Michael Villet

Shear banding in polymer solutions

The current theoretical belief is that the steady-state shear banding in viscoelastic liquids requires a non-monotonic constitutive relationship between shear stress and shear rate. Although existing rheological studies conclude that the constitutive equation for entangled polymers is monotonic, recent experimental evidence suggests shear banding can nevertheless occur in polymer solutions. In this work, we predict, for the first time, steady state shear banding with a realistic monotonic constitutive theory for polymeric liquids. The key is that a proper account must be taken of the coupling of polymer stress to polymer concentration. We also predict multiple steady states at some shear rates as seen experimentally, with shear banding if the flow is ramped quickly enough from rest, but homogeneous linear shear flow otherwise.

Efficient field-theoretic simulation of polymer solutions

We present several developments that facilitate the efficient field-theoretic simulation of polymers by complex Langevin sampling. A regularization scheme using finite Gaussian excluded volume interactions is used to derive a polymer solution model that appears free of ultraviolet divergences and hence is well-suited for lattice-discretized field theoretic simulation. We show that such models can exhibit ultraviolet sensitivity, a numerical pathology that dramatically increases sampling error in the continuum lattice limit, and further show that this pathology can be eliminated by appropriate model reformulation by variable transformation. We present an exponential time differencing algorithm for integrating complex Langevin equations for field theoretic simulation, and show that the algorithm exhibits excellent accuracy and stability properties for our regularized polymer model. These developments collectively enable substantially more efficient field-theoretic simulation of polymers, and illustrate the importance of simultaneously addressing analytical and numerical pathologies when implementing such computations.

Numerical coarse-graining of fluid field theories

We present a formalism for the systematic numerical coarse-graining of field-theoretic models of fluids that draws upon techniques from both the Monte Carlo renormalization group and particle-based coarse-graining literature. A force-matching technique initially developed for coarse-graining particle-based interaction potentials is adapted to calculate renormalized field-theoretic coupling coefficients in a complex-valued field theory, and a related method is introduced for coarse-graining field-theoretic operators. The viability of this methodology is demonstrated by coarse-graining a field-theoretic model of a Gaussian-core fluid and thereby reducing lattice discretization errors.

Concentration fluctuations in polymer solutions under extensional flow

In this work, we extend the classical analysis of concentration fluctuations in polymer solutions under shear flow to consider the same phenomenology under extensional flow. Experimental work by van Egmond and Fuller [Macromolecules 26, 7182–7188 (1993)] revealed a four-lobe scattering pattern for a polystyrene solution in a planar extensional flow field. Similar to earlier results found in shear, they find the existence of finite-wavelength peak intensity locations. To investigate this phenomenon, we couple stress and concentration using a two-fluid model with fluctuations driven by thermal noise incorporated through a canonical Langevin approach. The polymer stress is governed by the Rolie–Poly model augmented with finite extensibility to account for large stretching of chains at high Weissenberg numbers. Perturbing the equations about homogeneous planar extensional flow for weak amplitude inhomogeneities, but arbitrary flow strength, we solve for the steady correlations. The resulting structure factor ...

Multilayer barrier films comprising nitrogen spacers between free-standing barrier layers

An encapsulation architecture for organic electronic devices utilizing nitrogen gas-phase spacers between free-standing barrier films is demonstrated. The nitrogen spacers act as sinks for permeating H2O and O2, delaying establishment of steady-state chemical potential gradients across the barriers and thereby reducing permeation rates. Water vapor transmission through nitrogen-spaced barriers was measured via the calcium optical transmission test. Substantial reductions in permeation rate were observed for a variety of barrier materials and configurations, suggesting a general and cost-effective approach for improving encapsulation performance. A low-cost polyethylene terephthalate film increases the calcium lifetime of a Cytop™-Kureha structure from 7000 to 12000 min.