Revisit to the intrinsic viscosity-molecular weight relationship of ionic polymers. 4. Viscosity behavior of ethylene glycol/water solutions of sodium poly(styrenesulfonate)

Yamanaka, Junpei; Araie, Hidemasa; Matsuoka, Hideki; Kitano, Hiromi; Ise, Norio; Yamaguchi, Takuji; Saeki, Susumu; Tsubokawa, Masakazu

doi:10.1021/ma00011a025

Cited by 21 publications

(16 citation statements)

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“…Results of the viscosity measurements are shown in Figure . It is assumed that for the salt concentration used the shear viscosity is independent of the shear rate in the range of S eff values used in this study (250 s -1 ≤ S eff ≤ 1150 s -1 ) …”

Section: Resultsmentioning

confidence: 99%

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Effect of Charge Density on the Dynamic Behavior of Polyelectrolytes in Aqueous Solution

1996

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Dynamic light scattering experiments and measurements of surface tension and viscosity of aqueous solutions of poly(2-vinylpyridine) quaternized with ethyl bromide are carried out as function of the charge density and polyelectrolyte concentration (Mw ) 2.9 × 10 5 , Mw/Mn ) 1.11; Re, degree of quaternization, 0.09 e Re e 0.46). The polyelectrolytes are dissolved in an aqueous solution of potassium bromide (cs ) 1 × 10 -2 c + , c + ) 1 mol dm -3 ). Their concentrations c jp are in the range 0.1c j + e c jp e 27c j + (c j + ) 1 g dm -3 ). The reduced variable Λ ()Recm/cs) is used to characterize the composition of the solutions (cm, molar volume concentration of the repeat unit of the polymer backbone). Monomodal and bimodal dynamic modes characterized by the apparent diffusion coefficients Ds and Df (index s, slow; index f, fast) are found under the following conditions: monomodal, 0.03 e Λ e 0.1; bimodal, 0.1 e Λ e 8. A third dynamic mode characterized by the apparent diffusion coefficient Dint (index int, intermediate) appears at Λ J 1 with small values of Re in the range 0.09 e Re e 0.15 (Ds < Dint < Df). It is assumed that the third mode reflects dynamic properties of hydrophobic domains formed by uncharged segments of the polymer backbone at low values of Re. Hydrophobic interactions show up also in surface tension and viscosity measurements. A model proposed by Lee and Schurr (J. Polym. Sci. 1975, 13, 873) describes the experimental Df data of the fast diffusive mode with two fit parameters (Zeff, effective number of charges of a polyion; Dp, diffusion coefficient of a polyion). Zeff is smaller by a factor of 5-7 than the value calculated on the basis of Re.

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Section: Resultsmentioning

confidence: 99%

“…It is assumed that for the salt concentration used the shear viscosity is independent of the shear rate in the range of S eff values used in this study (250 s -1 e S eff e 1150 s -1 ). 21 The slope and the intercept of the straight lines increase with increasing charge density of the polyelectrolytes.…”

Section: Viscositymentioning

confidence: 97%

Effect of Charge Density on the Dynamic Behavior of Polyelectrolytes in Aqueous Solution

1996

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“…In the former case, the dilution produces continuous changes in the nature of the electrostatic environments of individual polyions, leading to large changes in both intra-and inter-polyion interactions. 10 These changes result in characteristic viscosity curves different from that for nonionic polymers. Once the salts are.…”

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confidence: 99%

Monte Carlo Simulation Studies of Conformational Properties of Polyelectrolytes with Maleic Acid Units

