Chain self-diffusion in aqueous salt-free solutions of sodium poly(styrenesulfonate)

Oostwal, M. G.; Blees, M.H.; Bleijser, J. De; Leyte, J. C.

doi:10.1021/ma00078a028

Cited by 44 publications

(67 citation statements)

References 11 publications

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“…The chain length dependence of viscosity in semidilute unentangled solution is shown in Figure 8 for both NaPAMS and sodium poly(styrene sulfonate) NaPSS at c ϭ 0.002M. 15,25,26 Witten and Pincus predict sp ϳ N 2 , while Dobrynin et al predict sp ϳ N. In Figure 8a, we find sp ϳ N 2.4Ϯ0.6 , if we force a power law to fit the data. Figure 8(b) plots the same data in exponential form, resulting in the conclusion that the data are best described by an exponential function.…”

Section: Resultsmentioning

confidence: 82%

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Semidilute solution rheology of polyelectrolytes with no added salt

Krause¹,

Tan²,

Colby³

1999

J. Polym. Sci. B Polym. Phys.

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We report rheological data on anionic polyelectrolyte solutions of variable chain length and concentration, specifically sodium poly(2‐acrylamido‐2‐methylpropanesulfonate), with no added salt. Our results are consistent with literature data on the sodium salt of sulfonated polystyrene. We find a strong dependence of viscosity η on chain length: η ∼ M2.4. This is in reasonable agreement with the scaling theory proposed by Witten and Pincus (η ∼ M2) and is much stronger than the scaling prediction of Dobrynin et al. (η ∼ M). The ratio of the viscosity and relaxation time gives the modulus at the relaxation time, which is experimentally consistent with the kT per chain expected by Dobrynin et al., and much smaller than the kT per charged monomer expected by Witten and Pincus (upon which the η ∼ M2 prediction is based). Thus, we are forced to draw a conclusion for polyelectrolytes that seems to be a recurring one in polymer dynamics: The modulus is in quantitative agreement with theory, but the relaxation time is poorly understood. This exemplifies the fact that frictional and/or hydrodynamic interactions are not properly accounted for in scaling theories of polymer dynamics. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 3429–3437, 1999

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Section: Resultsmentioning

confidence: 82%

“…Chain length dependence of specific viscosity at c ϭ 0.002M for both NaPAMS (filled circles) and NaPSS15,25,26 (open triangles). This concentration was chosen so that all seven samples are in the semidilute unentangled concentration regime.…”

mentioning

confidence: 99%

Semidilute solution rheology of polyelectrolytes with no added salt

Krause¹,

Tan²,

Colby³

1999

J. Polym. Sci. B Polym. Phys.

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“…Therefore, due to the diffusion coefficient dispersity, at high b values the signal deviates from a simple single exponential and a mono-exponential fit leads to a significant underestimation of the average diffusion coefficient D . To fit the data satisfactorily, it is then necessary to take into account this departure [16,19,[36][37][38][39], using for example the following second order expansion:…”

Section: Nuclear Magnetic Resonancementioning

confidence: 99%

Ionization of short weak polyelectrolytes: when size matters

Dolce

Mériguet

2016

Colloid Polym Sci

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The ionization of short weak polyelectrolytes in dilute solutions is investigated by 1 H Nuclear Magnetic Resonance (NMR). The increase of the pH of the medium causes both the ionization of the polyacids and, due to the intramolecular repulsions, the swelling of the chains. As a result, a noticeable effect of the pH change on the NMR chemical shift δ , and on the self-diffusion coefficient D is observed. The ionization of the polyelectrolyte occurs at higher pH as the length of the chain increases. The variation of the selfdiffusion coefficient with pH exhibits the opposite dependence on the length of the chain. However, no detectable effect of the length of the polyelectrolyte chain on the evolution of the chemical shift with pH is observed. These apparent contradictions are examined to clarify the impact of the chain length on the polyelectrolyte properties, and the counterion role in the ionization process.

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“…However, it has to be taken into account that the diffusion coefficient for polyelectrolytes changes with concentration [2,32]. For dilute solutions of polyelectrolytes the diffusion coefficient determined by light scattering obeys a D ∼ c h 0 dependence [33] with h ranging from −0.1 to −1.0 [2].…”

Section: Description Of the Adsorption As Diffusion Controlled Processmentioning

confidence: 99%

Adsorption of anionic polyelectrolytes to dioctadecyldimethylammonium bromide monolayers

Engelking

Menzel

2001

The European Physical Journal E

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Monolayers of dioctadecyldimethylammonium bromide (DODA) at the air/water interface were used as model for charged surfaces to study the adsorption of anionic polyelectrolytes. After spreading on a pure water surface the monolayers were compressed and subsequently transferred onto a polyelectrolyte solution employing the Fromherz technique. The polyelectrolyte adsorption was monitored by recording the changes in surface pressure at constant area. For poly(styrene sulfonate) and carboxymethylcellulose the plot of the surface pressure as function of time gave curves which indicate a direct correlation between the adsorbed amount and surface pressure as well as a solely diffusion controlled process. In the case of rigid rod-like poly(p-phenylene sulfonate)s the situation is more complicated. Plotting the surface pressure as function of time results in a curve with sigmoidal shape, characterized by an induction period. The induction period can be explained by a domain formation, which can be treated like a crystallization process. Employing the Avrami expression developed for polymer crystallization, the change in the surface pressure upon adsorption of rigid rod-like poly(p-phenylene sulfonate)s can be described.

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Chain self-diffusion in aqueous salt-free solutions of sodium poly(styrenesulfonate)

Cited by 44 publications

References 11 publications

Semidilute solution rheology of polyelectrolytes with no added salt

Semidilute solution rheology of polyelectrolytes with no added salt

Ionization of short weak polyelectrolytes: when size matters

Adsorption of anionic polyelectrolytes to dioctadecyldimethylammonium bromide monolayers

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