Using molecular simulations and a modified Classical Nucleation Theory, we study the nucleation, under flow, of a variety of liquids: different water models, Lennard-Jones and hard sphere colloids. Our approach enables us to analyze a wide range of shear rates inaccessible to brute-force simulations. Our results reveal that the variation of the nucleation rate with shear is universal. A simplified version of the theory successfully captures the non-monotonic temperature dependence of the nucleation behavior, which is shown to originate from the violation of the Stokes-Einstein relation.
Simulations using the Forward Flux Sampling method have shown a nonmonotonic de- pendence of the homogeneous nucleation rate on the shear rate for a sheared two dimensional Ising model [R. J. Allen et al, arXiv cond-mat/0805.3029]. For quasi-equilibrium systems (i.e. in the absence of shear), Classical Nucleation Theory (CNT) predicts the dependence of the critical cluster size and the nucleation rate on the external magnetic field. We investigate the behaviour of the sheared Ising model as a function of the external field. At low exter- nal field strength, the same nonmonotonic behaviour hold…
One of the most ubiquitous and technologically important phenomena in nature is the nucleation of homogeneous flowing systems. The microscopic effects of shear on a nucleating system are still imperfectly understood, although in recent years a consistent picture has emerged. The opposing effects of shear can be split into two major contributions for simple liquids: increase of the energetic cost of nucleation, and enhancement of the kinetics. In this perspective, we describe the latest computational and theoretical techniques which have been developed over the past two decades. We collate and …
We present an experiment on crystallization of packings of macroscopic granular spheres. This system is often considered to be a model for thermally driven atomic or colloidal systems. Cyclically shearing a packing of frictional spheres, we observe a first order phase transition from a disordered to an ordered state. The ordered state consists of crystallites of mixed FCC and HCP symmetry that coexist with the amorphous bulk. The transition, initiated by homogeneous nucleation, overcomes a barrier at 64.5% volume fraction. Nucleation consists predominantly of the dissolving of small nuclei and…
We study numerically the crystallization process in a supersaturated suspension of repulsive colloidal particles driven by simple shear flow. The effect of the shear flow on crystallization is two-fold: while it suppresses the initial nucleation, once a large enough critical nucleus has formed its growth is enhanced by the shear flow. Combining both effects implies an optimal strain rate at which the overall crystallization rate has a maximum. To gain insight into the underlying mechanisms, we employ a discrete state model describing the transitions between the local structural configurations …
Hydrodynamic flow can have complex and far-reaching consequences on the rate of homogenous nucleation. We present a general formalism for calculating the nucleation rates of simply sheared systems. We have derived an extension to the conventional Classical Nucleation Theory, explicitly embodying the shear rate. Seeded Molecular Dynamics simulations form the backbone of our approach. The framework can be used for moderate supercoolings, at which temperatures brute-force methods are practically infeasible. The competing energetic and kinetic effects of shear arise naturally from the equations. W…
We present results from a physical experiment which demonstrates that a sheared granular medium behaves in a manner analogous to earthquake activity. The device consists of an annular plate rotating over a granular medium in a stick-slip fashion. Previous observations by us include a bounded critical state with a power law distribution of event energy consistent with the Gutenberg-Richter law, here we also reveal stair-case seismicity, clustering, foreshocks, aftershocks and seismic quiescence. Subcritical and supercritical regimes have also been observed by us depending on the system configur…
We compute rates and pathways for nucleation in a sheared two dimensional Ising model with Metropolis spin flip dynamics, using Forward Flux Sampling (FFS). We find a peak in the nucleation rate at intermediate shear rate. We analyse the origin of this peak using modified shear algorithms and committor analysis. We find that the peak arises from an interplay between three shear-mediated effects: shear-enhanced cluster growth, cluster coalescence and cluster breakup. Our results show that complex nucleation behaviour can be found even in a simple driven model system. This work also demonstrates…
