Theory of the Miscibility of Fullerenes in Random Copolymer Melts

Dadmun, Mark D; Sumpter, Bobby G; Schweizer, Kenneth; Banerjee, Debapriya

Title: Theory of the Miscibility of Fullerenes in Random Copolymer Melts

Full Record
Other Related Research

Abstract

We combine polymer integral equation theory and computational chemistry methods to study the interfacial structure, effective interactions, miscibility and spatial dispersion mechanism of fullerenes dissolved in specific random AB copolymer melts characterized by strong non-covalent electron donor-acceptor interactions with the nanofiller. A statistical mechanical basis is developed for designing random copolymers to optimize fullerene dispersion at intermediate copolymer compositions. Pair correlation calculations reveal a strong sensitivity of interfacial packing near the fullerene to copolymer composition and adsorption energy mismatch. The potential of mean force between fullerenes displays rich trends, often non-monotonic with copolymer composition, reflecting a non-additive competition between direct filler attractions and polymer-mediated bridging and steric stabilization. The spinodal phase diagrams are in qualitative agreement with recent solubility limit experimental observations on three systems, and testable predictions are made for other random copolymers. The distinctive non-monotonic variation of miscibility with copolymer composition is found to be primarily a consequence of composition-dependent, spatially short-range attractions between the A and B monomers with the fullerene. A remarkably rich, polymer-specific temperature dependence of the spinodal diagram is predicted which reflects the thermal sensitivity of spatial correlations which can result in fullerene miscibility either increasing or decreasing with cooling. The calculations are contrastedmore »« less

Authors:

Dadmun, Mark D ^[1]; Sumpter, Bobby G ^[1]; Schweizer, Kenneth ^[2]; Banerjee, Debapriya ^[3]

ORNL
University of Illinois
University of Illinois, Urbana-Champaign

Publication Date:: Tue Jan 01 00:00:00 EST 2013

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). National Center for Computational Sciences (NCCS)

Sponsoring Org.:: USDOE Office of Science (SC)

OSTI Identifier:: 1096315

DOE Contract Number:: DE-AC05-00OR22725

Resource Type:: Journal Article

Journal Name:: Macromolecules

Additional Journal Information:: Journal Volume: TBD

Country of Publication:: United States

Language:: English

Citation Formats


                    Dadmun, Mark D, Sumpter, Bobby G, Schweizer, Kenneth, and Banerjee, Debapriya. Theory of the Miscibility of Fullerenes in Random Copolymer Melts.  United States: N. p., 2013. 
        Web.

Copy to clipboard


                    Dadmun, Mark D, Sumpter, Bobby G, Schweizer, Kenneth, & Banerjee, Debapriya. Theory of the Miscibility of Fullerenes in Random Copolymer Melts.  United States.

Copy to clipboard


                    Dadmun, Mark D, Sumpter, Bobby G, Schweizer, Kenneth, and Banerjee, Debapriya. 2013.  
        "Theory of the Miscibility of Fullerenes in Random Copolymer Melts".  United States.

Copy to clipboard


                    
@article{osti_1096315,

  title        = {Theory of the Miscibility of Fullerenes in Random Copolymer Melts},

  author       = {Dadmun, Mark D and Sumpter, Bobby G and Schweizer, Kenneth and Banerjee, Debapriya},

  abstractNote = {We combine polymer integral equation theory and computational chemistry methods to study the interfacial structure, effective interactions, miscibility and spatial dispersion mechanism of fullerenes dissolved in specific random AB copolymer melts characterized by strong non-covalent electron donor-acceptor interactions with the nanofiller. A statistical mechanical basis is developed for designing random copolymers to optimize fullerene dispersion at intermediate copolymer compositions. Pair correlation calculations reveal a strong sensitivity of interfacial packing near the fullerene to copolymer composition and adsorption energy mismatch. The potential of mean force between fullerenes displays rich trends, often non-monotonic with copolymer composition, reflecting a non-additive competition between direct filler attractions and polymer-mediated bridging and steric stabilization. The spinodal phase diagrams are in qualitative agreement with recent solubility limit experimental observations on three systems, and testable predictions are made for other random copolymers. The distinctive non-monotonic variation of miscibility with copolymer composition is found to be primarily a consequence of composition-dependent, spatially short-range attractions between the A and B monomers with the fullerene. A remarkably rich, polymer-specific temperature dependence of the spinodal diagram is predicted which reflects the thermal sensitivity of spatial correlations which can result in fullerene miscibility either increasing or decreasing with cooling. The calculations are contrasted with a simpler effective homopolymer model and the random structure Flory-Huggins model. The former appears to be qualitatively reasonable but can incur large quantitative errors since it misses preferential packing of monomers near nanoparticles, while the latter appears to fail qualitatively due to its neglect of all spatial correlations.},

  doi          = {},

  url          = {https://www.osti.gov/biblio/1096315},
  journal      = {Macromolecules},
number       = ,

  volume       = TBD,

  place        = {United States},

  year         = {Tue Jan 01 00:00:00 EST 2013},

  month        = {Tue Jan 01 00:00:00 EST 2013}

}

Copy to clipboard

Journal Article:

