Linear viscoelastic response and steady shear viscosity of native cellulose in 1-ethyl-3-methylimidazolium methylphosphonate

Xun Chen; Siwei Liang; Shih Wa Wang; Ralph H. Colby

doi:10.1122/1.4990049

Linear viscoelastic response and steady shear viscosity of native cellulose in 1-ethyl-3-methylimidazolium methylphosphonate

Xun Chen, Siwei Liang, Shih Wa Wang, Ralph H. Colby

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Abstract

Oscillatory and steady shear of cellulose in 1-ethyl-3-methylimidazolium methylphosphonate {[EMIm][P(OCH₃)(H)O₂]} were studied for cellulose concentrations from 0.017 to 10 wt. %, spanning the dilute, semidilute unentangled and entangled regimes. The overlap concentration of our cellulose in [EMIm][P(OCH₃)(H)O₂] is 0.065 wt. % and the entanglement concentration is 8× larger (0.5 wt. %). The concentration dependences of specific viscosity, relaxation time, and terminal modulus suggest that [EMIm][P(OCH₃)(H)O₂] is a good solvent for cellulose. Compared with the cellulose/1-butyl-3-methyl imidazolium chloride ([BMIm]Cl) system, this native cellulose in [EMIm][P(OCH₃)(H)O₂] has lower c∗ and c_e, and much higher extent of entanglement. A significantly wider than expected rubbery plateau for the entangled solutions and failure of the Cox-Merz rule suggest that cellulose in [EMIm][P(OCH₃)(H)O₂] is not simply a flexible polymer in a good solvent. The relaxation mode distribution in the terminal regime is much broader for cellulose in [EMIm][P(OCH₃)(H)O₂] compared with the same cellulose in [BMIm]Cl. The delocalized phosphonate anion likely binds to hydroxyl groups on multiple cellulose chains, acting as temporary crosslinks.

Original language	English (US)
Pages (from-to)	81-87
Number of pages	7
Journal	Journal of Rheology
Volume	62
Issue number	1
DOIs	https://doi.org/10.1122/1.4990049
State	Published - Jan 1 2018

All Science Journal Classification (ASJC) codes

Materials Science(all)
Condensed Matter Physics
Mechanics of Materials
Mechanical Engineering

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title = "Linear viscoelastic response and steady shear viscosity of native cellulose in 1-ethyl-3-methylimidazolium methylphosphonate",

abstract = "Oscillatory and steady shear of cellulose in 1-ethyl-3-methylimidazolium methylphosphonate {[EMIm][P(OCH3)(H)O2]} were studied for cellulose concentrations from 0.017 to 10 wt. %, spanning the dilute, semidilute unentangled and entangled regimes. The overlap concentration of our cellulose in [EMIm][P(OCH3)(H)O2] is 0.065 wt. % and the entanglement concentration is 8× larger (0.5 wt. %). The concentration dependences of specific viscosity, relaxation time, and terminal modulus suggest that [EMIm][P(OCH3)(H)O2] is a good solvent for cellulose. Compared with the cellulose/1-butyl-3-methyl imidazolium chloride ([BMIm]Cl) system, this native cellulose in [EMIm][P(OCH3)(H)O2] has lower c∗ and ce, and much higher extent of entanglement. A significantly wider than expected rubbery plateau for the entangled solutions and failure of the Cox-Merz rule suggest that cellulose in [EMIm][P(OCH3)(H)O2] is not simply a flexible polymer in a good solvent. The relaxation mode distribution in the terminal regime is much broader for cellulose in [EMIm][P(OCH3)(H)O2] compared with the same cellulose in [BMIm]Cl. The delocalized phosphonate anion likely binds to hydroxyl groups on multiple cellulose chains, acting as temporary crosslinks.",

author = "Xun Chen and Siwei Liang and Wang, {Shih Wa} and Colby, {Ralph H.}",

note = "Funding Information: Funding from the National Science Foundation, DMR-1506589 BMAT/SusChEM program is gratefully acknowledged. Publisher Copyright: {\textcopyright} 2017 The Society of Rheology.",

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doi = "10.1122/1.4990049",

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T1 - Linear viscoelastic response and steady shear viscosity of native cellulose in 1-ethyl-3-methylimidazolium methylphosphonate

AU - Chen, Xun

AU - Liang, Siwei

AU - Wang, Shih Wa

AU - Colby, Ralph H.

PY - 2018/1/1

Y1 - 2018/1/1

N2 - Oscillatory and steady shear of cellulose in 1-ethyl-3-methylimidazolium methylphosphonate {[EMIm][P(OCH3)(H)O2]} were studied for cellulose concentrations from 0.017 to 10 wt. %, spanning the dilute, semidilute unentangled and entangled regimes. The overlap concentration of our cellulose in [EMIm][P(OCH3)(H)O2] is 0.065 wt. % and the entanglement concentration is 8× larger (0.5 wt. %). The concentration dependences of specific viscosity, relaxation time, and terminal modulus suggest that [EMIm][P(OCH3)(H)O2] is a good solvent for cellulose. Compared with the cellulose/1-butyl-3-methyl imidazolium chloride ([BMIm]Cl) system, this native cellulose in [EMIm][P(OCH3)(H)O2] has lower c∗ and ce, and much higher extent of entanglement. A significantly wider than expected rubbery plateau for the entangled solutions and failure of the Cox-Merz rule suggest that cellulose in [EMIm][P(OCH3)(H)O2] is not simply a flexible polymer in a good solvent. The relaxation mode distribution in the terminal regime is much broader for cellulose in [EMIm][P(OCH3)(H)O2] compared with the same cellulose in [BMIm]Cl. The delocalized phosphonate anion likely binds to hydroxyl groups on multiple cellulose chains, acting as temporary crosslinks.

AB - Oscillatory and steady shear of cellulose in 1-ethyl-3-methylimidazolium methylphosphonate {[EMIm][P(OCH3)(H)O2]} were studied for cellulose concentrations from 0.017 to 10 wt. %, spanning the dilute, semidilute unentangled and entangled regimes. The overlap concentration of our cellulose in [EMIm][P(OCH3)(H)O2] is 0.065 wt. % and the entanglement concentration is 8× larger (0.5 wt. %). The concentration dependences of specific viscosity, relaxation time, and terminal modulus suggest that [EMIm][P(OCH3)(H)O2] is a good solvent for cellulose. Compared with the cellulose/1-butyl-3-methyl imidazolium chloride ([BMIm]Cl) system, this native cellulose in [EMIm][P(OCH3)(H)O2] has lower c∗ and ce, and much higher extent of entanglement. A significantly wider than expected rubbery plateau for the entangled solutions and failure of the Cox-Merz rule suggest that cellulose in [EMIm][P(OCH3)(H)O2] is not simply a flexible polymer in a good solvent. The relaxation mode distribution in the terminal regime is much broader for cellulose in [EMIm][P(OCH3)(H)O2] compared with the same cellulose in [BMIm]Cl. The delocalized phosphonate anion likely binds to hydroxyl groups on multiple cellulose chains, acting as temporary crosslinks.

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Linear viscoelastic response and steady shear viscosity of native cellulose in 1-ethyl-3-methylimidazolium methylphosphonate

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