The nonlinear flow behaviour of a viscoelastic gel formed due to entangled, cylindrical micelles in aqueous solutions of the surfactant CTAT has been studied. On subjecting the system to a step shear rate lying above a certain value, the shear and normal stresses show interesting time dependent behaviour. The analysis of the measured time series shows the existence of a finite correlation dimension and a positive Lyapunov exponent, unambiguously implying that the dynamics can be described by that of a dynamical system with a strange attractor whose dimension increases with the increase in shea…
Classical nucleation theory offers a good framework for understanding the common features of new phase formation processes in metastable homogeneous media at rest. However, nucleation processes in liquids are ubiquitously affected by hydrodynamic flow, and there is no satisfactory understanding of whether shear promotes or slows down the nucleation process. We developed a classical nucleation theory for sheared systems starting from the molecular level of the Becker-Doering master kinetic equation and we analytically derived a closed-form expression for the nucleation rate. The theory accounts…
We report canonical and grand-canonical lattice Monte Carlo simulations of the self-assembly of addressable structures comprising hundreds of distinct component types. The nucleation behaviour, in the form of free-energy barriers to nucleation, changes significantly as the co-ordination number of the building blocks is changed from 4 to 8 to 12. Unlike tetrahedral structures - which roughly correspond to DNA bricks that have been studied in experiment - the shapes of the free-energy barriers of higher co-ordination structures depend strongly on the supersaturation, and such structures require …
Collections of non-Brownian particles suspended in a viscous fluid and subjected to oscillatory shear at very low Reynolds number have recently been shown to exhibit a remarkable dynamical phase transition separating reversible from irreversible behaviour as the strain amplitude or volume fraction are increased. We present a simple model for this phenomenon, based on which we argue that this transition lies in the universality class of the conserved DP models or, equivalently, the Manna model. This leads to predictions for the scaling behaviour of a large number of experimental observables. No…
The nonequilibrium dynamical behaviour that arises when two ordered two-dimensional monolayers of particles are sheared over each other is studied in Brownian dynamics simulations. A curious sequence of nonequilibrium states is observed as the driving rate is increased, the most striking of which is a sliding state with irregular alternation between disordered and ordered states. We comment on possible mechanisms underlying these cycles, and experiments that could observe them.
Using Dynamic Light Scattering in heterodyne mode, we measure velocity profiles in a much studied system of wormlike micelles (CPCl/NaSal) known to exhibit both shear-banding and stress plateau behavior. Our data provide evidence for the simplest shear-banding scenario, according to which the effective viscosity drop in the system is due to the nucleation and growth of a highly sheared band in the gap, whose thickness linearly increases with the imposed shear rate. We discuss various details of the velocity profiles in all the regions of the flow curve and emphasize on the complex, non-Newtoni…
A variety of complex fluids under shear exhibit complex spatio-temporal behaviour, including what is now termed rheological chaos, at moderate values of the shear rate. Such chaos associated with rheological response occurs in regimes where the Reynolds number is very small. It must thus arise as a consequence of the coupling of the flow to internal structural variables describing the local state of the fluid. We propose a coupled map lattice (CML) model for such complex spatio-temporal behaviour in a passively sheared nematic liquid crystal, using local maps constructed so as to accurately de…
Self-organization, and transitions from reversible to irreversible behaviour, of interacting particle assemblies driven by externally imposed stresses or deformation is of interest in comprehending diverse phenomena in soft matter. They have been investigated in a wide range of systems, such as colloidal suspensions, glasses, and granular matter. In different density and driving regimes, such behaviour is related to yielding of amorphous solids, jamming, and memory formation, \emph{etc.} How these phenomena are related to each other has not, however, been much studied. In order to obtain a uni…
We study the flow behaviour of a twist-bend nematic $(N_{TB})$ liquid crystal. It shows three distinct shear stress ($σ$) responses in a certain range of temperatures and shear rates ($\dotγ$). In Region-I, $σ\sim\sqrt{\dotγ}$, in region-II, the stress shows a plateau, characterised by a power law $σ\sim{\dotγ}^α$, where $α\sim0.1-0.4$ and in region-III, $σ\sim\dotγ$. With increasing shear rate, $σ$ changes continuously from region-I to II, whereas it changes discontinuously with a hysteresis from region-II to III. In the plateau (region-II), we observe a dynamic stress fluctuations, exhibitin…
