Shear-induced disruption and recovery of microphase-separated network structure of a BSB triblock copolymer in dibutyl phthalate

Hendra Tan, Hiroshi Watanabe, Yumi Matsumiya, Toshiji Kanaya, Yoshiaki Takahashi

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

Rheological and structural properties were examined for a 30 wt % solution of a 1,4-butadiene-styrene-1,4-butadiene (BSB) triblock copolymer (Ms = 108 × 103, MB = 13.3 × 103 for each B block) in an S-selective solvent, dibutyl phthalate (DBP). At equilibrium at 25 °C, a bcc lattice of the unsolved, soft (rubbery) B domains connected by the middle S blocks (a lattice-type network) was formed to exhibit the elastic behavior against small strains. This lattice-type network was disrupted under steady shear to lose its elasticity, and the strongest disruption occurred at an intermediate shear rate (γ̇) close to a frequency of B/S concentration fluctuation. This disruption behavior was similar to that of a BS/DBP diblock micellar lattice system. However, for the BSB/DBP system, an order of magnitude increase of γ̇ resulted in a minor change (by a factor <30%) of a time tr required for the full recovery of the elasticity during a quiescent rest after the preshear. This result, quantitatively different from that seen for the BS/DBP diblock system, was related to the bridge-type configuration of the middle S blocks of BSB: Under the steady shear, a large fraction of the bridges in the flowing defect region would be converted into loops. Thus, the re-formation of the bridges in this region (a process absent in the BS/DBP system) should be required for the full recovery of the elasticity of the BSB/DBP system. This bridge re-formation, leading to a recovery of the order of the B domain arrangement and allowing the coexisting loops to exhibit the elasticity, should be accompanied by a transient mixing of the B and S block and thus gave the very weakly γ̇-dependent tr determined by the mixing enthalpy.

Original languageEnglish
Pages (from-to)2886-2893
Number of pages8
JournalMacromolecules
Volume36
Issue number8
DOIs
Publication statusPublished - Apr 22 2003

Fingerprint

Dibutyl Phthalate
Styrene
Butadiene
Block copolymers
Recovery
Elasticity
1,3-butadiene
Shear deformation
Structural properties
Enthalpy
Defects

All Science Journal Classification (ASJC) codes

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

Cite this

Shear-induced disruption and recovery of microphase-separated network structure of a BSB triblock copolymer in dibutyl phthalate. / Tan, Hendra; Watanabe, Hiroshi; Matsumiya, Yumi; Kanaya, Toshiji; Takahashi, Yoshiaki.

In: Macromolecules, Vol. 36, No. 8, 22.04.2003, p. 2886-2893.

Research output: Contribution to journalArticle

Tan, Hendra ; Watanabe, Hiroshi ; Matsumiya, Yumi ; Kanaya, Toshiji ; Takahashi, Yoshiaki. / Shear-induced disruption and recovery of microphase-separated network structure of a BSB triblock copolymer in dibutyl phthalate. In: Macromolecules. 2003 ; Vol. 36, No. 8. pp. 2886-2893.
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abstract = "Rheological and structural properties were examined for a 30 wt {\%} solution of a 1,4-butadiene-styrene-1,4-butadiene (BSB) triblock copolymer (Ms = 108 × 103, MB = 13.3 × 103 for each B block) in an S-selective solvent, dibutyl phthalate (DBP). At equilibrium at 25 °C, a bcc lattice of the unsolved, soft (rubbery) B domains connected by the middle S blocks (a lattice-type network) was formed to exhibit the elastic behavior against small strains. This lattice-type network was disrupted under steady shear to lose its elasticity, and the strongest disruption occurred at an intermediate shear rate (γ̇) close to a frequency of B/S concentration fluctuation. This disruption behavior was similar to that of a BS/DBP diblock micellar lattice system. However, for the BSB/DBP system, an order of magnitude increase of γ̇ resulted in a minor change (by a factor <30{\%}) of a time tr∞ required for the full recovery of the elasticity during a quiescent rest after the preshear. This result, quantitatively different from that seen for the BS/DBP diblock system, was related to the bridge-type configuration of the middle S blocks of BSB: Under the steady shear, a large fraction of the bridges in the flowing defect region would be converted into loops. Thus, the re-formation of the bridges in this region (a process absent in the BS/DBP system) should be required for the full recovery of the elasticity of the BSB/DBP system. This bridge re-formation, leading to a recovery of the order of the B domain arrangement and allowing the coexisting loops to exhibit the elasticity, should be accompanied by a transient mixing of the B and S block and thus gave the very weakly γ̇-dependent tr∞ determined by the mixing enthalpy.",
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AU - Takahashi, Yoshiaki

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