Crossover between Athermal Jamming and the Thermal Glass Transition of Suspensions.

The non-Newtonian flow behavior of thermal and athermal disordered systems of dispersed uniform particles at high densities have strikingly similar features. By investigating the flow curves of yield-stress fluids and colloidal glasses having different volume fractions, particle sizes, and interactions, we show that both thermal and athermal systems exhibit power-law scaling with respect to the glass and jamming point, respectively, with the same exponents. All yield-stress flow curves can be scaled onto a single universal curve using the Laplace pressure as the stress scale for athermal systems and the osmotic pressure for the thermal systems. Strikingly, the details of interparticle interactions do not matter for the rescaling, showing that they are akin to usual phase transitions of the same universality class. The rescaling allows us to predict the flow properties of these systems from the volume fraction and known material properties.

Universal rescaling of flow curves for yield-stress fluids close to jamming.

The experimental flow curves of four different yield-stress fluids with different interparticle interactions are studied near the jamming concentration. By appropriate scaling with the distance to jamming all rheology data can be collapsed onto master curves below and above jamming that meet in the shear-thinning regime and satisfy the Herschel-Bulkley and Cross equations, respectively. In spite of differing interactions in the different systems, master curves characterized by universal scaling exponents are found for the four systems. A two-state microscopic theory of heterogeneous dynamics is presented to rationalize the observed transition from Herschel-Bulkley to Cross behavior and to connect the rheological exponents to microscopic exponents for the divergence of the length and time scales of the heterogeneous dynamics. The experimental data and the microscopic theory are compared with much of the available literature data for yield-stress systems.

Glassy boundary layers vs enhanced mobility in capped polymer films.

Molecular-dynamics simulations have been carried out for a coarse-grained model of a random AB-copolymer confined between two crystalline substrates. The strength of substrate-polymer interactions, and the distance between the two substrates have been varied in a wide range. For thick films the film-averaged segmental mobility decreases for intermediate adsorption strengths, but start to increase for very high substrate-polymer attraction strength. We saw that this non-monotonic behavior is caused by a very strong heterogeneity of the segmental dynamics above the glass-transition temperature: the segmental mobility slows down drastically close to adsorbing substrates, but strongly increases in the middle part of the film. This effect, and its sensitive dependence on film thickness, are explained by finite-size effects in confinement, in combination with glassy boundary layers. It is demonstrated that film-averaged mobility as often measured cannot be understood without resolving local mobility in space and time.

Mechanical properties and local mobility of atactic-polystyrene films under constant-shear deformation.

We have performed molecular-dynamics simulations of atactic polystyrene thin films to study the effect of shear rate, pressure, and temperature on the stress-strain behaviour, the relevant energetic contributions and non-affine displacements of polymer chains during constant-shear deformation. Under this deformation sliding motion is observed at high shear rates between the top substrate and top polymer layer, which disappears when the shear rate decreases. At low shear rates stick-slip motion of the whole film with respect to the bottom substrate takes place. We found that at low shear rates the yield stress logarithmically depends on the shear rate; this behaviour can be explained in terms of the Eyring model. It was also observed that an increase in the normal pressure leads to an increase in the yield stress in agreement with experiments. The contributions to the total shear stress and energy are mainly given by the excluded-volume interactions. It corresponds to a local translational dynamics under constant shear in which particles are forced to leave their original cages much earlier as compared to the case of the isotropic, non-sheared film. Moreover, it was observed that under constant-shear deformation the polymer glass is deformed non-affinely. As a result, the middle part of the film is much more deformed than the layers close to the supporting substrates, meaning that the well-known effect of shear-banding occurs.

The microstructure of petroleum vacuum residue films for bituminous concrete: a microscopy approach.

