A mean-field phase diagram for conformationally symmetric diblock melts using the standard Gaussian polymer model is presented. Our calculation, which traverses the weak- to strong-segregation regimes, is free of traditional approximations. Regions of stability are determined for disordered (DIS) melts and for ordered structures including lamellae (L), hexagonally packed cylinders (H), body-centered cubic spheres (QIm3m), close-packed spheres (CPS), and the bicontinuous cubic network with Ia3d symmetry (QIa3d). The CPS phase exists in narrow regions along the order−disorder transition for χN ≥ 17.67. Results suggest that the QIa3d phase is not stable above χN ∼ 60. Along the L/QIa3d phase boundaries, a hexagonally perforated lamellar (HPL) phase is found to be nearly stable. Our results for the bicontinuous Pn3m cubic (QPn3m) phase, known as the OBDD, indicate that it is an unstable structure in diblock melts. Earlier approximation schemes used to examine mean-field behavior are reviewed, and compa...

Unifying Weak- and Strong-Segregation Block Copolymer Theories

This study describes the development and validation of Computational Fluid Dynamics (CFD) methodology for the simulation of dispersed two-phase flows. A two-fluid (Euler-Euler) methodology previously developed at Imperial College is adapted to high phase fractions. It employs averaged mass and momentum conservation equations to describe the time-dependent motion of both phases and, due to the averaging process, requires additional models for the inter-phase momentum transfer and turbulence for closure. The continuous phase turbulence is represented using a two-equation k − ε−turbulence model which contains additional terms to account for the effects of the dispersed on the continuous phase turbulence. The Reynolds stresses of the dispersed phase are calculated by relating them to those of the continuous phase through a turbulence response function. The inter-phase momentum transfer is determined from the instantaneous forces acting on the dispersed phase, comprising drag, lift and virtual mass. These forces are phase fraction dependent and in this work revised modelling is put forward in order to capture the phase fraction dependency of drag and lift. Furthermore, a correlation for the effect of the phase fraction on the turbulence response function is proposed. The revised modelling is based on an extensive survey of the existing literature. The conservation equations are discretised using the finite-volume method and solved in a solution procedure, which is loosely based on the PISO algorithm, adapted to the solution of the two-fluid model. Special techniques are employed to ensure the stability of the procedure when the phase fraction is high or changing rapidely. Finally, assessment of the methodology is made with reference to experimental data for gas-liquid bubbly flow in a sudden enlargement of a circular pipe and in a plane mixing layer. Additionally, Direct Numerical Simulations (DNS) are performed using an interface-capturing methodology in order to gain insight into the dynamics of free rising bubbles, with a view towards use in the longer term as an aid in the development of inter-phase momentum transfer models for the two-fluid methodology. The direct numerical simulation employs the mass and momentum conservation equations in their unaveraged form and the topology of the interface between the two phases is determined as part of the solution. A novel solution procedure, similar to that used for the two-fluid model, is used for the interface-capturing methodology, which allows calculation of air bubbles in water. Two situations are investigated: bubbles rising in a stagnant liquid and in a shear flow. Again, experimental data are used to verify the computational results.

Computational fluid dynamics of dispersed two-phase flows at high phase fractions

Slip occurs in the flow of two-phase systems because of the displacement of the disperse phase away from solid boundaries. This arises from steric, hydrodynamic, viscoelastic and chemical forces and constraints acting on the disperse phase immediately adjacent to the walls. The enrichment of the boundary near the wall with the continuous (and usually low-viscosity) phase means that any flow of the fluid over the boundary is easier because of the lubrication effect. Because this effect is usually confined to a very narrow layer — with typical thickness of 0.1–10 μm—it so resembles the slip of solids over surfaces that it has historically been given the same terminology. The restoring force for all the forces that cause an increase in concentration is usually osmotic, and this will always limit the effective slip. In dilute systems, concentration gradients can be present over relatively large distances out from walls, giving what might be interpreted on an overall basis as a thick solvent-only layer. However, as the concentration of the system increases, the layer gets thinner and thinner because it is more difficult to create with the large reverse osmotic force present. However, the enormous increase in the bulk viscosity with increase in concentration means that although thinner, the layer becomes, paradoxically, even more important. Slip manifests itself in such a way that viscosity measured in different size geometries gives different answers if calculated the normal way — in particular the apparent viscosity decreases with decrease in geometry size (e.g. tube radius). Also, in single flow curves unexpected lower Newtonian plateaus are sometimes seen, with an apparent yield stress at even lower stresses. Sudden breaks in the flow curve can also be seen. Large particles as the disperse phase (remember flocs are large particles), with a large dependence of viscosity on the concentration of the dispersed phase are the circumstances which can give slip, especially if coupled with smooth walls and small flow dimensions. The effect is usually greatest at low speeds/flow rates. When the viscometer walls and particles carry like electrostatic charges and the continuous phase is electrically conducted, slip can be assumed. In many cases we need to characterise the slip effects seen in viscometers because they will also be seen in flow in smooth pipes and condults in manufacturing plants. This is usually done by relating the wall shear stress to a slip velocity using a power-law relationship. When the bulk flow has also been characterized, the flow in real situations can be calculated. To characterise slip, it is necessary to change the size of the geometry, and the results extrapolated to very large size to extract unambigouos bulk-flow and slip data respectively. A number of mathematical manipulations are necessary to retrieve these data. We can make attempts to eliminate slip by altering the physical or chemical character of the walls. This is usually done physically by roughening or profiling, but in the extreme, a vane can be used. This latter geometry has the advantage of being easy to make and clean. In either case—by extrapolation or elimination—we end up with the bulk flow properties. This is important in situations where we are trying to understand the microstructure/flow interactions.

