In light of recent advancements in the constitutive modelling of bidisperse and polydisperse entangled linear polymers, we present a new multi fluid generalization of the classic two fluid approximation for flows of inhomogeneous polymer blends. As an application of the model, we consider predictions for the linear and nonlinear dynamics of shear induced demixing (SID) instabilities in blends with bidisperse and lognormal molecular weight distributions. We find that even in the absence of any chemical contrast between component chains, an imposed flow can induce a demixing instability provided there is sufficient contrast in the size of the two chains. The lower bound polydispersity for SID coincides with the point where elastic forces (kT per entanglement) scaled by the contrast between chains (e.g. polydispersity index minus one) exceed the entropic forces for mixing (kT per chain). For bi-disperse blends, we show that the non-linear dynamics of SID strongly resemble what has previously been shown for SID in entangled polymer solutions.
At the same solid volume fraction, bidisperse and polydisperse suspensions display lower viscosities, and weaker normal stress response, compared to monodisperse suspensions. The reduction of viscosity associated with size distribution can be explained by an increase of the maximum flowable, or jamming, solid fraction $ϕ_m$. In this work, dense suspensions are simulated under strong shearing, where thermal motion and repulsive forces are negligible, but we allow for particle contact with a mild frictional interaction with interparticle friction coefficient of $μ = 0.2$. Aspects of bidisperse s…
There is a growing consensus that shear thickening of concentrated dispersions is driven by the formation of stress-induced frictional contacts. The Wyart-Cates (WC) model of this phenomenon, in which the microphysics of the contacts enters solely via the fraction $f$ of contacts that are frictional, can successfully fit flow curves for suspensions of weakly polydisperse spheres. However, its validity for "real-life", polydisperse suspensions has yet to be seriously tested. By performing systematic simulations on bidisperse mixtures of spheres, we show that the WC model applies only in the mon…
Using Brownian dynamics simulations we perform a systematic investigation of the shear-induced migration of colloidal particles subject to Poiseuille flow in both cylindrical and planar geometry. We find that adding an attractive component to the interparticle interaction enhances the migration effect, consistent with recent simulation studies of platelet suspensions. Monodisperse, bidisperse and polydisperse systems are studied over a range of shear rates, considering both steady states and the transient dynamics arising from the onset of flow. For bidisperse and polydisperse systems size seg…
Polydispersity is inevitable in industrially produced polymers. Established theories of polymer dynamics and rheology, however, were mostly built on monodisperse linear polymers. Dynamics of polydisperse polymers is yet to be fully explored -- especially how chains of different lengths affect the dynamics of one another in a mixture. This study explored the dynamics of bidisperse polymer melts using molecular dynamics and a bead-spring chain model. Binary mixtures between a moderately entangled long-chain species and an unentangled or marginally entangled short-chain species were investigated.…
We show that an analogy between crowding in fluid and jammed phases of hard spheres captures the density dependence of the kissing number for a family of numerically generated jammed states. We extend this analogy to jams of mixtures of hard spheres in $d=3$ dimensions, and thus obtain an estimate of the random close packing (RCP) volume fraction, $ϕ_{\textrm{RCP}}$, as a function of size polydispersity. We first consider mixtures of particle sizes with discrete distributions. For binary systems, we show agreement between our predictions and simulations, using both our own and results reported…
Recently a novel class of responsive uncharged polymer brushes has been proposed [Klushin et al, J. Chem. Phys. 154, 074904 (2021)] where the brush-forming chains have an affinity to the substrate. For sufficiently strong surface interactions, a fraction of chains condenses into a near-surface layer, while the remaining ones form the outer brush with a reduced grafting density. The dense layer and the more tenuous outer brush can be seen as coexisting microphases. The effective grafting density of the outer brush is controlled by the adsorption strength and can be changed reversibly as a respo…
Spinodal demixing of systems into two phases having very different viscosities leads to viscoelastic networks, i.e. gels. Here we consider demixing in a colloidal system where one phase is a nematic liquid crystal with a strongly anisotropic viscosity. We combine real space analysis of a sepiolite clay system with molecular dynamics computer simulation. We find a long-lived network with many of the characteristics of a colloidal gel. Remarkably the anisotropic viscosity means that flow is possible within the nematic network, but only along the network, which thus preserves its structure, leadi…
Numerical analysis of capillarity-driven thinning rheometry for polydisperse polymer solutions
Massachusetts Institute of Technology（麻省理工学院）；University of Lausanne（洛桑大学）；Okinawa Institute of Science and Technology Graduate University（冲绳科学技术大学院大学）；University of the Basque Country UPV/EHU（巴斯克大学）