Selected carbon-rich refinery residues ('binders') mixed with mineral particles can form composite materials ('bituminous concrete') with bulk mechanical properties comparable to those of cement concrete. The microstructural mechanism underlying the remarkable composite properties has been related to the appearance of a rigid percolating network consisting of asphaltenes and mineral particles [Wilbrink M. et al. (2005) Rigidity percolation in dispersions with a structured visco-elastic matrix. Phys. Rev. E71, 031402]. In this paper, we explore the microstructure of thin binder films of varying thickness with a number of microscopic characterization techniques, and attempt to relate the observed microstructure to the distinctive mechanical behaviour. Two binders, only one of which has been proven to be suitable for bituminous concrete were investigated, and their microstructure compared. Both binders show the formation of asphaltene aggregates. The binder suitable for bituminous concrete is distinguished by the fact that the asphaltenes show a stronger tendency towards such aggregation, due to a higher concentration and less stabilization in the maltene phase. They also show a clear affinity to other species (such as waxes) and may act as nucleation sites for crystals and aggregates of those species.

Deforming glassy polystyrene: Influence of pressure, thermal history, and deformation mode on yielding and hardening.

The toughness of a polymer glass is determined by the interplay of yielding, strain softening, and strain hardening. Molecular-dynamics simulations of a typical polymer glass, atactic polystyrene, under the influence of active deformation have been carried out to enlighten these processes. It is observed that the dominant interaction for the yield peak is of interchain nature and for the strain hardening of intrachain nature. A connection is made with the microscopic cage-to-cage motion. It is found that the deformation does not lead to complete erasure of the thermal history but that differences persist at large length scales. Also we find that the strain-hardening modulus increases with increasing external pressure. This new observation cannot be explained by current theories such as the one based on the entanglement picture and the inclusion of this effect will lead to an improvement in constitutive modeling.

Shear banding and yield stress in soft glassy materials.

Shear localization is a generic feature of flows in yield stress fluids and soft glassy materials but is incompletely understood. In the classical picture of yield stress fluids, shear banding happens because of a stress heterogeneity. Using recent developments in magnetic resonance imaging velocimetry, we show here for a colloidal gel that even in a homogeneous stress situation shear banding occurs, and that the width of the flowing band is uniquely determined by the macroscopically imposed shear rate rather than the stress. We present a simple physical model for flow of the gel showing that shear banding (localization) is a flow instability that is intrinsic to the material, and confirm the model predictions for our system using rheology and light scattering.

Time scales and mechanisms of relaxation in the energy landscape of polymer glass under deformation: direct atomistic modeling.

Molecular-dynamics simulation is used to explore the influence of thermal and mechanical history of typical glassy polymers on their deformation. Polymer stress-strain and energy-strain developments have been followed for different deformation velocities, also in closed extension-recompression loops. The latter simulate for the first time the experimentally observed mechanical rejuvenation and overaging of polymers, and energy partitioning reveals essential differences between mechanical and thermal rejuvenation. All results can be qualitatively interpreted by considering the ratios of the relevant time scales: for cooling down, for deformation, and for segmental relaxation.

Non-Gaussian nature of glassy dynamics by cage to cage motion.

A model based on a single Brownian particle moving in a periodic effective field is used to understand the non-Gaussian dynamics in glassy systems of cage escape and subsequent recaging, often thought to be caused by a heterogeneous glass structure. The results are compared to molecular-dynamics simulations of systems with varying complexity: quasi-two-dimensional colloidlike particles, atactic polystyrene, and a dendritic glass. The model nicely describes generic features of all three topologically different systems, in particular around the maximum of the non-Gaussian parameter. This maximum is a measure for the average distance between cages.

The optimal structure-conductivity relation in epoxy-phthalocyanine nanocomposites.

Phthalcon-11 (aquocyanophthalocyaninatocobalt (III)) forms semiconducting nanocrystals that can be dispersed in epoxy coatings to obtain a semiconducting material with a low percolation threshold. We investigated the structure-conductivity relation in this composite and the deviation from its optimal realization by combining two techniques. The real parts of the electrical conductivity of a Phthalcon-11/epoxy coating and of Phthalcon-11 powder were measured by dielectric spectroscopy as a function of frequency and temperature. Conducting atomic force microscopy (C-AFM) was applied to quantify the conductivity through the coating locally along the surface. This combination gives an excellent tool to visualize the particle network. We found that a large fraction of the crystals is organized in conducting channels of fractal building blocks. In this picture, a low percolation threshold automatically leads to a conductivity that is much lower than that of the filler. Since the structure-conductivity relation for the found network is almost optimal, a drastic increase in the conductivity of the coating cannot be achieved by changing the particle network, but only by using a filler with a higher conductivity level.

