Hydrodynamic Screening and Diffusion in Entangled Polymer Solutions

Shiwa, Yuh

doi:10.1103/physrevlett.58.2102

Cited by 36 publications

(25 citation statements)

References 18 publications

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“…3 with the prediction of a renormalization group calculation from [67] shown as the dashed curve thukumar and Edwards [64]. The data reported by Amis et al [38] and the lower molecular weight data reported by Yu et al [60] and Wiltzius et al [61] deviate systematically from those plotted in Fig.…”

Section: (2)mentioning

confidence: 41%

“…4 shows that plotting ~e/Rh vs. 16/9.Aa.M.C yields a universal curve using the empirical relation Rh = 1.6 x 10-2.M ~ nm [9]. The dotted line is the predicted behavior from a renormalization group theory calculation by Shiwa [67]. Again the calculated prefactor underestimates the experimentally observed concentration dependence.…”

Section: (2)mentioning

confidence: 89%

“…1 and 3 that the experimental data do not support this interpretation. Renormalization group treatment for dynamic properties has not been performed as extensively as for static properties and is complicated by the combined effect of screening excluded volume hydrodynamic interactions as well as topological constraints [67][68][69]. The effect of the latter on ~e is expected to be small for the good solvents systems discussed here, but is important for theta systems, which are discussed in the following section.…”

Section: (2)mentioning

confidence: 96%

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Static and dynamic behavior of semidilute polymer solutions

Brown

Nicolai

1990

Colloid & Polymer Sci

125

150

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Section: (2)mentioning

confidence: 41%

Section: (2)mentioning

confidence: 89%

Section: (2)mentioning

confidence: 96%

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Static and dynamic behavior of semidilute polymer solutions

Brown

Nicolai

1990

Colloid & Polymer Sci

125

150

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“…To address this possibility, following the work of Schurtenberger and coworkers, we use evidence based upon theoretical and experimental studies of light scattering from semidilute solutions of linear, flexible polymers of known molecular weight (35)(36)(37)(86)(87)(88)(89)(90)(91)(92)(93)(94). In particular, we shall compare our data to the work of Ohta, Oono, and co-workers, who express the degree of overlap or entanglement of such polymers in terms of the quantity X ) 16 / 9 A 2 cM, where we have neglected the polydispersity, which they include.…”

Section: B) Examination Of the First-order Effect Of Intermicellar Inmentioning

confidence: 99%

Laser Light Scattering Evidence for a Common Wormlike Growth Structure of Mixed Micelles in Bile Salt− and Straight-Chain Detergent−Phosphatidylcholine Aqueous Systems: Relevance to the Micellar Structure of Bile