Other availability

Find in Google Scholar

Search WorldCat to find libraries that may hold this journal

Save / Share:

Export Metadata

Save to My Library

Similar records in OSTI.GOV collections:

Analytic PRISM theory of structurally asymmetric polymer blends and copolymers

Journal Article Schweizer, K - Macromolecules; (United States)

Analytic PRISM theory with the new molecular closures is applied to determine the effective chi-parameters and spinodal instability curves for structurally asymmetric polymer alloys. Compressibility effects are found to be very important, and the use of a literal incompressible RPA-like approximation is shown to incur qualitative errors in most cases. A rich and nonadditive dependence of phase transition temperatures and apparent SANS chi-parameters on backbone stiffness asymmetry, attractive interaction potential asymmetry, and thermodynamic variables is found for binary homopolymer blends. A novel strategy for designing miscible mixtures based on a cancellation, or compensation, of the relevant asymmetries is identified. Themore »« less
https://doi.org/10.1021/ma00074a029
Controlling effective interactions and spatial dispersion of nanoparticles in multiblock copolymer melts

Journal Article Banerjee, Debapriya; Schweizer, Kenneth - Journal of Polymer Science. Part B, Polymer Physics

The microscopic Polymer Reference Interaction Site Model theory is employed to study, for the first time, the effective interactions, spatial organization, and miscibility of dilute spherical nanoparticles in non-microphase separating, chemically heterogeneous, compositionally symmetric AB multiblock copolymer melts of varying monomer sequence or architecture. The dependence of nanoparticle wettability on copolymer sequence and chemistry results in interparticle potentials-of-mean force that are qualitatively different from homopolymers. An important prediction is the ability to improve nanoparticle dispersion via judicious choice of block length and monomer adsorption-strengths which control both local surface segregation and chain connectivity induced packing constraints and frustration. The degreemore »« less
https://doi.org/10.1002/polb.23752
Communication: Cosolvency and cononsolvency explained in terms of a Flory-Huggins type theory

Journal Article Dudowicz, Jacek; Freed, Karl; Douglas, Jack - Journal of Chemical Physics

Standard Flory-Huggins (FH) theory is utilized to describe the enigmatic cosolvency and cononsolvency phenomena for systems of polymers dissolved in mixed solvents. In particular, phase boundaries (specifically upper critical solution temperature spinodals) are calculated for solutions of homopolymers B in pure solvents and in binary mixtures of small molecule liquids A and C. The miscibility (or immiscibility) patterns for the ternary systems are classified in terms of the FH binary interaction parameters (χ{sub αβ}) and the ratio r = ϕ{sub A}/ϕ{sub C} of the concentrations ϕ{sub A} and ϕ{sub C} of the two solvents. The trends in miscibility are comparedmore »« less
https://doi.org/10.1063/1.4932061
Effect of matrix chemical heterogeneity on effective filler interactions in model polymer nanocomposites.

Conference Hall, Lisa

The microscopic Polymer Reference Interaction Site Model theory has been applied to spherical and rodlike fillers dissolved in three types of chemically heterogeneous polymer melts: alternating AB copolymer, random AB copolymers, and an equimolar blend of two homopolymers. In each case, one monomer species adsorbs more strongly on the filler mimicking a specific attraction, while all inter-monomer potentials are hard core which precludes macrophase or microphase separation. Qualitative differences in the filler potential-of-mean force are predicted relative to the homopolymer case. The adsorbed bound layer for alternating copolymers exhibits a spatial moduluation or layering effect but is otherwise similar tomore »« less
Impact of Monomer Sequence, Composition and Chemical Heterogeneity on Copolymer-Mediated Effective Interactions between Nanoparticles in Melts

Journal Article Hall, Lisa; Schweizer, Kenneth - Macromolecules

The microscopic polymer reference interaction site model theory is applied to study the structural correlations of dilute spherical nanoparticles dissolved in AB copolymer melts of variable architecture (alternating, random), composition, and monomernanoparticle adsorption strengths that span the depletion, steric stabilization, and bridging regimes. Comparison of the calculations of the monomerparticle pair correlations and polymer-mediated nanoparticle potential of mean force (PMF) with the behavior of reference homopolymers and a binary AB blend are also performed. All intermonomer potentials are hard core, which precludes polymer macrophase or microphase separation, thereby allowing the consequences of differential monomer wettability on nanoparticle spatial organization tomore »« less
https://doi.org/10.1021/ma200079z

Similar Records