Skip to main content Accessibility help
×
Home
  • Print publication year: 2011
  • Online publication date: August 2012

5 - Solvent and small-molecule motion

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.

References
[1] T. G., Hiss and E. L., Cussler. Diffusion in high viscosity liquids. A. I. Ch. E. Journal, 19 (1973), 698–703.
[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.
[3] B. R., Hammond and R. H., Stokes. Diffusion in binary liquid mixtures. Trans. Far. Soc., 51 (1955), 1641–1649.
[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.
[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.
[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.
[7] C., Treiner and R. M., Fuoss. Electrolyte–solvent interaction. XVI. Quaternary salts in cyanoethylsucrose-acetonitrile mixtures. J. Phys. Chem., 69 (1965), 2576–2581.
[8] W., Heber-Green. Studies on the viscosity and conductivity of some aqueous solutions. J. Chem. Soc., 98 (1908), 2023–2063.
[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.
[10] G. D. J., Phillies. Translational diffusion coefficient of macroparticles in solvents of high viscosity. J. Phys. Chem., 85 (1981), 2838–2843.
[11] A. C., Fernandez and G. D. J., Phillies. Temperature dependence of the diffusion coefficient of polystyrene latex spheres. Biopolymers, 22 (1983), 593–595.
[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.
[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.
[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.
[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.
[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.
[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.
[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.
[19] P. P., Craig and N., Sutin. Mossbauer effect in liquids: Influence of diffusion broadening. Phys. Rev. Lett., 11 (1963), 460–464.
[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.
[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.
[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.
[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.
[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.
[25] S., Pickup and F. D., Blum. Self-diffusion of toluene in polystyrene solutions. Macromolecules, 22 (1989), 3961–3968.
[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.
[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.
[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.
[29] D. N., Pinder. Polymer self-diffusion in ternary solutions and the monomer and segmental self-diffusion coefficients. Macromolecules, 23 (1990), 1724–1729.
[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.
[31] R., Kosfeld and L., Zumkley. Mobility of small molecules in polymer systems. Berichte Bunsenges Phys. Chem., 83 (1979), 392–396.
[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.
[33] J., Komiyama and R. M., Fuoss. Conductance in water-poly (vinyl alcohol) mixtures. Proc. Natl. Acad. Sci. USA, 69 (1972), 829–833.
[34] H., Tao, T. P., Lodge, and E. D., von Meerwall. Diffusivity and viscosity of concentrated hydrogenated polybutadiene solutions. Macromolecules, 33 (2000), 1747–1758.
[35] A. R., Altenberger and M., Tirrell. On the theory of self-diffusion in a polymer gel. J. Chem. Phys., 80 (1984), 2208–2213.
[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.
[37] A. C., Ouano and R., Pecora. Rotational relaxation of chlorobenzene in poly (methyl methacrylate). 2. Theoretical Interpretation. Macromolecules, 13 (1980), 1173–1177.
[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.
[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.
[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.
[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.
[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.
[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.
[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.
[45] J. R., Krahn and T. P., Lodge. Spatial heterogeneity of solvent dynamics in multicomponent polymer solutions. J. Phys. Chem., 99 (1995), 8338–8348.
[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.
[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.
[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.
[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.
[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.