Linear shear and nonlinear extensional rheology of unentangled supramolecular side-chain polymers

Guanghui Cui, Victor A. H. Boudara, Qian Huang, Guilhem P. Baeza, Andrew J. Wilson, Ole Hassager, Daniel J. Read, Johan Mattsson*

*Corresponding author for this work

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Abstract

Supramolecular polymers are important within a wide range of applications including printing, adhesives, coatings, cosmetics, surgery, and nano-fabrication. The possibility to tune polymer properties through the control of supramolecular associations makes these materials both versatile and powerful. Here, we present a systematic investigation of the linear shear rheology for a series of unentangled ethylhexyl acrylate-based polymers for which the concentration of randomly distributed supramolecular side groups is systematically varied. We perform a detailed investigation of the applicability of time temperature superposition (TTS) for our polymers; small amplitude oscillatory shear rheology is combined with stress relaxation experiments to identify the dynamic range over which TTS is a reasonable approximation. Moreover, we find that the “sticky-Rouse” model normally used to interpret the rheological response of supramolecular polymers fits our experimental data well in the terminal regime, but is less successful in the rubbery plateau regime. We propose some modifications to the “sticky-Rouse” model, which includes more realistic assumptions with regard to (i) the random placement of the stickers along the backbone, (ii) the contributions from dangling chain ends, and (iii) the chain motion upon dissociation of a sticker and reassociation with a new co-ordination which involves a finite sized “hop” of the chain. Our model provides an improved description of the plateau region. Finally, we measure the extensional rheological response of one of our supramolecular polymers. For the probed extensional flow rates, which are small compared to the characteristic rates of sticker dynamics, we expect a Rouse-type description to work well. We test this by modeling the observed strain hardening using the upper convected Maxwell model and demonstrate that this simple model can describe the data well, confirming the prediction and supporting our determination of sticker dynamics based on linear shear rheology.
Original languageEnglish
JournalJournal of Rheology
Volume62
Issue number5
Pages (from-to)1155-1174
Number of pages20
ISSN0148-6055
DOIs
Publication statusPublished - 2018

Cite this

Cui, Guanghui ; Boudara, Victor A. H. ; Huang, Qian ; Baeza, Guilhem P. ; Wilson, Andrew J. ; Hassager, Ole ; Read, Daniel J. ; Mattsson, Johan. / Linear shear and nonlinear extensional rheology of unentangled supramolecular side-chain polymers. In: Journal of Rheology. 2018 ; Vol. 62, No. 5. pp. 1155-1174.
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title = "Linear shear and nonlinear extensional rheology of unentangled supramolecular side-chain polymers",
abstract = "Supramolecular polymers are important within a wide range of applications including printing, adhesives, coatings, cosmetics, surgery, and nano-fabrication. The possibility to tune polymer properties through the control of supramolecular associations makes these materials both versatile and powerful. Here, we present a systematic investigation of the linear shear rheology for a series of unentangled ethylhexyl acrylate-based polymers for which the concentration of randomly distributed supramolecular side groups is systematically varied. We perform a detailed investigation of the applicability of time temperature superposition (TTS) for our polymers; small amplitude oscillatory shear rheology is combined with stress relaxation experiments to identify the dynamic range over which TTS is a reasonable approximation. Moreover, we find that the “sticky-Rouse” model normally used to interpret the rheological response of supramolecular polymers fits our experimental data well in the terminal regime, but is less successful in the rubbery plateau regime. We propose some modifications to the “sticky-Rouse” model, which includes more realistic assumptions with regard to (i) the random placement of the stickers along the backbone, (ii) the contributions from dangling chain ends, and (iii) the chain motion upon dissociation of a sticker and reassociation with a new co-ordination which involves a finite sized “hop” of the chain. Our model provides an improved description of the plateau region. Finally, we measure the extensional rheological response of one of our supramolecular polymers. For the probed extensional flow rates, which are small compared to the characteristic rates of sticker dynamics, we expect a Rouse-type description to work well. We test this by modeling the observed strain hardening using the upper convected Maxwell model and demonstrate that this simple model can describe the data well, confirming the prediction and supporting our determination of sticker dynamics based on linear shear rheology.",
author = "Guanghui Cui and Boudara, {Victor A. H.} and Qian Huang and Baeza, {Guilhem P.} and Wilson, {Andrew J.} and Ole Hassager and Read, {Daniel J.} and Johan Mattsson",
year = "2018",
doi = "10.1122/1.5012349",
language = "English",
volume = "62",
pages = "1155--1174",
journal = "Journal of Rheology",
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publisher = "Society of Rheology",
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Linear shear and nonlinear extensional rheology of unentangled supramolecular side-chain polymers. / Cui, Guanghui; Boudara, Victor A. H.; Huang, Qian; Baeza, Guilhem P.; Wilson, Andrew J.; Hassager, Ole; Read, Daniel J.; Mattsson, Johan.