The solidification behaviour of suspensions of alumina particles during directional solidification is investigated here by in situ observations using X-ray radiography and tomography. The objective of this study is to assess the influence of particle size on the solidification behaviour of the suspensions during the early stages of solidification. Four powders with particle size in the range 0.2-3.4μm (median size) were investigated. Solidification is obtained by cooling at a constant rate, starting from room temperature. Attention is specifically paid to the nucleation and growth behaviour of…
We study low-salt, binary aqueous suspensions of charged colloidal spheres of size ratio Phi = 0.57, number densities below the eutectic number density n_E, and number fractions of p = 1.00-0.40. The typical phase obtained by solidification from a homogeneous shear-melt is a substitutional alloy of body centred cubic structure. In strictly gas-tight vials, the polycrystalline solid is stable against melting and further phase transformation for extended times. For comparison, we prepare the same samples also by slow and mechanically undisturbed deionization in commercial slit cells. These cells…
The crystallisation of entangled polymers from their melt is investigated using computer simulation with a coarse-grained model. Using hybrid Monte Carlo simulations enables us to probe the behaviour of long polymer chains. We identify solid-like beads with a centrosymmetry local order parameter and compute the nucleation free-energy barrier at relatively high supercooling with adaptive-bias windowed umbrella sampling. Our results demonstrate that the critical nucleus sizes and the heights of free-energy barriers do not significantly depend on the molecular weight of the polymer; however, the …
Granular material exposed to shear shows a variety of unique phenomena: Reynolds dilatancy, positional order and orientational order effects may compete in the shear zone. We study granular packings consisting of macroscopic prolate, oblate and spherical grains and compare their behaviour. X-ray tomography is used to determine the particle positions and orientations in a cylindrical split bottom shear cell. Packing densities and the arrangements of individual particles in the shear zone are evaluated. For anisometric particles, we observe the competition of two opposite effects. One the one ha…
The pair correlation function of charge stabilized colloidal particles under strongly sheared conditions is studied using the analytical intermediate asymptotics method recently developed in [L. Banetta and A. Zaccone, Phys. Rev. E 99, 052606 (2019)] to solve the steady-state Smoluchowski equation for medium to high values of the Péclet number; the analytical theory works for dilute conditions. A rich physical behaviour is unveiled for the pair correlation function of colloids interacting via the repulsive Yukawa (or Debye-Hückel) potential, in both the extensional and compressional sectors of…
Over the last number of years several simulation methods have been introduced to study rare events such as nucleation. In this paper we examine the crystal nucleation rate of hard spheres using three such numerical techniques: molecular dynamics, forward flux sampling and a Bennett-Chandler type theory where the nucleation barrier is determined using umbrella sampling simulations. The resulting nucleation rates are compared with the experimental rates of Harland and Van Megen [J. L. Harland and W. van Megen, Phys. Rev. E 55, 3054 (1997)], Sinn et al. [C. Sinn et al., Prog. Colloid Polym. Sci. …
Nucleation processes are at the heart of a large number of phenomena, from cloud formation to protein crystallization. A recently emerging area where nucleation is highly relevant is the initiation of filamentous protein self-assembly, a process that has broad implications from medicine to nanotechnology. As such, spontaneous nucleation of protein fibrils has received much attention in recent years with many theoretical and experimental studies focussing on the underlying physical principles. In this paper we make a step forward in this direction and explore the early time behaviour of filamen…
A systematic experimental study of dispersions of charged colloidal spheres is presented on the effect of steady shear flow on nucleation and crystal-growth rates. In addition, the non-equilibrium phase diagram as far as the melting line is concerned is measured. Shear flow is found to strongly affect induction times, crystal growth rates and the location of the melting line. The main findings are that (i) the crystal growth rate for a given concentration exhibits a maximum as a function of the shear rate, (ii) contrary to the monotonous increase of the growth rate with increasing concentratio…
