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Long-time dynamics of charged colloidal suspensions: hydrodynamic interaction effects

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  • Nägele, Gerhard
  • Baur, Peter

Abstract

For charge-stabilized suspensions, we study the influence of hydrodynamic interactions (HI) and electrostatic interactions on the dynamic structure factor S(q,t), and on the long-time self-diffusion coefficient DsL. Both types of interactions give rise to memory effects, which lead to a slower and non-exponential decay of S(q,t), and which cause DsL to be smaller than the short-time self-diffusion coefficient DsS. A global measure of the non-exponential decay of S(q,t) is the non-exponentiality factor Δ(q), which can be determined experimentally by dynamic light scattering. We derive microscopic expressions for the one-particle irreducible memory functions associated with Δ(q) and DsL, based on the generalized Smoluchowski equation and on a projection operator method developed recently by Kawasaki. HI are accounted for by a far-field expansion of the two-body hydrodynamic mobility tensors, by including the leading terms. We calculate Δ(q) and DsL by constructing a novel mode-coupling approximation scheme which accounts for HI, and we extend the theory to moderately polydisperse suspensions. Our results for the measurable non-exponentiality factor compare well with available experimental data. The effect of HI in charge-stabilized colloids is to reduce the non-exponentiality of S(q,t), and to cause an unexpected enhancement of DsL. Our calculations clearly demonstrate the importance of HI at volume fractions even as low as 10−3.

Suggested Citation

  • Nägele, Gerhard & Baur, Peter, 1997. "Long-time dynamics of charged colloidal suspensions: hydrodynamic interaction effects," Physica A: Statistical Mechanics and its Applications, Elsevier, vol. 245(3), pages 297-336.
  • Handle: RePEc:eee:phsmap:v:245:y:1997:i:3:p:297-336
    DOI: 10.1016/S0378-4371(97)00307-5
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    References listed on IDEAS

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    1. Pusey, P.N. & Van Megen, W. & Underwood, S.M. & Bartlett, P. & Ottewill, R.H., 1991. "Colloidal fluids, crystals and glasses," Physica A: Statistical Mechanics and its Applications, Elsevier, vol. 176(1), pages 16-27.
    2. Nägele, G. & Medina-Noyola, M. & Klein, R. & Arauz-Lara, J.L., 1988. "Time-dependent self-diffusion in model suspensions of highly charged Brownian particles," Physica A: Statistical Mechanics and its Applications, Elsevier, vol. 149(1), pages 123-163.
    3. Cichocki, B. & Hinsen, K., 1992. "Dynamic computer simulation of concentrated hard sphere suspensions," Physica A: Statistical Mechanics and its Applications, Elsevier, vol. 187(1), pages 133-144.
    4. Osborn, C. Tim & Liacuna, Felix & Linsenbigler, Michael, 1992. "Conservation Reserve Programs: Enrollment Statistics for Signup Periods, 1-11 and Fiscal Years 1990-92," Statistical Bulletin 154773, United States Department of Agriculture, Economic Research Service.
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