Search

We report on the unusual response of a well-characterized entangled comb polymer in simple shear flow. The polymer with highly entangled backbone (about 16 entanglements) and on average 29 long branches (about 3 entanglements each) has been extensively characterized by interaction chromatography and its rheology carefully studied under controlled conditions using a special cone partitioned-plate geometry. We observe that the start-up shear stress becomes roughly rate independent above a certain critical rate, related to the relaxation time of the branches. Within the rate-independent region, the start-up shear stress displays a double overshoot. We interpret these observations in light of tube-based pompom dynamics. The key idea is that for sufficiently long branches the main stress overshoot, which reflects backbone stretching and orientation, is preceded by the withdrawal of branches into the backbone tube. The excellent quantitative comparison between the simulations and experiments supports the proposed mechanism of the double stress overshoot.

Ordering induced by shear flow can be used to direct the assembly of particles in suspensions. Flow-induced ordering is determined by the balance between a range of forces, such as direct interparticle, Brownian, and hydrodynamic forces. The latter are modified when dealing with viscoelastic rather than Newtonian matrices. In particular, 1D stringlike structures of spherical particles have been observed to form along the flow direction in shear thinning viscoelastic fluids, a phenomenon not observed in Newtonian fluids at similar particle volume fractions. Here we report on the formation of freestanding crystalline patches in planes parallel to the shearing surfaces. The novel microstructure is formed when particles are suspended in viscoelastic, wormlike micellar solutions and only when the applied shear rate exceeds a critical value. In spite of the very low volume fraction (less than 0.01), particles arrange themselves in 2D crystalline patches along the flow direction. This is a bulk phenomenon because 2D crystals form throughout the whole gap between plates, with the gap thickness being much larger than the particle size. Shear flow may hence be an easy method to drive particles into crystalline order in suspensions with viscoelastic properties. The crystalline structure reported here could be used to design new materials with special mechanical, optical, thermal, or electric properties.

When particles are dispersed in viscoelastic rather than Newtonian media, the hydrodynamics will be changed entailing differences in suspension rheology. The disturbance velocity profiles and stress distributions around the particle will depend on the viscoelastic material functions. Even in inertialess flows, changes in particle rotation and migration will occur. The problem of the rotation of a single spherical particle in simple shear flow in viscoelastic fluids was recently studied to understand the effects of changes in the rheological properties with both numerical simulations [D’Avino et al., J. Rheol. 52 (2008) 1331–1346] and experiments [Snijkers et al., J. Rheol. 53 (2009) 459–480]. In the simulations, different constitutive models were used to demonstrate the effects of different rheological behavior. In the experiments, fluids with different constitutive properties were chosen. In both studies a slowing down of the rotation speed of the particles was found, when compared to the Newtonian case, as elasticity increases. Surprisingly, the extent of the slowing down of the rotation rate did not depend strongly on the details of the fluid rheology, but primarily on the Weissenberg number defined as the ratio between the first normal stress difference and the shear stress. In the present work, a quantitative comparison between the experimental measurements and novel simulation results is made by considering more realistic constitutive equations as compared to the model fluids used in previous numerical simulations [D’Avino et al., J. Rheol. 52 (2008) 1331–1346]. A multimode Giesekus model with Newtonian solvent as constitutive equation is fitted to the experimentally obtained linear and nonlinear fluid properties and used to simulate the rotation of a torque-free sphere in a range of Weissenberg numbers similar to those in the experiments. A good agreement between the experimental and numerical results is obtained. The local torque and pressure distributions on the particle surface calculated by simulations are shown.