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  5. Conformation of cellulose-based polyelectrolytes and development of microflow scattering approaches
 
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Conformation of cellulose-based polyelectrolytes and development of microflow scattering approaches
File(s)
Gonzalez Lopez-C-2016-PhD-Thesis.pdf (12.91 MB)
Thesis
Author(s)
Gonzalez Lopez, Carlos
Type
Thesis or dissertation
Abstract
The work reported on this thesis is primarily a small angle neutron scattering (SANS) and rheology study of cellulose derivative polyelectrolyte Sodium Carboxymethyl Cellulose (NaCMC) in aqueous solutions. We measure, for the first time using SANS, the relevant structural length scales as a function of polymer (cp) in aqueous salt free and NaCl solutions. The intrinsic persistence length is measured by SANS to be 55 A, characteristic of a semi-flexible polymer. In salt-free solutions, the correlation length is found to scale as cp^-1/2 across the entire semi-dilute and concentrated range. Both SANS and viscosity measurements are in general agreement with scaling theory predictions for flexible polyelectrolytes in salt free solution. The crossover between the semidilute and concentrated regimes cannot be explained as arising from the overlapping of correlation and electrostatic blobs, and appears to relate to the intrinsic persistence length of the polymer. As expected, the addition of salt leads to a decrease in viscosity and an increase in the correlation length. Flexible scaling theory cannot describe the variation of these two quantities accurately, as it neglects the intrinsic rigidity of the chains. The scaling picture put forward by Odijk appears to be correct in the high salt limit, although it suffers from several approximations, namely the use of a simplified expansion factor and an inaccurate expression from the excluded volume. Once these are corrected, theory and experiment show good agreement. We finally report the combination of SANS with microfluidics, which is a useful technique to probe the soft matter dynamics under flow, and illustrate it with well-known strongly scattering liquid crystal systems, quantifying alignment through a contraction-expansion flow field. Different microfabrication techniques and materials are discussed in terms of their compatibility with SANS. Finally, we outline a roadmap for microfluidic SANS, enabling the spatiotemporal investigation of conformational changes under flow, focusing on low scattering systems, including NaCMC in solution.
Version
Open Access
Date Issued
2014-12
Date Awarded
2016-03
URI
http://hdl.handle.net/10044/1/58271
DOI
https://doi.org/10.25560/58271
Advisor
Cabral, Joao
Sponsor
Engineering and Physical Sciences Research Council
Unilever (Firm)
Grant Number
CASE award 1000087X, PS-2010-0651
Publisher Department
Chemical Engineering
Publisher Institution
Imperial College London
Qualification Level
Doctoral
Qualification Name
Doctor of Philosophy (PhD)
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