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Conformation and Phase Behavior of Sodium Carboxymethyl Cellulose in the Presence of Mono- and Divalent Salts

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    Conformation and Phase Behavior of Sodium Carboxymethyl Cellulose in the Presence of Mono- and Divalent Salts
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    Macromolecules

    Cite this: Macromolecules 2020, 53, 4, 1451–1463
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    https://doi.org/10.1021/acs.macromol.9b02228
    Published February 11, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    We report a small-angle neutron scattering (SANS) study of semidilute aqueous solutions of sodium carboxymethyl cellulose (NaCMC), in the presence of mono- (Na+) and divalent salts (Mg2+, Ca2+, Zn2+, and Ba2+). A degree of substitution of 1.3 is selected to ensure that, in salt-free solution, the polymer is molecularly dissolved. We find that Na+ and Mg2+ salt addition yields H-type phase behavior, while Ca2+, Zn2+, and Ba2+ instead yield a mixed H/L-type phase behavior dependent on the NaCMC concentration (cp), in the decreasing order of the salt concentration required to induce turbidity (at a fixed cp). Charge screening by addition of NaCl induces the disappearance of the characteristic polyelectrolyte correlation peak and eventually yields scattering profiles with a q–1 dependence over nearly 3 decades in the wavenumber q. By fitting a descriptive model to data with excess Na+, we obtain a correlation length ξ′ = 1030 cp–0.72 Å with cp in g L–1. Addition of Mg2+, which does not interact specifically with NaCMC carboxylate groups, yields an analogous screening behavior to that of Na+, albeit at lower salt concentrations, in line with its higher ionic strength. At low salt concentration, addition of specifically interacting Ca2+, Zn2+, and Ba2+ yields a comparatively greater screening of the polyelectrolyte correlation peak, and at concentrations above the phase boundary, results in excess scattering at low-q, compatible with the formation of 20–40 nm clusters. This behavior is interpreted as due to the reduction in charge density along the chain, promoting interchain association and multichain domain formation resulting in visible turbidity. Overall, drawing analogies with NaCMC at a lower degree of substitution, where hydrophobic association takes place, our findings provide a framework to describe the solution structure and phase behavior of NaCMC in salt-free and salt solutions.

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    • Scattering contrasts; overlap concentration of this NaCMC sample as a function of added salt (NaCl) concentration; modeling NaCMC phase behavior; partial molar volume determination of this NaCMC sample; fitting of the Horkay model to NaCMC in the presence of NaCMC; other models for the excess scattering observed with divalent salt addition (PDF)

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    Macromolecules

    Cite this: Macromolecules 2020, 53, 4, 1451–1463
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.macromol.9b02228
    Published February 11, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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