Modification as a Route to Novel Bilayered Morphologies in Binary Block Copolymer/Homopolymer Blends journal July 1998
Design and Synthesis of Network-Forming Triblock Copolymers Using Tapered Block Interfaces journal March 2012
Phase Behavior of Tapered Diblock Copolymers from Self-Consistent Field Theory journal November 2013
Controlled ionic conductivity via tapered block polymer electrolytes journal January 2015
Manipulating ordering transitions in interfacially modified block copolymers journal January 2009
Phase behavior of gradient copolymer solutions: a Monte Carlo simulation study journal January 2012
Segmental dynamics in lamellar phases of tapered copolymers journal January 2016
Density functional theory for inhomogeneous polymer systems. I. Numerical methods journal December 2002
Density functional theory for inhomogeneous polymer systems. II. Application to block copolymer thin films journal December 2002
Surface forces in polymer fluids: A comparison between simulations and density functional theory journal January 2004
Interfacial properties of statistical copolymer brushes in contact with homopolymer melts journal April 2011
Efficient continuum model for simulating polymer blends and copolymers journal December 1996
Effects of compositional polydispersity on gradient copolymer melts journal February 2013
Fluctuation effects on the order-disorder transition in polydisperse copolymer melts journal December 2013
Fluids density functional theory and initializing molecular dynamics simulations of block copolymers journal March 2016
Surface Energies and Self-Assembly of Block Copolymers on Grafted Surfaces journal September 2011
Structure and Properties of Tapered Block Polymers of Styrene and Isoprene journal July 1980
Structure and Properties of Tapered Block Polymers of Styrene and Isoprene II. Dynamic Mechanical Responses and Their Structural Interpretations journal October 1983
Using tapered interfaces to manipulate nanoscale morphologies in ion-doped block polymers journal May 2015
Properties of Random and Block Copolymers of Butadiene and Styrene. I. Dynamic Properties and Glassy Transition Temperatures journal May 1969

Cited By (3)

Designing Electrostatic Interactions via Polyelectrolyte Monomer Sequence journal March 2019
Sequence and entropy-based control of complex coacervates journal November 2017
Micro- to macro-phase separation transition in sequence-defined coacervates journal January 2020

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36 MATERIALS SCIENCE