A new equation of state for athermal chains

Honnell, Kevin G.; Hall, Carol K.

doi:10.1063/1.456026

Cited by 257 publications

(159 citation statements)

References 38 publications

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“…Keeping this parameter fixed, we adjust d DFT , for each polymer concentration, so that the corresponding experimental bulk osmotic pressure, Π exp , is reproduced. The latter is estimated by a semi-empirical equation of state (EOS), suggested by Cohen et al 37 The DFT predictions for osmotic pressure, Π DFT (d DFT ) is obtained via a Generalized Flory-dimer treatment of the excluded volume 32,38 . Our chosen value for d DFT is thus obtained from the relation Π DFT (d DFT ) = Π exp (at each investigated polymer concentration).…”

Section: Model and Theorymentioning

confidence: 99%

Theoretical predictions of structures in dispersions containing charged colloidal particles and non-adsorbing polymers

Xie

Turesson

Woodward

et al. 2016

Phys. Chem. Chem. Phys.

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We develop a theoretical model to describe structural effects on a specific system of charged colloidal polystyrene particles, upon the addition of non-adsorbing PEG polymers. This system has previously been investigated experimentally, by scattering methods, so we are able to quantitatively compare predicted structure factors with corresponding experimental data. Our aim is to construct a model that is coarse-grained enough to be computationally manageable, yet detailed enough to capture the important physics. To this end, we utilize classical polymer density functional theory, wherein all possible polymer configurations are accounted for, subject to a mean-field Boltzmann weight. We make efforts to counteract drawbacks with this mean-field approach, resulting in structural predictions that agree very well with computationally more demanding simulations. Electrostatic interactions are handled at the fully non-linear Poisson-Boltzmann level, and we demonstrate that a linearization leads to less accurate predictions. The particle charge is an experimentally unknown parameter. We define the surface charge such that the experimental and theoretical gel point at equal polymer concentration coincide. Assuming a fixed surface charge for a certain salt concentration, we find very good agreement between measured and predicted structure factors across a wide range of polymer concentrations. We also present predictions for other structural quantities, such as radial distribution functions, and cluster size distributions. Finally, we demonstrate that our model predicts the occurrence of

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Section: Model and Theorymentioning

confidence: 99%

Theoretical predictions of structures in dispersions containing charged colloidal particles and non-adsorbing polymers

Xie

Turesson

Woodward

et al. 2016

Phys. Chem. Chem. Phys.

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show abstract

“…50 The detailed manner in which this is incorporated into DFT has been described elsewhere, 44,47 and will not be presented here. The relevance of this part of the total functional will also be evaluated in this work, via comparisons with results obtained using a different choice.…”

Section: Theoretical Considerationsmentioning

confidence: 99%

Polyelectrolyte Adsorption on Solid Surfaces: Theoretical Predictions and Experimental Measurements

Xie¹,

Nylander²,

Piculell³

et al. 2013

Langmuir

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This work utilizes a combination of theory and experiments, to explore the adsorption of two different cationic polyelectrolytes onto oppositely charged silica surfaces, at pH 9.Both polymers, Poly(diallyldimethylammonium chloride), PDADMAC, and Poly(4-vinyl Nmethylpyridinium iodide), PVNP, are highly charged, and highly soluble in water. Another important aspect is that a silica surface carries a relatively high surface charge density, at this pH level. This means that we have specifically chosen to investigate adsorption under conditions where electrostatics can be expected to dominate the interactions. Of specific focus in this work is the response of the adsorption to the addition of simple salt, i.e. a process * To whom correspondence should be addressed 1 where electrostatics is gradually screened out. Theoretical predictions from a recently developed correlation-corrected classical density functional theory for polyelectrolytes, are evaluated by direct quantitative comparisons with corresponding experimental data, as obtained by ellipsometry measurements. We find that, at low concentrations of simple salt, the adsorption increases with ionic strength, reaching a maximum at intermediate levels (about 200 mM). The adsorption then drops, but retains a finite level even at very high salt concentrations, indicating the presence of non-electrostatic contributions to the adsorption. In the theoretical treatment, the strength of this relatively modest, but otherwise largely unknown, non-electrostatic surface affinity, was estimated by matching predicted and experimental slopes of adsorption curves at high ionic strength. Given these estimates for the non-electrostatic part, experimental adsorption data are essentially captured with quantitative accuracy by the classical density functional theory.

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“…The range of the potential need not be the actual diameter of the hard-sphere segments, because connectivity ͑in a way͒ renormalizes the pair interaction. 16 To be able to study the influence of this renormalization, we introduce a segment fusion parameter defined as…”

Section: Modelmentioning

confidence: 99%

Density-functional theory of the crystallization of hard polymeric chains

Sushko

Schoot

Michels

2001

The Journal of Chemical Physics

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We study how connectivity influences the crystallization of fully flexible model polymers by applying a recently advanced amalgamation of the Green-function description of polymers, and the density-functional theory of simple liquids. Our calculations show that the model polymers only crystallize if the effective Kuhn length of the chains is sufficiently large compared with the range of the hard-core interaction between the segments. Also shown is the importance of bond-length fluctuations for the stability of the crystal phase.

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A new equation of state for athermal chains

Cited by 257 publications

References 38 publications

Theoretical predictions of structures in dispersions containing charged colloidal particles and non-adsorbing polymers

Theoretical predictions of structures in dispersions containing charged colloidal particles and non-adsorbing polymers

Polyelectrolyte Adsorption on Solid Surfaces: Theoretical Predictions and Experimental Measurements

Density-functional theory of the crystallization of hard polymeric chains

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