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5 - Solvent and small-molecule motion

Published online by Cambridge University Press:  05 August 2012

George D. J. Phillies
George D. J. Phillies
Affiliation:
Worcester Polytechnic Institute, Massachusetts
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Summary

Introduction

The next four chapters treat motion related to single polymer molecules. This chapter examines the solvent molecules surrounding the chains. Chapter 6 examines motions of modest parts of chains. Chapters 7 and 8 review rotational and translational diffusion of single chains through polymer solutions.

It had long been assumed that the solvent in a polymer solution provides a neutral hydrodynamic background, and that the properties of the solvent in a solution, such as viscosity, are the same as the properties found in the neat solvent.We know now that this simple assumption is incorrect. Just as the solvent can alter properties of the polymer, so also do polymers alter the properties of the surrounding solvent. Translational and rotational mobilities of solvent molecules may be reduced or increased by the presence of nearby polymer chains. Models for polymer dynamics that assume that the solvent has the same properties as the neat liquid are therefore unlikely to be entirely accurate.

Our focus here is the motion of small molecules in highly viscous fluids. We begin with the motion of small molecules through simple solvents and small-molecule mixtures. Molecular translation and rotation through polymer solutions are then treated. Finally, we examine high-frequency viscoelastic behavior. Important experimental techniques sensitive to these physical properties include nuclear magnetic resonance, depolarized light scattering, Mossbauer spectroscopy, nuclear resonant scattering, and oscillatory electrical birefringence.

Motion in large-viscosity simple solvents

This section examinesmotion (diffusion, conductance, electrophoreticmobility) of rigid probes through simple solvents and small-molecule solutions.

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Phenomenology of Polymer Solution Dynamics , pp. 94 - 115
Publisher: Cambridge University Press
Print publication year: 2011