Constant-pressure simulations with dissipative particle dynamics.

Dissipative particle dynamics (DPD) is a mesoscopic simulation method for studying hydrodynamic behavior of complex fluids. Ideally, a mesoscopic model should correctly represent the thermodynamic and hydrodynamic properties of a real system beyond certain length and time scales. Traditionally defined DPD quite successfully mimics hydrodynamics but is not flexible enough to accurately describe the thermodynamics of a real system. The so-called multibody DPD (MDPD) is a pragmatic extension of the classical DPD that allows one to prescribe the thermodynamic behavior of a system with only a small performance impact. In an earlier paper [S. Y. Trofimov, E. L. F. Nies, and M. A. J. Michels, J. Chem. Phys. 117, 9383 (2002)] we much improved the accuracy of the MDPD model for strongly nonideal systems, which are of most practical interest. The ability to correctly reproduce the equation of state of realistic systems in turn makes simulations at constant pressure sensible and useful. This situation of constant-pressure conditions is very common in experimental studies of (soft) condensed matter but has so far remained unexplored with the traditional DPD. Here, as a proof of concept, we integrate a modified version of the Andersen barostat into our improved MDPD model and make an evaluation of the performance of the new model on a set of single- and multicomponent systems. The modification of the barostat suppresses the "unphysical" volume oscillations after a sudden pressure change and simplifies the equilibration of the system.

Unified description of charge-carrier mobilities in disordered semiconducting polymers.

From a numerical solution of the master equation for hopping transport in a disordered energy landscape with a Gaussian density of states, we determine the dependence of the charge-carrier mobility on temperature, carrier density, and electric field. Experimental current-voltage characteristics in devices based on semiconducting polymers are excellently reproduced with this unified description of the mobility. At room temperature it is mainly the dependence on carrier density that plays an important role, whereas at low temperatures and high fields the electric field dependence becomes important. Omission in the past of the carrier-density dependence has led to an underestimation of the hopping distance and the width of the density of states in these polymers.

Rigidity percolation in dispersions with a structured viscoelastic matrix.

This paper deals with rigidity percolation in composite materials consisting of a dispersion of mineral particles in a microstructured viscoelastic matrix. The viscoelastic matrix in this specific case is a hydrocarbon refinery residue. In a set of model random composites the mean interparticle surface-to-surface distance was controlled, changing particle volume fraction phi and particle number density independently. This was achieved by mixing two sets of monodisperse particles with widely differing radii (0.35 microm and 17.5 microm) with the matrix. A scaling exponent of 3.9 +/- 0.6 for the storage modulus G' vs phi- phi(c) was observed above a threshold phi(c) , in good agreement with theoretical values for rigidity percolation. It is found that at the rigidity-percolation threshold the pore structure, as characterized by the mean surface-to-surface distance for the filler, rather than the filler volume fraction, is similar for different types of composites. This behavior is explained from the internal structure of the viscoelastic matrix, which consists of fractal solid aggregates dissolved in a viscous medium; the effective radius of these aggregates and the mean surface-to-surface distance together determine whether or not the aggregates are capable of providing rigidity to the composite. The explanation is further supported by a qualitative comparison with effective-medium calculations. These indicate that the observed breakdown of time-temperature superposition near phi(c) is due to the appearance of a time scale characteristic for the mechanical interplay between the viscous binder phase and the purely elastic solid particles.

Amplification of chirality in helical supramolecular polymers beyond the long-chain limit.