Various experiments evidence spatial heterogeneities in sheared yield stress fluids. To account for heterogeneities in the velocity gradient direction, we use a simple model corresponding to a non-monotonous local constitutive curve and study a simple shear geometry. Different types of boundary conditions are considered. Under controlled macroscopic shear stress $Σ$, we find homogeneous flow in the bulk and a hysteretic macroscopic stress - shear rate curve. Under controlled macroscopic shear rate $\dotΓ$, shear banding is predicted within a range of values of $\dotΓ$. For small shear rates, s…
We report the observation of dynamical behaviour in dilute, aqueous solutions of a surfactant CTAT (cetyl trimethylammonium p-toluenesulphonate), below the overlap concentration c$^{\star}$. At these concentrations, CTAT forms cylindrical micelles and shows a pronounced shear thickening transition above a concentration-dependent critical shear rate $\dotγ_{c}$. An analysis of the time-series of the stress relaxations at controlled shear rates in the shear-thickening regime shows the existence of correlation dimensions greater than two and positive Lyapunov exponents. This indicates the existen…
We study in detail the application of renormalisation theory to models of cluster aggregation and fragmentation of relevance to nucleation and growth processes. In particular, we investigate the Becker-Doring (BD) equations, originally formulated to describe and analyse non-equilibrium phase transitions, but more recently generalised to describe a wide range of physicochemical problems. We consider here rate coefficients which depend on the cluster size in a power-law fashion, but now perturbed by small amplitude random noise. Power-law rate coefficients arise naturally in the theory of surfac…
We analyse base-pair breathing in a DNA sequence of 12 base-pairs with a defective base at its centre. We use both all-atom molecular dynamics (MD) simulations and a system of stochastic differential equations (SDE). In both cases, Fourier analysis of the trajectories reveals self-organised critical behaviour in the breathing of base-pairs. The Fourier Transforms (FT) of the interbase distances show power-law behaviour with gradients close to -1. The scale-invariant behaviour we have found provides evidence for the view that base-pair breathing corresponds to the nucleation stage of large-scal…
When sheared, most elastic solids such as metals, rubbers and polymer hydrogels dilate in the direction perpendicular to the shear plane. This well-known behaviour known as the Poynting effect is characterized by a positive normal stress. Surprisingly, biopolymer gels made of fibrous proteins such as fibrin and collagen, as well as many biological tissues exhibit the opposite effect, contracting under shear and displaying a negative normal stress. Here we show that this anomalous behaviour originates from the open network structure of biopolymer gels, which facilitates interstitial fluid flow …
The incredible thermo-mechanical properties of biological materials arise from the microscopic scale due to a complex hierarchical mechanism, regulated by microinstabilities at the molecular level. The description of such complex structures is allowed by both the know-how introduced by the advent of SMFS experiments and the possibility of correctly mimicking their behaviour at the lowest scales. In this thesis, different classes of models with non convex-energies are introduced to describe the important features of phase transition, decohesion and damage under different conditions of applied f…
We study the behaviour of cubic blue phases under shear flow via lattice Boltzmann simulations. We focus on the two experimentally observed phases, Blue Phase I (BPI) and Blue Phase II (BPII). The disclination network of Blue Phase II continuously breaks and reforms under steady shear, leading to an oscillatory stress response in time. For larger shear rates, the structure breaks up into a Grandjean texture with a cholesteric helix lying along the flow gradient direction. Blue Phase I leads to a very different response. Here, oscillations are only possible for intermediate shear rates -- very …
Pressure sensitivity in non-local flow behaviour of dense hydrogel particle suspensions
Van der Waals-Zeeman Institute, Institute of Physics, University of Amsterdam（阿姆斯特丹大学范德瓦耳斯-泽曼研究所物理学院）；Physical Chemistry and Soft Matter, Wageningen University & Research（瓦赫宁根大学与研究物理化学与软物质系）；Institute of Process and Particle Engineering, Graz University of Technology（格拉茨工业大学工艺与颗粒工程研究所）；Department of Mechanical Engineering, Indian Institute of Technology Bombay（印度孟买理工学院机械工程系）；Institute of Physics, Otto von Guericke University Magdeburg（马格德堡奥托·冯·格里克大学物理研究所）；School of Engineering, Brown University（布朗大学工程学院）
