Ball-of-yarn conformation of a linear gradient copolymer in a homopolymer melt

Nicholas B. Tito, Scott Thomas Milner, Jane E.G. Lipson

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

The conformation of a linear gradient copolymer chain in a homopolymer melt is investigated using theory and numerical solutions of self-consistent field equations. In the limit of large comonomer immiscibility and chain length, it is found that the copolymer collapses into a globule with monomers self-assembled into a "ball-of-yarn" conformation. The spatial heterogeneity of monomers within the globule is in striking contrast to the "tadpole" conformation of a collapsed symmetric diblock copolymer and the disordered globular state of a collapsed homopolymer or random copolymer. By simple free energy calculations, we find that the same thermodynamic factors which drive a melt of linear gradient copolymers to self-assemble into lamellar microphases in the strong-segregation regime act to drive a single copolymer to self-assemble its own monomers into the yarn ball conformation when in a homopolymer melt with which it is immiscible. Moreover, by considering self-assembly of monomers within the globule of a collapsed copolymer, we find that the thermodynamic stability of a linear gradient is less than a symmetric diblock-a conclusion that is not possible to obtain by assuming that the copolymers pack their monomers randomly upon collapse.

Original languageEnglish (US)
Pages (from-to)7607-7620
Number of pages14
JournalMacromolecules
Volume45
Issue number18
DOIs
StatePublished - Sep 25 2012

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Homopolymerization
Conformations
Yarn
Copolymers
Monomers
Chain length
Self assembly
Free energy
Block copolymers
Thermodynamic stability
Solubility
Thermodynamics

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Tito, Nicholas B. ; Milner, Scott Thomas ; Lipson, Jane E.G. / Ball-of-yarn conformation of a linear gradient copolymer in a homopolymer melt. In: Macromolecules. 2012 ; Vol. 45, No. 18. pp. 7607-7620.
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Ball-of-yarn conformation of a linear gradient copolymer in a homopolymer melt. / Tito, Nicholas B.; Milner, Scott Thomas; Lipson, Jane E.G.

In: Macromolecules, Vol. 45, No. 18, 25.09.2012, p. 7607-7620.

Research output: Contribution to journalArticle

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