The optical activity of helical homopolymers devoid of chiral centers increases drastically when a small amount of homochiral monomers is incorporated into them. We study this so-called sergeants-and-soldiers effect of chirality amplification in solutions of helical supramolecular polymers with a theoretical model that bears a strong resemblance to a one-dimensional, two-component Ising model. In the limit of very long self-assembled helical polymers, the strength of the sergeants-and-soldiers effect depends strongly on the free energy of a helix reversal and less so on the concentration of aggregating material. Outside the long-chain limit, we find the reverse--that is, a strong concentration dependence and a weak dependence on the helix-reversal energy. Our treatment gives an excellent agreement with recently published circular-dichroism measurements on mixed aggregates of discotic molecules in the solvents water and n-butanol, at two different overall concentrations.

Structure and transport properties of liquid clusters in a drying porous medium.

The structure and transport properties of drying water clusters in porous media have been studied with a site-bond invasion percolation (IP) model. In this model an invader (air) enters a lattice (porous network) filled with defender (water) via a sequence of invasion steps. The decision to invade a site (pore) is made on the basis of the resistance of the bonds (throats). It is found that the backbone of the defender network and its transport properties are the same as in ordinary percolation (OP). In particular the strength exponent of the backbone beta(B)=0.99+/-0.03, the correlation length exponent nu=0.88, and the conductivity exponent mu=1.99+/-0.04 are the same as in OP. The total network deviates from networks generated with OP: on short length scales the formation of branches is suppressed because pores with many empty neighbors are preferentially invaded. The differences between our IP results and the outcomes of OP are a consequence of the invasion mechanism. This makes clear that the details of the invasion process are important for understanding the transport properties in a drying network.

The physics of surfactant dissolution.

We have examined the early stages of surfactant dissolution and mesophase formation using a dimer-solvent model with phase behaviour representative of surfactant-water systems. We use an orientational order parameter to characterize systematically the appearance of mesophases. We find the process is diffusion controlled, and the appearance of mesophases is governed adiabatically by the equilibrium phase diagram from the earliest point at which the orientational order parameter can reliably distinguish between mesophases, when only a few repeat spacings of the mesophase microstructures are present. In real systems, such a stage would correspond to times of the order of a few microseconds after the initial contact.

Influence of buoyancy on drainage of a fractal porous medium.

The influence of stabilizing hydrostatic pressure gradients on the drainage of a fractal porous medium is studied. The invasion process is treated with invasion percolation (IP) in a gradient. Fractality is mimicked by randomly closing bonds of a network. Two length scales govern the problem: the characteristic length of the pore structure xi(s) and a length scale xi(g) above which buoyancy determines the structure of the cluster. When xi(s)xi(g), gravity becomes important and xi(g) scales with the bond number B as xi(g) proportional, variant B-0.57, as in ordinary IP, while the fractal dimension becomes equal to the Euclidean one. When xi(g)xi(s) the fractal dimension of the invading cluster equals the Euclidean one and xi(g) proportional, variant B-0.69.

Mesoscale simulations of surfactant dissolution and mesophase formation.

The evolution of the contact zone between pure surfactant and solvent has been studied by mesoscale simulation. It is found that mesophase formation becomes diffusion controlled and follows the equilibrium phase diagram adiabatically almost as soon as individual mesophases can be identified, corresponding to times in real systems of order 10 micros.

Drying processes in the presence of temperature gradients--pore-scale modelling.

The influence of temperature gradients on the drying of water-saturated porous networks has been studied. We have focussed on the influence of the temperature on the drying process via the equilibrium vapor density rhoe, because this is the most sensitive parameter with respect to variations of the temperature T. We have used a 2D model which accounts for both capillary and buoyancy forces. Invasion events by air or water are handled by standard rules of invasion percolation in a gradient (IPG). Vapor fluxes are calculated by solving a discretized version of the Laplace equation. In the model the temperature T varies linearly from the open side T0 to the closed side TL. The temperature gradients strongly influence the cluster evolution during the process, because they facilitate vapor transport through wet regions. When T0TL, the front movement is enhanced and the air ingress in the wet region behind the front is inhibited. The behavior of 3D systems differs from that of 2D systems, because the point where air percolates the system and the point where the water network breaks up in isolated clusters do not coincide. Before the latter fragmentation point the temperature will mainly influence the drying rates. After this point also the water distribution becomes sensitive to the temperature profile.