Micellar Solutions of Associative Triblock Copolymers:  The Relationship between Structure and Rheology

We report the rheology of the micellar solutions formed from narrow-molecular-weight poly(ethylene oxide) chains fully endcapped with C16 or C18 alkanes and correlate the viscoelasticity, characterized by the high-frequency modulus G ∞‘ and a single relaxation time λ, with the measured characteristi...

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Published in:Macromolecules Vol. 32; no. 15; pp. 5139 - 5146
Main Authors: Pham, Q. T, Russel, W. B, Thibeault, J. C, Lau, W
Format: Journal Article
Language:English
Published: Washington, DC American Chemical Society 27-07-1999
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Abstract We report the rheology of the micellar solutions formed from narrow-molecular-weight poly(ethylene oxide) chains fully endcapped with C16 or C18 alkanes and correlate the viscoelasticity, characterized by the high-frequency modulus G ∞‘ and a single relaxation time λ, with the measured characteristics of the micellar solutions. Scaling G ∞‘ by p 3/2 kT/τ R H 3 (p = aggregation number, R H = hydrodynamic radius, 1/τ = attractive virial coefficient, k = Boltzmann's constant, and T = temperature) and plotting against the hydrodynamic volume fraction of micelles collapses the two sets of data. The relaxation time scales as the diffusion time, μ R c 3/kT, for a free hydrophobe escaping from a micellar core of radius R c times a Boltzmann factor accounting for an association energy that increases linearly with hydrophobe length. The low shear viscosity follows as η o = λ G ∞‘.
AbstractList We report the rheology of the micellar solutions formed from narrow-molecular-weight poly(ethylene oxide) chains fully endcapped with C16 or C18 alkanes and correlate the viscoelasticity, characterized by the high-frequency modulus G ∞‘ and a single relaxation time λ, with the measured characteristics of the micellar solutions. Scaling G ∞‘ by p 3/2 kT/τ R H 3 (p = aggregation number, R H = hydrodynamic radius, 1/τ = attractive virial coefficient, k = Boltzmann's constant, and T = temperature) and plotting against the hydrodynamic volume fraction of micelles collapses the two sets of data. The relaxation time scales as the diffusion time, μ R c 3/kT, for a free hydrophobe escaping from a micellar core of radius R c times a Boltzmann factor accounting for an association energy that increases linearly with hydrophobe length. The low shear viscosity follows as η o = λ G ∞‘.
Author Thibeault, J. C
Pham, Q. T
Lau, W
Russel, W. B
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Issue 15
Keywords Ethylene oxide polymer
Monodispersed polymer
Shear viscosity
End group
Shear modulus
Solution structure
Concentration effect
Hydrophobic group
Property structure relationship
Aqueous solution
Experimental study
Micellar solution
Language English
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Snippet We report the rheology of the micellar solutions formed from narrow-molecular-weight poly(ethylene oxide) chains fully endcapped with C16 or C18 alkanes and...
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SubjectTerms Applied sciences
Exact sciences and technology
Organic polymers
Physicochemistry of polymers
Properties and characterization
Solution and gel properties
Title Micellar Solutions of Associative Triblock Copolymers:  The Relationship between Structure and Rheology
URI http://dx.doi.org/10.1021/ma990215x
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