Shear thinning in dilute polymer solutions.

We use bead-spring models for a polymer coupled to a solvent described by multiparticle collision dynamics to investigate shear thinning effects in dilute polymer solutions. First, we consider the polymer motion and configuration in a shear flow. For flexible polymer models we find a sharp increase in the polymer radius of gyration and the fluctuations in the radius of gyration at a Weissenberg number approximately 1. We then consider the polymer viscosity and the effect of solvent quality, excluded volume, hydrodynamic coupling between the beads, and finite extensibility of the polymer bonds. We conclude that the excluded volume effect is the major cause of shear thinning in polymer solutions. Comparing the behavior of semiflexible chains, we find that the fluctuations in the radius of gyration are suppressed when compared to the flexible case. The shear thinning is greater and, as the rigidity is increased, the viscosity measurements tend to those for a multibead rod.

[1]  S. Muller,et al.  Flow light scattering studies of polymer coil conformation in solutions under shear: effect of solvent quality , 1999 .

[2]  S. Hess,et al.  Rotation and deformation of a finitely extendable flexible polymer molecule in a steady shear flow , 2002 .

[3]  P. E. Rouse A Theory of the Linear Viscoelastic Properties of Dilute Solutions of Coiling Polymers , 1953 .

[4]  G. Thurston,et al.  Influence of Finite Number of Chain Segments, Hydrodynamic Interaction, and Internal Viscosity on Intrinsic Birefringence and Viscosity of Polymer Solutions in an Oscillating Laminar Flow Field , 1967 .

[5]  J. G. Torre,et al.  Non-Newtonian Viscosity of Dilute Polymer Solutions , 2005 .

[6]  Hans Christian Öttinger,et al.  The effects of bead inertia on the Rouse model , 1988 .

[7]  R. Prabhakar,et al.  Multiplicative separation of the influences of excluded volume, hydrodynamic interactions and finite extensibility on the rheological properties of dilute polymer solutions , 2004 .

[8]  Hiroshi Noguchi,et al.  Fluid vesicles with viscous membranes in shear flow. , 2004, Physical review letters.

[9]  Douglas E. Smith,et al.  Single-polymer dynamics in steady shear flow. , 1999, Science.

[10]  Gaussian chains with excluded volume and hydrodynamic interaction: shear rate dependence of radius of gyration, intrinsic viscosity and flow birefringence , 1996 .

[11]  H. C. Oettinger,et al.  Calculation of various universal properties for dilute polymer solutions undergoing shear flow , 1991 .

[12]  C M Pooley,et al.  Kinetic theory derivation of the transport coefficients of stochastic rotation dynamics. , 2005, The journal of physical chemistry. B.

[13]  T. Ihle,et al.  Stochastic rotation dynamics: a Galilean-invariant mesoscopic model for fluid flow. , 2001, Physical review. E, Statistical, nonlinear, and soft matter physics.

[14]  Rodrigo E. Teixeira,et al.  Shear Thinning and Tumbling Dynamics of Single Polymers in the Flow-Gradient Plane , 2005 .

[15]  Hiroshi Noguchi,et al.  Dynamics of fluid vesicles in shear flow: effect of membrane viscosity and thermal fluctuations. , 2005, Physical review. E, Statistical, nonlinear, and soft matter physics.

[16]  Hiroshi Noguchi,et al.  Folding path in a semiflexible homopolymer chain: A Brownian dynamics simulation , 2000 .

[17]  J. F. Ryder,et al.  Transport coefficients of a mesoscopic fluid dynamics model , 2003, cond-mat/0302451.

[18]  Rodrigo E. Teixeira,et al.  Dynamics of DNA in the flow-gradient plane of steady shear flow: Observations and simulations , 2005 .

[19]  H. C. Öttinger Consistently averaged hydrodynamic interaction for Rouse dumbbells. Series expansions , 1986 .

[20]  M. Muthukumar,et al.  Brownian dynamics simulation of bead–rod chains under shear with hydrodynamic interaction , 1999 .

[21]  D. J. Montgomery,et al.  The physics of rubber elasticity , 1949 .

[22]  Gerhard Gompper,et al.  Rod-like colloids and polymers in shear flow: a multi-particle-collision dynamics study , 2004 .

