Ordering transitions of fluoroalkyl-ended poly(ethylene glycol): Rheology and SANS

Giyoong Tae; Julia A. Kornfield; Jeffrey A. Hubbell; Jyotsana Lal

doi:10.1021/ma011809e

Ordering transitions of fluoroalkyl-ended poly(ethylene glycol): Rheology and SANS

Giyoong Tae, Julia A. Kornfield, Jeffrey A. Hubbell, Jyotsana Lal

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Abstract

Aqueous solutions of associative polymers consisting of poly(ethylene glycol) (PEG) (6K or 10K g/mol) terminated at both ends with hydrophobic fluoroalkyl segments, -(CH₂)₂C_nF_2n+1 (n = 6, 8, or 10), exhibit ordering transitions with increasing concentration. The hydrophobic cores of the micelle-like aggregates order into a body-centered-cubic (bcc) structure, as observed by small-angle neutron scattering. The aggregation number of the hydrophobic core N_ag is determined by the length of the hydrophobic end group and is insensitive to polymer concentration or temperature. Ordering is enhanced by reducing PEG length for a given end group (hence, similar N_ag) or by increasing end group length (larger N_ag) for a given PEG length. This micelle packing effect is manifested in changes in the viscoelastic properties. Specifically, the single-relaxation behavior in the dynamic moduli changes upon ordering as a new low-frequency elastic plateau appears, and in creep a linear response changes to yielding behavior.

Original language	English (US)
Pages (from-to)	4448-4457
Number of pages	10
Journal	Macromolecules
Volume	35
Issue number	11
DOIs	https://doi.org/10.1021/ma011809e
State	Published - May 21 2002

ASJC Scopus subject areas

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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title = "Ordering transitions of fluoroalkyl-ended poly(ethylene glycol): Rheology and SANS",

abstract = "Aqueous solutions of associative polymers consisting of poly(ethylene glycol) (PEG) (6K or 10K g/mol) terminated at both ends with hydrophobic fluoroalkyl segments, -(CH2)2CnF2n+1 (n = 6, 8, or 10), exhibit ordering transitions with increasing concentration. The hydrophobic cores of the micelle-like aggregates order into a body-centered-cubic (bcc) structure, as observed by small-angle neutron scattering. The aggregation number of the hydrophobic core Nag is determined by the length of the hydrophobic end group and is insensitive to polymer concentration or temperature. Ordering is enhanced by reducing PEG length for a given end group (hence, similar Nag) or by increasing end group length (larger Nag) for a given PEG length. This micelle packing effect is manifested in changes in the viscoelastic properties. Specifically, the single-relaxation behavior in the dynamic moduli changes upon ordering as a new low-frequency elastic plateau appears, and in creep a linear response changes to yielding behavior.",

author = "Giyoong Tae and Kornfield, {Julia A.} and Hubbell, {Jeffrey A.} and Jyotsana Lal",

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AU - Tae, Giyoong

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AU - Lal, Jyotsana

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N2 - Aqueous solutions of associative polymers consisting of poly(ethylene glycol) (PEG) (6K or 10K g/mol) terminated at both ends with hydrophobic fluoroalkyl segments, -(CH2)2CnF2n+1 (n = 6, 8, or 10), exhibit ordering transitions with increasing concentration. The hydrophobic cores of the micelle-like aggregates order into a body-centered-cubic (bcc) structure, as observed by small-angle neutron scattering. The aggregation number of the hydrophobic core Nag is determined by the length of the hydrophobic end group and is insensitive to polymer concentration or temperature. Ordering is enhanced by reducing PEG length for a given end group (hence, similar Nag) or by increasing end group length (larger Nag) for a given PEG length. This micelle packing effect is manifested in changes in the viscoelastic properties. Specifically, the single-relaxation behavior in the dynamic moduli changes upon ordering as a new low-frequency elastic plateau appears, and in creep a linear response changes to yielding behavior.

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