Viscosity and Scaling of Semiflexible Polyelectrolyte NaCMC in Aqueous Salt Solutions
File(s)CMC Lopez 2016 revised.pdf (1013.6 KB)
Accepted version
Author(s)
Lopez, CG
Colby, RH
Graham, P
Cabral, JT
Type
Journal Article
Abstract
We investigate the viscosity dependence on concentration and molecular weight of semiflexible polyelectrolyte sodium carboxymethylcellulose (NaCMC) in aqueous salt-free and NaCl solutions. Combining new measurements and extensive literature data, we establish relevant power laws and crossovers over a wide range of degree of polymerization (N) as well as polymer (c) and salt (cs) concentrations. In salt-free solution, the overlap concentration shows the expected c* ∝ N–2 dependence, and the entanglement crossover scales as ce ∝ N–0.6±0.3, in strong disagreement with scaling theory for which ce ∝ c* is expected, but matching the behavior found for flexible polyelectrolytes. A second crossover, to a steep concentration dependence for specific viscosity (ηsp ∝ c3.5±0.2), commonly assigned to the concentrated regime, is shown to follow c** ∝ N–0.6±0.2 (with c**/ce ≃ 6) which thus suggests instead a dynamic crossover, possibly related to entanglement. The scaling of c* and ce in 0.01 and 0.1 M NaCl shows neutral polymer in good solvent behavior, characteristic of highly screened polyelectrolyte solutions. This unified scaling picture enables the estimation of viscosity of ubiquitous NaCMC solutions as a function of N, c, and cs and establishes the behavior expected for a range of semiflexible polyelectrolyte solutions.
Date Issued
2016-12-30
Date Acceptance
2016-12-01
Citation
Macromolecules, 2016, 50 (1), pp.332-338
ISSN
0024-9297
Publisher
American Chemical Society
Start Page
332
End Page
338
Journal / Book Title
Macromolecules
Volume
50
Issue
1
Copyright Statement
© 2016 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Macromolecules, after peer review and technical editing by the publisher. To access the final edited and published work see https://dx.doi.org/10.1021/acs.macromol.6b02261
Identifier
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000391898000032&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
Subjects
Science & Technology
Physical Sciences
Polymer Science
SODIUM CARBOXYMETHYL CELLULOSE
ANGLE NEUTRON-SCATTERING
POLY(N-HEXYL ISOCYANATE) SOLUTIONS
SIZE-EXCLUSION CHROMATOGRAPHY
ENTANGLED SEMIDILUTE SOLUTION
ZERO-SHEAR VISCOSITY
MIXED-SOLVENT MEDIA
INTRINSIC VISCOSITIES
POLYMER-SOLUTIONS
MOLECULAR-WEIGHT
03 Chemical Sciences
09 Engineering
Polymers
Publication Status
Published