We study non-equilibrium pair interactions between microscopic particles moving through a model shear-thinning fluid. Prior efforts to model pair interactions in non-Newtonian fluids have largely focused on constitutive models derived from polymer-chain kinetic theories focusing on conformational degrees of freedom, but neglecting the details of microstructural evolution beyond a single polymer length scale. To elucidate the role of strong structural distortion in mediating pair interactions in Brownian suspensions, we formulate and solve a Smoluchowski equation describing the detailed evolution of the particle configuration between and around a pair of microscopic probes driven at fixed velocity by an external force through a colloidal dispersion. To facilitate analysis, we choose a model system of Brownian hard spheres that do not interact hydrodynamically; while simple, this ‘freely draining’ model permits insight into connections between microstructure and rheology. The flow induces a non-equilibrium particle density gradient that gives rise to both viscous drag and an interactive force between the probes. The drag force acts to slow the centre-of-mass velocity of the pair, while the interactive force arising from osmotic pressure gradients can lead to attraction or repulsion, as well as deterministic reorientation of the probes relative to the external force. The degree to which the microstructure is distorted, and the shape of that distortion, depend on the arrangement of the probes relative to one another and their orientation to the driving force. It also depends on the magnitude of probe velocity relative to the Brownian velocity of the suspension. When only thermal fluctuations set probe velocity, the equilibrium depletion attraction is recovered. For weak forcing, long-ranged interactions mediated via the bath-particle flux give rise to entropic forces on the probes. The linear response is a viscous drag that slows forward motion; only the weakly nonlinear response can produce relative motion–attraction, repulsion or reorientation of the probes. We derive entropic coupling tensors, similar in ethos to pair hydrodynamic tensors, to describe this behaviour. The structural symmetry that permits this analogy is lost when forcing becomes strong, revealing instabilities in system behaviour. Far from equilibrium, the interactive force depends explicitly on the initial probe separation, orientation and strength of forcing; widely spaced probes interact through the distorted microstructure, whereas the behaviour of closely spaced probes is largely set by excluded-volume effects. In this regime, a pair of closely spaced probes sedimenting side-by-side tend to attract and reorient to permit alignment of their line-of-centres with the flow, while widely spaced probes fall without reorienting. Our results show qualitative agreement with experimental observations and provide a potential connection to the observed column instability in shear-thinning fluids.

Abstract

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We derive a thermodynamically consistent framework for incorporating entanglement dynamics into constitutive equations for flowing polymer melts. We use this to combine the convected constraint release (CCR) dynamics of Ianniruberto-Marriccui into a finitely-extensible version of the Rolie-Poly model, and also include an anisotropic mobility as in the Giesekus model. The reversible dynamics are obtained from a free energy that describes both a finitely-extensible conformation tensor and an ideal gas of entanglements along the chain. The dissipative dynamics give rise to coupled kinetic equations for the conformation tensor and entanglements, whose coupling terms describe shear-induced disentanglement. The relaxation dynamics of the conformation tensor follow the GLaMM and Rolie-Poly models, and account for reptation, retraction and CCR. We propose that the relaxation time τ ν for entanglement recovery is proportional to the Rouse time τ R which governs polymer stretch within the tube. This which matches recent molecular dynamics simulations, and corresponds to relaxing the entanglement number before the entire polymer anisotropy has relaxed on the longer reptation time τ d .

We derive a thermodynamically consistent framework for incorporating entanglement dynamics into constitutive equations for flowing polymer melts. We use this to combine the convected constraint release (CCR) dynamics of Ianniruberto–Marriccui into a finitely extensible version of the Rolie–Poly model, and also include an anisotropic mobility as in the Giesekus model. The reversible dynamics are obtained from a free energy that describes both a finitely extensible conformation tensor and an ideal gas of entanglements along the chain. The dissipative dynamics give rise to coupled kinetic equations for the conformation tensor and entanglements, whose coupling terms describe shear-induced disentanglement. The relaxation dynamics of the conformation tensor follow the GLaMM and Rolie–Poly models, and account for reptation, retraction, and CCR. We propose that the relaxation time [Formula: see text] for entanglement recovery is proportional to the Rouse time [Formula: see text] which governs polymer stretch within the tube. This matches recent molecular dynamics simulations and corresponds to relaxing the entanglement number before the entire polymer anisotropy has relaxed on the longer reptation time [Formula: see text]. Our model suggests that claimed signatures of slow re-entanglement on the reptation time in step-strain experiments may be interpreted as arising from anisotropies in reptation dynamics.