Huang, Q, Costanzo, S, Das, C orcid.org/0000-0002-1454-6210 et al. (1 more author) (2017) Stress growth and relaxation of dendritically branched macromolecules in shear and uniaxial extension. Journal of Rheology, 61 (1). pp. 35-47. ISSN 0148-6055
Abstract
We present unique nonlinear rheological data of well-defined symmetric Cayley-tree poly(methyl methacrylates) in shear and uniaxial extension. Earlier work has shown that their linear viscoelasticity is governed by the hierarchical relaxation of different generations, whereas the segments between branch points are responsible for their substantial strain hardening as compared to linear homopolymers of the same total molar mass at the same value of imposed stretch rate. Here, we extend that work in order to obtain further experimental evidence that will help understanding the molecular origin of the remarkable properties of these highly branched macromolecules. In particular, we address three questions pertinent to the specific molecular structure: (i) is steady state attainable during uniaxial extension? (ii) what is the respective transient response in simple shear? and (iii) how does stress relax upon cessation of extension or shear? To accomplish our goal we utilize state-of-the-art instrumentation, i.e., filament stretching rheometry (FSR) and cone-partitioned plate (CPP) shear rheometry for polymers with 3 and 4 generations, and complement it with state-of-the-art modeling predictions using the Branch-on-Branch (BoB) algorithm. The data indicates that the extensional viscosity reaches a steady state value, whose dependence on extension rate is identical to that of entangled linear and other branched polymer melts. Nonlinear shear is characterized by transient stress overshoots and the validity of the Cox-Merz rule. Remarkably, nonlinear stress relaxation is much broader and slower in extension compared to shear. It is also slower at higher generation, and rate-independent for rates below the Rouse rate of the outer segment. For extension, the relaxation time is longer than that of the linear stress relaxation, suggesting a strong ‘elastic memory’ of the material. These results are 2 described by BoB semi-quantitatively, both in linear and nonlinear shear and extensional regimes. Given the fact that the segments between branch points are less than 3 entanglements long, this is a very promising outcome that gives confidence in using BoB for understanding the key features. Moreover, the response of the segments between generations controls the rheology of the Cayley trees. Their substantial stretching in uniaxial extension appears responsible for strain hardening, whereas coupling of stretches of different parts of the polymer appears to be the origin of the slower subsequent relaxation of extensional stress. Concerning the latter effect, for which predictions are not available, it is hoped that the present experimental findings and proposed framework of analysis will motivate further developments in the direction of molecular constitutive models for branched and hyperbranched polymers.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2016 by The Society of Rheology, Inc. This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. The following article has been accepted by Journal of Rheology. After it is published, it will be found at http://scitation.aip.org/content/sor/journal/jor2. Uploaded in accordance with the publisher's self-archiving policy. |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Mathematics (Leeds) > Applied Mathematics (Leeds) |
Depositing User: | Symplectic Publications |
Date Deposited: | 03 Nov 2016 10:23 |
Last Modified: | 15 Apr 2017 22:32 |
Published Version: | https://doi.org/10.1122/1.4966040 |
Status: | Published |
Publisher: | AIP Publishing |
Identification Number: | 10.1122/1.4966040 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:106926 |