[23]  H. C. Öttinger Consistently averaged hydrodynamic interaction for Rouse dumbbells in steady shear flow , 1985 .

[24]  P. Gennes Scaling Concepts in Polymer Physics , 1979 .

[25]  R. Bird Dynamics of Polymeric Liquids , 1977 .

[26]  H. R. Warner,et al.  Kinetic Theory and Rheology of Dilute Suspensions of Finitely Extendible Dumbbells , 1972 .

[27]  J. Koelman,et al.  Simulating microscopic hydrodynamic phenomena with dissipative particle dynamics , 1992 .

[28]  R. Tanner,et al.  Rheology of Bead-NonLinear Spring Chain Macromolecules , 1989 .

[29]  C. Manke,et al.  Effects of solvent quality on the dynamics of polymer solutions simulated by dissipative particle dynamics , 2002 .

[30]  D. Ermak,et al.  Brownian dynamics with hydrodynamic interactions , 1978 .

[31]  J. M. Yeomans,et al.  Dynamics of short polymer chains in solution , 2000 .

[32]  H. C. Öttinger Gaussian approximation for Rouse chains with hydrodynamic interaction , 1989 .

[33]  K. Binder,et al.  Polymer chain dynamics derived from the Kramers potential: A treatment of the Rouse model with and without excluded volume interaction , 1988 .

[34]  K. S. Kumar,et al.  Universal consequences of the presence of excluded volume interactions in dilute polymer solutions undergoing shear flow. , 2004, The Journal of chemical physics.

[35]  R. Winkler,et al.  Star polymers in shear flow. , 2006, Physical review letters.

[36]  J. F. Ryder,et al.  Kinetics of the polymer collapse transition: the role of hydrodynamics. , 2005, Physical review. E, Statistical, nonlinear, and soft matter physics.

[37]  J. G. Torre,et al.  Simulation of non-linear models for polymer chains in flowing solutions , 1995 .

[38]  Ronald G. Larson,et al.  Brownian dynamics simulations of single DNA molecules in shear flow , 2000 .

[39]  T Ihle,et al.  Stochastic rotation dynamics. I. Formalism, Galilean invariance, and Green-Kubo relations. , 2003, Physical review. E, Statistical, nonlinear, and soft matter physics.

[40]  A. Peterlin Gradient Dependence of Intrinsic Viscosity of Freely Flexible Linear Macromolecules , 1960 .

[41]  H. Inagaki,et al.  Shear‐Rate Dependence of the Intrinsic Viscosity of Flexible Linear Macromolecules , 1966 .

[42]  W. Zylka Gaussian approximation and Brownian dynamics simulations for Rouse chains with hydrodynamic interaction undergoing simple shear flow , 1991 .

[43]  Philip LeDuc,et al.  Dynamics of individual flexible polymers in a shear flow , 1999, Nature.

[44]  J T Padding,et al.  Hydrodynamic and brownian fluctuations in sedimenting suspensions. , 2004, Physical review letters.

[45]  B. Zimm Dynamics of Polymer Molecules in Dilute Solution: Viscoelasticity, Flow Birefringence and Dielectric Loss , 1956 .

[46]  Oettinger Renormalization-group calculation of excluded-volume effects on the viscometric functions for dilute polymer solutions. , 1989, Physical review. A, General physics.

[47]  T Ihle,et al.  Stochastic rotation dynamics. II. Transport coefficients, numerics, and long-time tails. , 2003, Physical review. E, Statistical, nonlinear, and soft matter physics.

[48]  S. Edwards,et al.  The Theory of Polymer Dynamics , 1986 .

[49]  J Ravi Prakash Rouse Chains with Excluded Volume Interactions: Linear Viscoelasticity , 2001 .

[50]  Brownian dynamics simulation of macromolecules in steady shear flow , 1983 .

[51]  Juan J. de Pablo,et al.  Stochastic simulations of DNA in flow: Dynamics and the effects of hydrodynamic interactions , 2002 .

[52]  S. Edwards,et al.  The computer study of transport processes under extreme conditions , 1972 .

[53]  A. Malevanets,et al.  Mesoscopic model for solvent dynamics , 1999 .