In: Journal of Rheology, Vol. 62, No. 5, 2018, p. 1155-1174.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Linear shear and nonlinear extensional rheology of unentangled supramolecular side-chain polymers

AU - Cui, Guanghui

AU - Boudara, Victor A. H.

AU - Huang, Qian

AU - Baeza, Guilhem P.

AU - Wilson, Andrew J.

AU - Hassager, Ole

AU - Read, Daniel J.

AU - Mattsson, Johan

PY - 2018

Y1 - 2018

N2 - Supramolecular polymers are important within a wide range of applications including printing, adhesives, coatings, cosmetics, surgery, and nano-fabrication. The possibility to tune polymer properties through the control of supramolecular associations makes these materials both versatile and powerful. Here, we present a systematic investigation of the linear shear rheology for a series of unentangled ethylhexyl acrylate-based polymers for which the concentration of randomly distributed supramolecular side groups is systematically varied. We perform a detailed investigation of the applicability of time temperature superposition (TTS) for our polymers; small amplitude oscillatory shear rheology is combined with stress relaxation experiments to identify the dynamic range over which TTS is a reasonable approximation. Moreover, we find that the “sticky-Rouse” model normally used to interpret the rheological response of supramolecular polymers fits our experimental data well in the terminal regime, but is less successful in the rubbery plateau regime. We propose some modifications to the “sticky-Rouse” model, which includes more realistic assumptions with regard to (i) the random placement of the stickers along the backbone, (ii) the contributions from dangling chain ends, and (iii) the chain motion upon dissociation of a sticker and reassociation with a new co-ordination which involves a finite sized “hop” of the chain. Our model provides an improved description of the plateau region. Finally, we measure the extensional rheological response of one of our supramolecular polymers. For the probed extensional flow rates, which are small compared to the characteristic rates of sticker dynamics, we expect a Rouse-type description to work well. We test this by modeling the observed strain hardening using the upper convected Maxwell model and demonstrate that this simple model can describe the data well, confirming the prediction and supporting our determination of sticker dynamics based on linear shear rheology.

AB - Supramolecular polymers are important within a wide range of applications including printing, adhesives, coatings, cosmetics, surgery, and nano-fabrication. The possibility to tune polymer properties through the control of supramolecular associations makes these materials both versatile and powerful. Here, we present a systematic investigation of the linear shear rheology for a series of unentangled ethylhexyl acrylate-based polymers for which the concentration of randomly distributed supramolecular side groups is systematically varied. We perform a detailed investigation of the applicability of time temperature superposition (TTS) for our polymers; small amplitude oscillatory shear rheology is combined with stress relaxation experiments to identify the dynamic range over which TTS is a reasonable approximation. Moreover, we find that the “sticky-Rouse” model normally used to interpret the rheological response of supramolecular polymers fits our experimental data well in the terminal regime, but is less successful in the rubbery plateau regime. We propose some modifications to the “sticky-Rouse” model, which includes more realistic assumptions with regard to (i) the random placement of the stickers along the backbone, (ii) the contributions from dangling chain ends, and (iii) the chain motion upon dissociation of a sticker and reassociation with a new co-ordination which involves a finite sized “hop” of the chain. Our model provides an improved description of the plateau region. Finally, we measure the extensional rheological response of one of our supramolecular polymers. For the probed extensional flow rates, which are small compared to the characteristic rates of sticker dynamics, we expect a Rouse-type description to work well. We test this by modeling the observed strain hardening using the upper convected Maxwell model and demonstrate that this simple model can describe the data well, confirming the prediction and supporting our determination of sticker dynamics based on linear shear rheology.

U2 - 10.1122/1.5012349

DO - 10.1122/1.5012349

M3 - Journal article

VL - 62

SP - 1155

EP - 1174

JO - Journal of Rheology

JF - Journal of Rheology

SN - 0148-6055

IS - 5

ER -