A review of the slip (wall depletion) of polymer solutions, emulsions and particle suspensions in viscometers: its cause, character, and cure

Polymer melts with long-chain side branches and more than one junction point, such as commercial low density polyethylene (LDPE), have extensional rheology characterized by extreme strain hardening, while the shear rheology is very shear thinning, much like that of unbranched polymers. Working with the tube model for entangled polymer melts, we propose a molecular constitutive equation for an idealized polymer architecture, which, like LDPE, has multiple branch points per molecule. The idealized molecule, called a “pom-pom,” has a single backbone with multiple branches emerging from each end. Because these branches are entangled with the surrounding molecules, the backbone can readily be stretched in an extensional flow, producing strain hardening. In start-up of shear, however, the backbone stretches only temporarily, and eventually collapses as the molecule is aligned, producing strain softening. Here we develop a differential/integral constitutive equation for this architecture, and show that it predicts rheology in both shear and extension that is qualitatively like that of LDPE, much more so than is possible with, for example, the K-BKZ integral constitutive equation.

Molecular constitutive equations for a class of branched polymers: The pom-pom polymer

The viscoelastic properties of high molecular weight polymeric liquids are dominated by topological constraints on a molecular scale. In a manner similar to that of entangled ropes, polymer chains can slide past but not through each other. Tube models of polymer dynamics and rheology are based on the idea that entanglements confine a chain to small fluctuations around a primitive path that follows the coarse-grained chain contour. Here we provide a microscopic foundation for these highly successful phenomenological models. We analyze the topological state of polymeric liquids in terms of primitive paths and obtain parameter-free, quantitative predictions for the plateau modulus, which agree with experiment for all major classes of synthetic polymers.

https://science.sciencemag.org/content/sci/303/5659/823.full.pdf

Rheology and microscopic topology of entangled polymeric liquids.

It is argued that the flow directly contributes a mechanism by which the topological obstacles are renewed. As a consequence, the chain diffusivity is increased (or, equivalently, the friction coefficient is decreased) in fast flows. Such a nonlinear effect is incorporated in a simple dumbbell model so as to produce a constitutive equation in closed form. An extension to the case of multiple relaxation times is also briefly considered. The predictions compare favourably with the Cox-Merz rule as well as with the behaviour of polymer melts in elongational flows.

Dynamics of entanglements: a nonlinear model consistent with the cox-merz rule

Analyse du comportement non-lineaire de la phase nematique de polymere en ecoulement cisaille en reduisant le probleme a son equivalent bidimensionnel On obtient des solutions pour la fonction de distribution d'orientation lorsqu'il existe une solution stationnaire Les contraintes correspondantes sont calculees Pour un domaine de vitesse de cisaillement, la difference de contrainte normale est negative

A description of the liquid-crystalline phase of rodlike polymers at high shear rates

A new model for Brownian dynamics simulations of entangled polymeric liquids is proposed here. Chains are coarse grained at the level of segments between consecutive entanglements; hence, the system is in fact a network of primitive chains. The model incorporates not only the “individual” mechanisms of reptation and tube length fluctuation, but also collective contributions arising from the 3D network structure of the entangled system, such as constraint release. Chain coupling is achieved by fulfilling force balance on the entanglement nodes. The Langevin equation for the nodes contains both the tension in the chain segments emanating from the node and an osmotic force arising from density fluctuations. Entanglements are modeled as slip links, each connecting two chain strands. The motion of monomers through slip links, which ultimately generates reptation as well as tube length fluctuations, is also described by a suitable Langevin equation. Creation and release of entanglements is controlled by the num...

Brownian simulations of a network of reptating primitive chains

Recent data by Hassager and co-workers [Bach et al. Macromolecules 2003, 36, 5174] of elongational viscosity of nearly monodisperse polystyrene melts are interpreted by including in the classical tube theories for entangled polymer dynamics an interchain repulsive contribution. The proposed theory predicts the observed power law of ηel vs e in a straightforward way and qualitatively explains the observed scaling with the polymer molecular mass. Possible generalizations are discussed.

Giuseppe Marrucci

Papers

Dynamics of entanglements: a nonlinear model consistent with the cox-merz rule

A description of the liquid-crystalline phase of rodlike polymers at high shear rates

Brownian simulations of a network of reptating primitive chains

Interchain Pressure Effect in Extensional Flows of Entangled Polymer Melts

Transient behavior of entangled polymers at high shear rates