Hirose

Onodera

Kawaguchi

et al. 1995

Polym J

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ABSTRACT:Conformational properties of polyelectrolyte chain with maleic acid units (MA polyelectrolyte) are investigated by a mean of Monte Carlo simulation. The polyelectrolyte chains are modeled as a self-avoiding walk on tetrahedral lattice with charges fixed. The each charge interacts through Debye-Hiickel potential and attraction energy from hydrogen bonding between un-ionized and ionized carboxyl groups in short-range. Mean-square end-to-end distance, (R 2 ), mean-square radius of gyration, (S 2 ), and mean conformational energy, (£), are simulated as a function of degree of polymerization (N) and dissociation (a), and salt concentration (Cs)-The dependence of (R 2 ) and (S 2 ) on N shows that MA polyelectrolyte chain assumes a rod like conformation at high a and low Cs. The simulation results provide an interpretation for characteristic viscometric behavior of MA polyelectrolytes which show a maximum in an intrinsic viscosity nearly at a= 0.5. The polymer dimensions in the region of a~ 0.5 increases with the energy of the hydrogen bonding assumed. The characteristic viscometric behavior of MA polyelectrolytes is deduced to result from the balance between repulsion from the electrostatic interaction and attraction from the hydrogen bonding in short-range. KEY WORDSMonte Carlo Simulation/ Conformation/ Hydrogen Bond / Polyelectrolyte / Intrinsic Viscosity/ Radius of Gyration/ Dielectric Constant/ Solution properties of macromolecules strongly depend on conformation of a polymer chain. The conformational properties of an un-charged polymer chain have been fairly understood by much theoretical, numerical, and experimental effort. 1 • 2 In contrast, the understanding of the conformation for a polyelectrolyte chain still remains many unanswered subjects. The difficulty in describing behavior of the polyelectrolyte solutions comes from electrostatic interaction among dense charges fixed on the polymer backbone, which depends on density and distribution of the charges of the polyelectrolyte, as well as solvent property. 3 · 4 The conformational properties of uncharged polymer is normally determined in terms of short-and long-range interactions. 1 The former is related to chain stiffness, persistence length of the polymer, Kuhn segment length, and the latter, to the excluded volume. This also holds for the conformational properties of polyelectrolyte chains. The investigation is, however, rather complicated because the electrostatic interaction affects concurrently on both short-and long-range in the polyelectrolyte chain. Two interpretations for the polyelectrolyte conformation have been established. One is the increase of electrostatic persistence length (Le) with increasing the electrostatic interaction for wormlike chain. 5 • 6 The total persistence length (L 1 ) of the polyelectrolyte chain is expressed by the sum of intrinsic persistence length (L 0 ) and Le.

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“…The BE approach is then applied to short DNA fragments in the range of 0.005−0.6 M monovalent salt where the electroviscous effect ranges from about 45% (20 bp) and 30% (40 bp) at low salt down to about 2% (20 and 40 bp) at high salt. Most viscosity studies appearing in the literature deal with high molecular weight polyelectrolytes where secondary and tertiary viscoelectric effects dominate. ,, It is hoped that the present study will stimulate further experimental work on the subject of the primary electroviscous effect of dilute, rigid macromolecules. The case study of the 20 and 40 bp DNA fragments shows that the effect is predicted to be large enough to observe.…”

Section: Discussionmentioning

confidence: 84%

“…Most viscosity studies appearing in the literature deal with high molecular weight polyelectrolytes where secondary and tertiary viscoelectric effects dominate. 5,46,47 It is hoped that the present study will stimulate further experimental work on the subject of the primary electroviscous effect of dilute, rigid macromolecules. The case study of the 20 and 40 bp DNA fragments shows that the effect is predicted to be large enough to observe.…”

Section: Discussionmentioning

confidence: 84%

The Primary Electroviscous Effect of Rigid Polyions of Arbitrary Shape and Charge Distribution

Allison

1998

Macromolecules

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The viscosity of a dilute suspension of charged rigid particles exceeds that of a suspension of identical, but uncharged particles, and this is called the primary electroviscous effect. This excess viscosity arises as a result of the distortion of the ion atmosphere surrounding the polyion due to the fluid shear field in which it is placed. Consequently, any theory of the primary electroviscous effect must account for this distortion. Booth (Proc. Roy. Soc. (London) 1950, 203A, 533) and later Sherwood (J. Fluid Mech. 1980, 101, 609) achieved this for a spherical polyion of uniform equilibrium surface potential by solving the coupled (low Reynold's number) Navier−Stokes, Poisson, and ion transport equations. The primary objective of the present work is to extend this approach to rigid model polyions of arbitrary shape and charge distribution. The coupled transport equations are solved by an iterative boundary element (BE) procedure applied previously to the closely related problem of electrophoresis (Allison, S. A. Macromolecules 1996, 29, 7391). In test cases on spheres containing single central charges, the BE results are found to be in very good agreement with Sherwood. The BE approach is then applied to spherical polyions containing noncentrosymmetric charge distributions as well as short (20−40 base pair) DNA models in the monovalent salt range 0.005−0.6 M. For the DNA fragments, the primary electroviscous effect ranges from about 2% to 30% (40 bp) or 45% (20bp) as the KCl concentration is reduced from 0.6 to 0.005 M, respectively. Substantially larger effects are predicted if the monovalent salt is Tris−acetate, and this is due primarily to the lower mobility of the Tris counterion relative to K+. A secondary objective is to make contact between the BE approach and “bead methods”, which have been successfully used in modeling the viscosity of rigid, but uncharged macromolecules of arbitrary shape.

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Revisit to the intrinsic viscosity-molecular weight relationship of ionic polymers. 4. Viscosity behavior of ethylene glycol/water solutions of sodium poly(styrenesulfonate)

Cited by 21 publications

References 1 publication

Effect of Charge Density on the Dynamic Behavior of Polyelectrolytes in Aqueous Solution

Effect of Charge Density on the Dynamic Behavior of Polyelectrolytes in Aqueous Solution

Monte Carlo Simulation Studies of Conformational Properties of Polyelectrolytes with Maleic Acid Units

The Primary Electroviscous Effect of Rigid Polyions of Arbitrary Shape and Charge Distribution

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