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References

[1] T. G., Hiss and E. L., Cussler. Diffusion in high viscosity liquids. A. I. Ch. E. Journal, 19 (1973), 698–703.Google Scholar
[2] R. H., Stokes, P. J., Dunlop, and J. R., Hall. The diffusion of iodine in some organic solvents. Trans. Far. Soc., 49 (1953), 886–890.Google Scholar
[3] B. R., Hammond and R. H., Stokes. Diffusion in binary liquid mixtures. Trans. Far. Soc., 51 (1955), 1641–1649.Google Scholar
[4] J. M., Stokes and R. H., Stokes. The conductances of some simple electrolytes in aqueous sucrose solutions at 25°. J. Phys. Chem., 60 (1956), 217–220.Google Scholar
[5] J. M., Stokes and R. H., Stokes. The conductances of some electrolytes in aqueous sucrose and mannitol solutions at 25°. J. Phys. Chem., 62 (1958), 497–499.Google Scholar
[6] M. V., Hollander and J. J., Barker. Measurement of diffusivity in a high-viscosity liquid. A. I. Ch. E. Journal, 9 (1963), 514–516.Google Scholar
[7] C., Treiner and R. M., Fuoss. Electrolyte–solvent interaction. XVI. Quaternary salts in cyanoethylsucrose-acetonitrile mixtures. J. Phys. Chem., 69 (1965), 2576–2581.Google Scholar
[8] W., Heber-Green. Studies on the viscosity and conductivity of some aqueous solutions. J. Chem. Soc., 98 (1908), 2023–2063.Google Scholar
[9] G. L., Pollack and J. J., Enyeart. Atomic test of the Stokes–Einstein law. II. Diffusion of Xe through liquid hydrocarbons. Phys. Rev. A, 31 (1985), 980–984.Google Scholar
[10] G. D. J., Phillies. Translational diffusion coefficient of macroparticles in solvents of high viscosity. J. Phys. Chem., 85 (1981), 2838–2843.Google Scholar
[11] A. C., Fernandez and G. D. J., Phillies. Temperature dependence of the diffusion coefficient of polystyrene latex spheres. Biopolymers, 22 (1983), 593–595.Google Scholar
[12] Y. F., Kiyachenko and Y. I., Litvinov. Increase in scale length in a liquid as the glass-transition temperature is approached. JETP Letters, 42 (1985), 266–269.Google Scholar
[13] P., Wiltzius and W., Saarloos. Absence of increase in length scale upon approaching the glass temperature in liquid glycerol. J. Chem. Phys., 94 (1991), 5061–5063.Google Scholar
[14] G. D. J., Phillies and D., Clomenil. Lineshape and linewidth effects in optical probe studies of glass-forming liquids. J. Phys. Chem., 96 (1992), 4196–4200.Google Scholar
[15] A., Meyer, H., Franz, J., Wuttke, et al. Nuclear resonant scattering of synchrotron radiation for the study of dynamics around the glass transition. Zeitschrift fuer Physik B, 103 (1997), 479–484.Google Scholar
[16] I., Sergueev, H., Franz, T., Asthalter, et al. Structural relaxation in a viscous liquid studied by quasielastic nuclear forward scattering. Phys. Rev. B, 66 (2002), 184210 1–8.Google Scholar
[17] I., Sergueev, U., Buerck, A. I., Chumakov, et al. Synchrotron-radiation-based per-turbed angular correlations used in the investigation of rotational dynamics in soft matter. Phys. Rev. B, 73 (2006), 024203 1–12.Google Scholar
[18] K. P., Singh and J. G., Mullen. Mossbauer study of Brownian motion in liquids: Colloidal cobaltous hydroxy stannate in glycerol, ethanol-glycerol, and aqueous-glycerol solutions. Phys. Rev. A, 6 (1972), 2354–2358.Google Scholar
[19] P. P., Craig and N., Sutin. Mossbauer effect in liquids: Influence of diffusion broadening. Phys. Rev. Lett., 11 (1963), 460–464.Google Scholar
[20] A., Abras and W. G., Mullen. Mossbauer study of diffusion in liquids: Dispersed Fe2+ in glycerol and aqueous-glycerol solutions. Phys. Rev. A, 6 (1972), 2343–2353.Google Scholar
[21] E. D., von Meerwall, E. J., Amis, and J. D., Ferry. Self-diffusion in solutions of polystyrene in tetrahydrofuran: Comparison of concentration dependences of the diffusion coefficient of polymer, solvent, and a ternary probe component. Macromolecules, 18 (1985), 260–266.Google Scholar
[22] B. D., Boss, E. O., Stejskal, and J. D., Ferry. Self-diffusion in high molecular weight polyisobutylene-benzene mixtures determined by the pulsed-gradient, spin-echo method. J. Phys. Chem., 71 (1967), 1501–1506.Google Scholar
[23] B. P., Chekal and J. M., Torkelson. Relationship between chain length and the concentration dependence of polymer and oligomer self-diffusion in solution. Macromolecules, 35 (2002), 8126–8138.Google Scholar
[24] Yu. B., Mel'nichenko, V. V., Klepko, and V. V., Shilov. Self-diffusion of small tracers in a polymer gel. Europhys. Lett., 13 (1990), 505–510.Google Scholar
[25] S., Pickup and F. D., Blum. Self-diffusion of toluene in polystyrene solutions. Macromolecules, 22 (1989), 3961–3968.Google Scholar
[26] M. C., Piton, R. G., Gilbert, B. E., Chapman, and P. W., Kuchel. Diffusion of oligomeric species in polymer solutions. Macromolecules, 26 (1993), 4472–4477.Google Scholar