et al. 1998

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We employed quasielastic and static light scattering to measure apparent values of the mean hydrodynamic radii (R h ) app , molecular weights (M app ), and radii of gyration (R g ) app in solutions containing mixed micelles composed of bile salts (cholate and taurochenodeoxycholate, both cholanoyl derivatives) and the glycoacyl chain detergent, octyl glucoside, with egg yolk phosphatidylcholine (EYPC) as functions of total lipid concentration (0.1-10 g/dL), EYPC/detergent molar ratio (0-1.2), and ionic strength (0.15-0.4 M NaCl) at 20°C and 1 atm. As the mixed micellar phase boundaries were approached by dilution, (R h ) app , M app , and (R g ) app values increased markedly by up to 20-fold. For each micellar system, the scaling ratios (R h ) app /M app 1/2 and (R g ) app /(R h ) app remained essentially constant at 0.018 nm/(g/mol) 1/2 and 1.5 (dimensionless), respectively, despite large variations in total lipid concentration, detergent molecular species, and ionic strength. Refined data analysis is inconsistent with a flat "mixed-disc" model for bile salt-EYPC micelles [Mazer, N. A., Benedek, G. B., and Carey, M. C. (1980) Biochemistry 19, 601] and octyl glucoside-EYPC micelles principally because the numerical value of (R h ) app /M app 1/2 corresponds to a hypothetical disk thickness of ∼1 nm, which is 4-fold smaller than the bimolecular width of EYPC molecules, and for a disk, (R g ) app /(R h ) app ratios should be close to 1 at low total lipid concentrations. Assuming disc-shaped micelles, we show that intermicellar excluded volume interactions would have only a minor effect on M app and cannot account for the unrealistic disk thickness. Instead, locally cylindrical, semiflexible wormlike micelles of diameter d ) 4 nm and persistence length p ) 17 nm in solution are compatible with the observed (R h ) app /M app 1/2 and (R g ) app /(R h ) app values when intermicellar excluded-volume interactions are considered. With EYPC/taurochenodeoxycholate ) 0.6 and EYPC/cholate ) 1.0 in 0.15 M NaCl, independent micelles grow upon dilution and use of the second virial coefficient [Egelhaaf, S. U., and Schurtenberger, P. (1994) J. Phys. Chem. 98, 8560] is adequate for estimating micellar weights. The systems EYPC/cholate ) 1.0 in 0.4 M NaCl, EYPC/cholate ) 1.2 in 0.15 M NaCl, and EYPC/octyl glucoside ) 0.13 in 0.15 M NaCl all form highly overlapping, semidilute polymer solutions, which mimic the observed scaling ratios. In such semidilute systems, use of the second virial coefficient alone to account for intermicellar interactions is inadequate for estimating micellar weights. The results of the present study, in combination with locations of known phase boundaries of the ternary bile salt-EYPCwater phase diagram at high dilution, suggest that elongation, as well as entanglement of wormlike mixed micelles may occur at concentrations approaching the micellar phase limit.Aqueous mixed micellar solutions of steroidal or straightchain detergents with long-chain phosphatidylcholine (PC) 1 are of considerable s...

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“…1,5 Unfortunately, there is far less unanimity amongst the theoretical estimates of this quantity, which range from 0 to about 1. [6][7][8][9][10][11][12][13][14][15][16] The calculation of k s can be quite involved ͑even at the theta point where excluded volume interactions can be neglected͒, so these disparities are not easily rationalized. 17 What is clear, however, is that the dynamical processes that are responsible for concentration dependence of chain friction are still only poorly understood.…”

Section: Introductionmentioning

confidence: 99%

The concentration dependent cooperative friction coefficient of dilute polymer solutions at the theta point

Cherayil

Freed

1996

The Journal of Chemical Physics

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We combine multiple scattering and renormalization group methods to calculate the leading order dimensionless virial coefficient k s for the friction coefficient of dilute polymer solutions under conditions where the osmotic second virial coefficient vanishes ͑i.e., at the theta point T ͒. Our calculations are formulated in terms of coupled kinetic equations for the polymer and solvent, in which the polymers are modeled as continuous chains whose configurations evolve under the action of random forces in the velocity field of the solvent. To lowest order in ⑀ϭ4Ϫd, we find that k s ϭ1.06. This result compares satisfactorily with existing experimental estimates of k s , which are in the range 0.7-0.8. It is also in good agreement with other theoretical results on chains and suspensions at T . Our calculated k s is also found to be identical to the leading order virial coefficient of the tracer friction coefficient at the theta point. We discuss possible reasons for the difficulties encountered when attempting to evaluate k s by extrapolating prior renormalization group calculations from semidilute concentrations to the infinitely dilute limit.

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Hydrodynamic Screening and Diffusion in Entangled Polymer Solutions

Cited by 36 publications

References 18 publications

Static and dynamic behavior of semidilute polymer solutions

Static and dynamic behavior of semidilute polymer solutions

Laser Light Scattering Evidence for a Common Wormlike Growth Structure of Mixed Micelles in Bile Salt− and Straight-Chain Detergent−Phosphatidylcholine Aqueous Systems: Relevance to the Micellar Structure of Bile

The concentration dependent cooperative friction coefficient of dilute polymer solutions at the theta point

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