[27] E. D., von Meerwall, S., Amelar, M. A., Smetzly, and T. P., Lodge. Solvent and probe diffusion in Aroclor solutions of polystyrene, polybutadiene, and polyisoprene. Macromolecules, 22 (1989), 295–304.Google Scholar
[28] R. A., Waggoner, F. D., Blum, and J. M. D., MacElroy. Dependence of the solvent diffusion coefficient on concentration in polymer solutions. Macromolecules, 26 (1993), 6841–6848.Google Scholar
[29] D. N., Pinder. Polymer self-diffusion in ternary solutions and the monomer and segmental self-diffusion coefficients. Macromolecules, 23 (1990), 1724–1729.Google Scholar
[30] M. B., Wisnudel and J. M., Torkelson. Small-molecule probe diffusion in polymer solutions: Studies by Taylor dispersion and phosphorescence quenching. Macromolecules, 29 (1996), 6193–6207.Google Scholar
[31] R., Kosfeld and L., Zumkley. Mobility of small molecules in polymer systems. Berichte Bunsenges Phys. Chem., 83 (1979), 392–396.Google Scholar
[32] M. B., Mustafa, D. L., Tipton, M. D., Barkley, and P. S., Russo. Dye diffusion in isotropic and liquid crystalline aqueous (hydroxypropyl) cellulose. Macromolecules, 26 (1992), 370–378.Google Scholar
[33] J., Komiyama and R. M., Fuoss. Conductance in water-poly (vinyl alcohol) mixtures. Proc. Natl. Acad. Sci. USA, 69 (1972), 829–833.Google Scholar
[34] H., Tao, T. P., Lodge, and E. D., von Meerwall. Diffusivity and viscosity of concentrated hydrogenated polybutadiene solutions. Macromolecules, 33 (2000), 1747–1758.Google Scholar
[35] A. R., Altenberger and M., Tirrell. On the theory of self-diffusion in a polymer gel. J. Chem. Phys., 80 (1984), 2208–2213.Google Scholar
[36] A. C., Ouano and R., Pecora. Rotational relaxation of chlorobenzene in poly (methyl methacrylate). 1. Temperature and concentration effects. Macromolecules, 13 (1980), 1167–1173.Google Scholar
[37] A. C., Ouano and R., Pecora. Rotational relaxation of chlorobenzene in poly (methyl methacrylate). 2. Theoretical Interpretation. Macromolecules, 13 (1980), 1173–1177.Google Scholar
[38] G., Fytas, A., Rizos, G., Floudas, and T. P., Lodge. Solvent mobility in polystyrene/Aroclor solutions by depolarized Rayleigh scattering. J. Chem. Phys., 93 (1990), 5096–5104.Google Scholar
[39] A., Rizos, G., Fytas, T. P., Lodge, and K. L., Ngai. Solvent rotational mobility in polystyrene/Aroclor and polybutadiene/Aroclor solutions. II. A photon correlation spectroscopic study. J. Chem. Phys., 95 (1991), 2980–2987.Google Scholar
[40] G., Floudas, G., Fytas, and W., Brown. Solvent mobility in poly (methyl methacrylate)/toluene solutions by depolarized and polarized light scattering. J. Chem. Phys., 96 (1992), 2164–2174.Google Scholar
[41] D. J., Gisser and M. D., Ediger. Modification of solvent rotational dynamics by the addition of small molecules or polymers. J. Phys. Chem., 97 (1993), 10818–10823.Google Scholar
[42] D. J., Gisser, B. S., Johnson, M. D., Ediger, and E. D., von Meerwall. Comparison of various measurements of microscopic friction in polymer solutions. Macromolecules, 26 (1993), 512–519.Google Scholar
[43] R. L., Morris, S., Amelar, and T. P., Lodge. Solvent friction in polymer solutions and its relation to the high frequency limiting viscosity. J. Chem. Phys., 89 (1988), 6523–6537.Google Scholar
[44] M. G., Minnick and J. L., Schrag. Polymer-solvent interaction effects in oscillatory flow birefringence studies of polybutadienes and polyisoprenes in Aroclor solvents. Macromolecules, 13 (1980), 1690–1695.Google Scholar
[45] J. R., Krahn and T. P., Lodge. Spatial heterogeneity of solvent dynamics in multicomponent polymer solutions. J. Phys. Chem., 99 (1995), 8338–8348.Google Scholar
[46] T., Yoshizaki, Y., Takaeda, and H., Yamakawa. On the correlation between the negative intrinsic viscosity and the rotatory relaxation time of solvent molecules in dilute polymer solutions. Macromolecules, 26 (1993), 6891–6896.Google Scholar
[47] T. P., Lodge and J. R., Krahn. Comment on “On the correlation between the negative intrinsic viscosity and the rotatory relaxation time of solvent molecules in dilute polymer solutions.” Macromolecules, 27 (1994), 6223–6224.Google Scholar
[48] B. J., Cooke and A. J., Matheson. Dynamic viscosity of dilute polymer solutions at high frequencies of alternating shear stress. J. Chem. Soc. Faraday Trans. 2, 72 (1975), 679–685.Google Scholar
[49] J. W. M., Noordermeer, J. D., Ferry, and N., Nemoto. Viscoelastic properties of polymer solutions in high-viscosity solvents and limiting high-frequency behavior. III. Poly(2-substituted methyl acrylates). Macromolecules, 8 (1975), 672–677.Google Scholar
[50] J. W. M., Noordermeer, O., Kramer, F. H. M., Nestler, J. L., Schrag, and J. D., Ferry. Viscoelastic properties of polymer solutions in high-viscosity solvents and limiting high-frequency behavior. II. Branched polystyrenes with star and comb structures. Macromolecules, 8 (1975), 539–544.Google Scholar

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